Energy Regeneration and Carbon Neutral System for Ultra-Efficient EV Battery Recycling

Abstract

The concepts disclosed herein relate to improved technologies for alkali metal extraction systems and ultra-efficient EV battery recycling systems. By using a solid electrolyte embedded in a matrix, alkali metals (such as lithium) can be more effectively separated from the feed solution. The energy used to initially extract lithium from the feed solution is stored as electrochemical energy, which is then recycled for subsequent extraction processing steps. This energy storage and energy recycling is carried out in a continuous, ultra-efficient, ongoing cycle. Because the irrecoverable energy losses incurred in each cycle are limited to negligible Joule heating of the system components and feed solution, the system can be sustainably powered using locally generated renewable energy.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims the benefit of and priority to U.S. patent application Ser. No. 17 / 948,030, filed Sep. 19, 2022, entitled "ENERGY RECLAMATION AND CARBON-NEUTRAL SYSTEM FOR ULTRA-EFFICIENT EV BATTERY RECYCLING," and U.S. patent application Ser. No. 17 / 948,055, filed Sep. 19, 2022, entitled "WATER-IMPERMEABLE CARBON-BASED ELECTROLYTE AND SEPARATION MEMBRANE AND FABRICATION THEREOF," both of which are assigned to the assignee herein.

[0002] The present invention relates to battery recycling, and more particularly to energy recovery for ion separation. [Background technology]

[0003] Currently, various membrane options are used to separate and recover alkali metals. For example, electrolyte membranes may rely on binders to hold the electrolyte membrane together. Alternatively, solid electrolyte particles may be sintered (or otherwise compressed) together into an electrolyte membrane of the desired shape. Additionally, soft materials may be easily processed into membrane layers. However, each of these current solutions may lead to low ionic conductivity, low membrane durability, low scalability, and / or low selectivity for alkali metals.

[0004] Furthermore, conventional alkali metal extraction systems are energy intensive (to separate the alkali metal from the feed solution). As global use of alkali metals, and lithium in particular (e.g., for all types of electric vehicles), continues to increase, reliance on conventional metal extraction systems will unsustainably increase ever-increasing energy demands and unnecessarily increase hazardous waste streams (e.g., extraction / leaching of lithium from minerals). Furthermore, producing the ever-increasing energy required by these conventional extraction systems will increase greenhouse gas emissions (e.g., by fossil fuel-burning power generation facilities).

[0005] Therefore, there is a need to address these and / or other problems associated with the prior art. Summary of the Invention

[0006] A system and method for recycling energy is provided. During use, lithium ions are transported from a feed solution to a first electrode through a first membrane comprising a first solid electrolyte embedded in a first matrix, and the transport of the lithium ions from the feed solution to the first electrode requires an input of energy. Furthermore, second ions are transported from the second electrode to the feed solution through a second membrane comprising a second solid electrolyte embedded in a second matrix, and the transport of the second ions from the second electrode to the feed solution occurs simultaneously with the transport of lithium ions from the feed solution to the first electrode. Furthermore, lithium ions are transported from the first electrode to the electrolyte solution through the first membrane, and the transport of lithium ions from the first electrode to the electrolyte solution recovers at least a portion of the input energy.

[0007] In one embodiment, the energy input can be stored in the form of electrochemical energy of lithium ions stored in the first electrode. Furthermore, by recovering at least a portion of the energy input, the carbon footprint of the production facility is reduced. In some instances, substantially all of the energy input to drive the initial separation of lithium from the feed solution can be recovered and then used to extract lithium from other feed solutions. In this way, the energy can be largely recovered and further reused through an ongoing recycling process.

[0008] Additionally, the input source of lithium ions (in the feed solution) may be based on at least one of lithium minerals, lithium-containing brine, recycled lithium batteries, or seawater.

[0009] The voltage drop may be proportional to the thickness of at least one of the first or second membranes (assuming the ohmic resistance of all other components of the system, including the non-membrane, is negligible compared to the ohmic resistance of the membrane). Furthermore, the voltage drop may be proportional to the ohmic resistance of at least one of the first or second membranes. Thus, a thicker membrane may require more energy input for the alkali metal to pass completely from the feed solution to the first electrode. The energy input will be equal to the recoverable energy (e.g., in the form of stored electrochemical energy) and the non-recoverable energy (e.g., heat).

[0010] Furthermore, each lithium ion may pass through a single particle of the first solid electrolyte of the first membrane. In this way, the transport of lithium ions through a single particle (rather than having to pass through multiple particles) may increase the efficiency of ion transport.

[0011] The first membrane and the second membrane may each be water-impermeable. Furthermore, the first membrane may be ion-selective for lithium ions, and similarly, the second membrane may be ion-selective for second ions. The second ions may include at least one of sodium, potassium, or hydrogen. It should be understood that any ions (or ions to be extracted) less reducible than lithium may be used as the second ions. Of course, it should be understood that using ions less reducible than lithium may not be a requirement for the second membrane.

[0012] Furthermore, the transport of lithium ions from the first electrolyte into the electrolyte solution through the first solid electrolyte can occur simultaneously with the uptake of second ions from the electrolyte solution into the second electrode through the second solid electrolyte. In this manner, as lithium ions are transported from the feed solution to the first electrode, second ions are transported from the second electrode to the feed solution. Furthermore, as lithium ions are transported from the first electrode to the electrolyte solution, second ions can be transported from the electrolyte solution to the second electrode. It should be understood that a first group of second ions can be associated with the transport of second ions from the second electrode to the feed solution, and a second group of second ions can be associated with the transport of second ions from the electrolyte solution to the second electrode.

[0013] In one embodiment, the first solid electrolyte may be at least one of LATP, LZP, LAGP, LiSICON, or LTO, and the second solid electrolyte is at least one of NaSICON or KFeO.

[0014] Additionally, the first membrane may function as an electrical buffer between the first electrode and at least one of the feed solution or the electrolyte solution, and the second membrane may similarly function as an electrical buffer between the second electrode and at least one of the feed solution or the electrolyte solution.

[0015] Additionally, the diameter of the first solid electrolyte may be at least 10 μm (microns), and the materials of the first matrix and the second matrix may be the same or may be different.

[0016] Furthermore, at least one of the first electrode or the second electrode can include a second electrolyte, a binder, active material particles, and a current collector. The second electrolyte can be liquid. Furthermore, one or more sides of the first electrode and the second electrode can be lined with an adhesive configured to prevent a feed solution containing lithium ions from reaching the active material particles of either the first electrode or the second electrode.

[0017] The system can be configured such that a first transport of lithium ions from the feed solution through the first solid electrolyte into the first electrode can occur simultaneously with an export of second ions from the second electrode through the second solid electrolyte into the feed solution, and a second transport of lithium ions from the first electrolyte through the first solid electrolyte into the electrolyte solution can occur simultaneously with an uptake of second ions from the electrolyte solution into the second electrode through the second solid electrolyte.

[0018] Disclosed is a membrane comprising a layer including a solid electrolyte embedded within a matrix. The solid electrolyte is configured to extract alkali metal ions and is ion-selective to alkali metals. Further, the layer is water-impermeable.

[0019] The membrane can be used to extract any or all of lithium, sodium, or potassium. The solid electrolyte can include at least one of LATP, LZP, LAGP, LiSICON, LTO, K2Fe4O7, or NaSICON.

[0020] Additionally, the matrix used may be densely cross-linked and hydrophobic, thereby preventing the diffusion of water (or at least any other feed solution). The membrane layer may function as an electrical buffer between the feed solution and the electrode. Additionally, the layer may be configured to extract ions from the feed solution and transport them to the electrode. The layer may be used as a polysulfide barrier or an air barrier.

[0021] Furthermore, the first side of the layer can interact with the feed solution, and the second side of the layer can interact with the electrode. The extracted ions can collect on at least one of the conductive surface of an intercalation active material, a conversion active material, a capacitive active material, an electrode, a capacitor, a pseudocapacitor active material, or an electrode.

[0022] A voltage drop may occur between a first side of the layer and a second side of the layer. Furthermore, the voltage drop may be proportional to the thickness of the layer, such that as the thickness increases, the voltage drop increases. Furthermore, the voltage drop may be adjusted by increasing the current I across the layer. Furthermore, the voltage drop may be a function of the thickness of the layer and the resistivity of the layer.

[0023] In use, fabrication of the membrane can include mechanically polishing a layer of the membrane to expose the solid electrolyte. In one embodiment, the diameter of the solid electrolyte can be at least 10 μm (microns) and / or can be configured or tailored to the desired ions to be extracted. In one embodiment, extraction of ions can cause a voltage drop.

[0024] The feed solution may include lithium ions, which may be supplied from a variety of sources, including, but not limited to, at least one of lithium minerals, lithium-containing brine, recycled lithium batteries, or seawater.

[0025] In one embodiment, at least one side of the layer can interact with an electrode, the electrode including a second electrolyte, a binder, active material particles, and a current collector. Further, the second electrolyte can be liquid, and one or more sides of the electrode can be lined with an adhesive configured to prevent a feed solution containing ions of an alkali metal from reaching the active material particles of the electrode.

[0026] Furthermore, the matrix molecules can be covalently bonded to the solid electrolyte particles. In this way, water (or any other solution containing other ions) can be prevented from passing through the space between the solid electrolyte particles and the matrix molecules. Furthermore, alkali metal ions can pass through the single particles of the solid electrolyte in the layer. [Brief explanation of the drawings]

[0027] [Figure 1A] 1 illustrates a system and method for carbon-neural energy regenerative battery recycling, according to one embodiment. [Figure 1B] 1 illustrates a solid electrolyte membrane, according to one embodiment. [Figure 2] 1 illustrates a method for making a solid electrolyte membrane, according to one embodiment. [Figure 3] 1 illustrates a process for mechanically polishing a solid electrolyte film, according to one embodiment. [Figure 4] 1 illustrates a roll-to-roll process for mechanically polishing a solid electrolyte film, according to one embodiment. [Figure 5] 1 illustrates an ion-selective solid electrolyte membrane, according to one embodiment. [Figure 6] 1 illustrates the voltage drop using a carbon-based membrane, according to one embodiment. [Figure 7] 1 shows a close-up view of graphitic carbon, according to one embodiment. [Figure 8] 1 illustrates a process for recovering energy from lithium extraction, according to one embodiment. [Figure 9] 1 illustrates a cell architecture, according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0028] Lithium has become present in nearly everything—electrical or electronic products, from batteries to armor plating, bicycle frames to glass, lubricants to ceramics, and many others. Traditional systems and methods for obtaining lithium extract it from raw materials, such as ores and / or mineral springs. It is well known that global demand for lithium will deplete all known commercially available sources of such material. Therefore, recycling lithium becomes essential. One source of lithium that is a candidate for recycling is from used lithium-containing batteries. However, to be sustainable, lithium extraction technologies must be energy-efficient and scalable.

[0029] This specification relates not only to a method for extracting lithium, but also to a method for recovering the energy expended to extract the lithium. During use, a voltage drop may occur when a membrane having a solid electrolyte is used to extract lithium ions from a feed solution. The extracted lithium ions may be stored on an electrode. If desired, the lithium ions may then be transferred from the electrode, which may then result in the release of the stored energy. In this manner, the extraction, storage, and release steps correspond to a typical anode and cathode assembly and typical energy injection / release based on ion flow.

[0030] Furthermore, the recycling technologies disclosed herein are scalable to meet the global EV battery recycling demand projected throughout this decade and subsequent decades. To illustrate the scale required, it is estimated that 10 TWh of EV battery capacity will be required between now and early 2030, with over 1 TWh required in calendar year 2025 alone. This demand, in turn, may require approximately 125,000 tonnes (or more) of lithium for EV batteries each year. It is recognized that a significantly high percentage of this lithium tonnage can be recycled from used batteries.

[0031] Given this large scale, a major challenge is the efficiency of reclamation. The technology disclosed herein achieves this challenge by extremely lowing the demand for energy required to perform energy recycling and, consequently, achieve lithium reclamation. For example, for a single plant recycling 500 tons of lithium per year, using the energy reclamation technology disclosed herein, the required continuous power demand could be as low as 44 KW (a number small enough to be provided by a bank of solar panels that could fit on the roof space of an EV battery plant). Thus, the present disclosure herein not only provides more efficient separation of lithium from the feed solution, but also provides significant energy reclamation associated with lithium extraction.

[0032] Thus, based on the ability to recover (extract) spent energy through the release of ions, a near-carbon-neutral system for ultra-efficient battery recycling may be possible. As the demand for lithium continues to increase, so too will the need to sustainably recycle and recover lithium from existing lithium-containing items. Furthermore, in the quest for greener energy, the present disclosure provides for the recovery of a significant portion of the energy spent to extract lithium ions, which in turn results in an environmentally prudent and responsible alternative to known methods and systems.

[0033] Furthermore, known separation membranes often crack and break over time, resulting in both time inefficiency and economic loss (in terms of having to replace the electrolyte). Furthermore, other membranes (e.g., adsorption membranes, etc.) can suffer from membrane fouling, which in turn can reduce membrane efficiency and lifespan. In contrast, the membranes disclosed herein are bound within a stable matrix that is not (or is much less) susceptible to membrane fouling or membrane cracking (e.g., as a result of volume expansion during extraction), which in turn extends the lifespan of the electrolyte and membrane, thereby overcoming such inefficiencies and losses.

[0034] Definition and Use of Diagrams Some of the terms used in this description are defined below for ease of reference. The presented terms and their respective definitions are not intended to be strictly limited to these definitions, and terms may be further defined by the use of the term in this disclosure. The term "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" should not necessarily be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete manner. As used in this application and the appended claims, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clear from the context, "X employs A or B" is intended to mean any of the natural inclusive permutations. That is, if X employs A, if X employs B, or if X employs both A and B, then "X employs A or B" is satisfied under any of the foregoing cases. As used herein, at least one of A or B means at least one of A, or at least one of B, or at least one of both A and B. In other words, the phrase is disjunctive. The articles "a" and "an," as used in this application and the appended claims, should generally be construed to mean "one or more" unless otherwise specified or unless the singular form is clearly intended from the context.

[0035] Various embodiments are described herein with reference to the figures. It should be noted that the figures are not drawn to scale, and that elements of similar structure or function are represented by similar reference numerals throughout the figures. It should also be noted that the figures are intended only to facilitate the description of the disclosed embodiments, and that the figures do not represent an exhaustive treatment of all possible embodiments, nor are they intended to impose any limitations on the scope of the claims. Furthermore, the illustrated embodiments need not depict all aspects or advantages of use in any particular environment.

[0036] Aspects or advantages described in connection with a particular embodiment are not necessarily limited to that embodiment and may be implemented in any other embodiments, even if not so illustrated. References throughout this specification to "some embodiments" or "other embodiments" refer to a particular feature, structure, material, or characteristic described in connection with the embodiment as being included in at least one embodiment. Thus, the appearances of the phrase "in some embodiments" or "in other embodiments" in various places throughout this specification do not necessarily refer to the same one or more embodiments. The disclosed embodiments are not intended to limit the scope of the claims.

[0037] Within the context of this specification, the term "membrane" shall be understood to refer to a barrier or backing that separates a solution from a filtrate. The solution may include any feed material / solution, and the filtrate may include the filtrate that has been filtered by the membrane. Additionally, a solid electrolyte (which may be embedded within the membrane) may refer to an electrolyte in a solid form that allows ions to move. Furthermore, the matrix may include an epoxy, a polymer matrix, an optional polymer binder, a multifunctional amine, and / or a multifunctional epoxide. In this manner, the matrix may provide the mechanical strength needed to keep the film intact throughout its operational lifetime, including preventing cracks from forming and acting as a barrier when the membrane is removed from water (or any other feed solution).

[0038] Within the context of this specification, the term "electrode" refers to an electrical conductor. An electrode may include an active material that can act as a host for extracted ions (such as lithium) and store an energy input for extraction in the form of electrochemical energy.

[0039] Description of exemplary embodiments 1A illustrates a system and method 101 for carbon-neural energy regenerative battery recycling, according to one embodiment. Optionally, the system and method 101 may be implemented in conjunction with any one or more of the embodiments described in any preceding and / or following figure(s) and / or their description. However, it should be understood that the system and method 101 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0040] Figure 1A is presented to illustrate the virtuous cycle that encompasses both the sustainability of lithium extraction and the sustainability of energy recycling.

[0041] As shown, the system and method 101 includes extracting lithium (step 103). The extraction of lithium may occur using a solid electrolyte membrane (such as solid electrolyte membrane 100 described in detail herein). Energy may be consumed in extracting the lithium (step 105).

[0042] In one embodiment, a voltage drop (such as voltage drop 612 due to lithium ion transport) may be due to ohmic resistance (V=IR). Because I (i.e., the desired current I) is generally determined by the desired extraction rate of Li, the extractor may be configured to minimize R to produce the lowest voltage drop V (e.g., corresponding to non-renewable electricity). Because resistance is proportional to film thickness and inversely proportional to conductivity, a system may be constructed to use a charge conducting component (e.g., a Li+ extraction film) with the smallest thickness and the greatest conductivity.

[0043] The extracted lithium ions are stored on the electrode. When energy is needed, a second electrolyte can be used to facilitate the removal and transfer of lithium ions from the electrode (step 107). Energy can be reclaimed in the removal and transfer of lithium ions from the electrode (step 109).

[0044] Thus, during operation, lithium can be extracted from the feed solution using the first membrane, stored on the electrode, and then transferred using the electrolyte solution. The energy required to extract lithium ions from the feed solution can be recovered as the lithium ions are transferred from the electrode. Once the lithium ions are transferred (to the electrolyte solution), they can be in the form of lithium carbonate (or equivalent). During operation, as lithium is extracted (per step 103), it can be removed from the feed solution and stored on the electrode. As the lithium ions are transported from the feed solution, they can then be replaced with other ions (such as sodium) that can be transported from the second electrode into the feed solution through the second membrane. The feed solution can then be removed and replaced with the electrolyte solution. For example, in various embodiments, the membrane can be physically removed from the feed solution (like a sponge being removed from a bath), or the membrane can be immersed in a tank containing electrolyte solution (where the electrolyte solution can be pumped in / out to exchange).

[0045] The lithium ions stored in the electrode can then be transported from the electrode to the electrolyte solution. This removal of the lithium ions (and their transport through the membrane) can result in the release of energy that can be recycled (e.g., via an external battery). In other words, the energy stored in the form of the electrochemical energy of the extracted lithium can be recycled upon lithium removal. As the lithium ions move from the electrode to the electrolyte solution, other ions (such as sodium) present in the electrolyte solution can move to the second electrode (through the second membrane). In this way, energy can be consumed as the lithium is transported to the electrode, and energy can be released as the lithium is transferred from the electrode. This release of energy can then be used to provide a large portion of the input energy required for lithium extraction (through lithium extraction step 103 and energy consumption step 105).

[0046] Thus, the act of extracting, storing, and then releasing lithium ions mimics the energy charge and discharge cycles of a battery, and can then provide high energy efficiency (by recovering the energy input).

[0047] With regard to the feed solution, previously used and exhausted batteries can be added to an aqueous solution, which can serve as a basis for extracting lithium ions. If higher selectivity (e.g., lithium ions) is desired, the first membrane (used to extract lithium ions) can be made thicker. More specifically, the thicker the membrane, the longer the distance water must travel, and therefore the lower the water permeation (diffusion rate through it). Therefore, a thicker membrane can have a higher selectivity for Li+ uptake via electrodialysis than for water uptake via diffusion. Furthermore, in one embodiment, the greater the thickness, the greater the voltage drop. In other words, since resistance scales linearly with thickness, the voltage drop can scale linearly with thickness.

[0048] For example, a first membrane can be tailored to the ions that pass through it. In this way, the membrane can be tailored so that, for example, larger ions can pass through the first membrane layer and, for example, smaller ions can pass through the second membrane layer. For example, a solid electrolyte material can be selected whose crystal structure has inherent selectivity for desired ions. The ease with which a particular ion passes through the solid electrolyte material can depend on the amount of energy required for the ion to "hop" between different sites in the crystal lattice. Ions that are too large or too small require more energy to hop between sites. Thus, for any given solid electrolyte structure, the "optimum" ion size with the lowest activation energy (and therefore the highest ionic conductivity and selectivity relative to other ions) can be tailored to the specific solid electrolyte structure. In this way, the structure of the crystal lattice (of the solid electrolyte) can be tailored to specific ions (if the activation energy is too high, the particular ion simply does not pass through the membrane or passes in small or trace amounts).

[0049] 1B illustrates a solid electrolyte membrane 100, according to one embodiment. Optionally, the solid electrolyte membrane 100 may be implemented in conjunction with any one or more of the embodiments described in any of the preceding and / or following figure(s) and / or the description thereof. However, it should be understood that the solid electrolyte membrane 100 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0050] In the context of this specification, solid electrolyte membrane 100 may be used to allow the passage of Li+ (or any pre-configured alkali metal) ions while preventing all other unwanted substances, such as water, from passing through the solid electrolyte or the substrate in which it is embedded. Furthermore, the structure of solid electrolyte membrane 100 is extremely durable, allowing operation for significant periods of time without structural degradation or performance degradation.

[0051] Of course, it should be understood that the solid electrolyte membrane 100 may be configured to allow the passage of any particular ion. Additionally, the solid electrolyte membrane 100 may be configured for high selectivity of ions (Na / Li, Na / K, etc.).

[0052] The solid electrolyte membrane 100 improves upon and solves problems previously associated with previous selective membranes. For example, when the solid electrolyte membrane 100 is used as an ion-selective membrane for electrochemical lithium extraction / recycling, the solid electrolyte membrane 100 can prevent the electrode from contacting water (which may adversely react with the electrode). Furthermore, the ion-selective membrane can prevent the need to directly immerse the electrode active material in a feed solution, which would dry out the electrode. Drying of the electrode can then make the electrode material vulnerable to the contents of the feed solution, which can lead to cracking upon removal from the solution. Furthermore, the ion-selective membrane can resist cracking upon removal from the feed solution due to the fact that the ion-selective membrane can be held together by a densely cross-linked matrix, which can prevent reorganization of the polymer structure (which can occur when a liquid with high surface tension, such as water, is removed from the ion-selective membrane).

[0053] Additionally, the solid electrolyte membrane 100 can be used as a polysulfide barrier, which can attenuate or even eliminate (almost completely) the polysulfide shuttle phenomenon in Li-S batteries. Furthermore, the solid electrolyte membrane 100 can protect Li metal (or any alkali metal) from air, enabling the use of Li-air batteries, which have the highest specific energy of any known lithium-ion battery chemistry. Thus, the solid electrolyte membrane 100 can be used as a conductive barrier to air.

[0054] As shown, the solid electrolyte 102 is embedded within a matrix 104. In one embodiment, the solid electrolyte 102 may be embedded in aluminized Mylar. The combination of the solid electrolyte 102 and the matrix 104 represents a membrane. In one embodiment, as shown, the feed solution 106 contains an alkali metal (Li +The membrane may contain a metal (e.g., lithium, iron, etc.) and a liquid (e.g., water, HO). The membrane may be impermeable to water so as to prevent water from crossing the solid electrolyte 102 and the matrix 104. In contrast, alkali metals (Li + , etc.) may not pass through the matrix 104, but may pass through the solid electrolyte 102. Those that pass through the membrane may be found in the filtrate 108. Furthermore, the membrane, in addition to repelling water, may also repel polysulfides, air (including, but not limited to, oxygen, nitrogen, carbon dioxide, etc.), etc.

[0055] The membrane may be comprised of solid electrolyte particles (illustrated as solid electrolyte 102) within a dense matrix (illustrated as matrix 104). Each individual solid electrolyte particle may completely traverse the membrane such that a Li+ ion (or any alkali metal ion) entering one side of the membrane enters the membrane through the same solid electrolyte particle as it exits the membrane (i.e., without having to cross any solid-solid interfaces). In one embodiment, completely traversing the membrane as a single particle may enable higher conductivity because the transport path may be more direct (especially compared to Li+ transport paths that cross many solid-solid interfaces, which in turn may have lower Li+ conductivity).

[0056] In one embodiment, the solid electrolyte membrane 102 may also prevent water from passing through the space between the solid electrolyte particles and the matrix 104. In one embodiment, this may be due to the fact that the matrix 104 may strongly interact with the solid electrolyte particles of the solid electrolyte 102. Furthermore, the solid electrolyte particles of the solid electrolyte 102 may be functionalized to improve their interaction with the matrix 104. For example, in one embodiment, when using the phosphate-rich solid electrolyte LATP, an acrylic acid derivative (such as 2-(aminoethyl) methacrylate) may be used to react with the surface phosphates (via Michael addition) to enrich the surface of the solid electrolyte 102 with amine groups. Thus, epoxide molecules from the matrix 104 may covalently bond with the solid electrolyte particles of the solid electrolyte 102.

[0057] In the solid electrolyte membrane 100, the alkali metal is shown as Li+, but it should be understood that any suitable ion may be selected. Depending on the ions to be separated, the solid electrolyte may be replaced with an appropriate material. For example, in one embodiment, if separation of Na+ is desired, then NASICON may be used instead of LiSICON as the solid electrolyte. Of course, it should be understood that any other ion (K+, Rb+, Cs+, etc.) may be separated based on the accompanying solid electrolyte material. Furthermore, it should be understood that LiSICON is a member of the solid NASICON family, consisting of ZrO6 octahedra and PO4 / SiO4 tetrahedra that share common corners, with Na+ in the interstitial spaces. LiSICON may have MO6 (M = Ti, Ge, Zr, Hf, Sn) octahedra and PO4 tetrahedra in the interstitial positions, as well as structural analogues to Li+. Such solid electrolytes may be highly resistant to decomposition and / or corrosion in water. It should be understood that other materials may function similarly (providing resistance to decomposition and / or corrosion in water).

[0058] Furthermore, the process can be tailored to achieve any desired volume fraction of solid electrolyte particles within the matrix. For example, a slurry can be cast in which all particles are the same size and hexagonally close-packed so that the volume fraction of particles within the cast film is maximized. For example, maximizing the volume fraction can include maximizing the volume for a given particle size distribution. In other words, if all particles are exactly the same size, hexagonal close-packing may be the most efficient way to utilize volume. However, in one embodiment, using particles of multiple sizes and / or different shapes may enable the use of even higher volume fractions of the film. The volume fraction of solid electrolyte particles can then be further increased by removing increasingly larger amounts of film on both sides (by polishing with an abrasive). In this way, any volume fraction of solid electrolyte particles can be achieved. Creating a film with a higher volume fraction of solid electrolyte may require polishing the film down to a thinner film, thereby removing a higher percentage of the initial film.

[0059] Furthermore, while the solid electrolyte membrane 100 is illustrated as having spherical solid electrolyte particles, it should be understood that the solid electrolyte 102 particles do not necessarily have to be spherical. For example, the solid electrolyte 102 particles may be donut-shaped, blood-spherical, and / or any other particularly desired shape (which may be produced based on a spray-drying process, particularly by adjusting the feed rate of the aqueous precursor to form the particles). Furthermore, the solid electrolyte 102 particles can be prepared by preparing a precursor solution, typically drying, followed by sintering to obtain non-spherical particles. Ball milling can then be used to reduce the particle size.

[0060] To maximize kinetic flow, it is recommended that ions traverse a single particle of the solid electrolyte 102. However, the solid electrolyte membrane 100 may include multiple layers of the solid electrolyte 102, which may allow ions to migrate or hop from one particle of the solid electrolyte 102 to another particle of the solid electrolyte 102. Having multiple layers of the solid electrolyte 102 may allow for a more uniform distribution of the particles within the matrix.

[0061] Additionally, multiple membranes (such as solid electrolyte membrane 100 and another of solid electrolyte membrane 100) can be stacked together to create thicker membranes (which may be used for ion selectivity, kinetic flow, higher filtering capabilities, etc.). In such embodiments, the individual layers of the multiple membranes can be bonded together with a Li+ (or any selected alkali metal ion) conductive adhesive, such as a matrix containing polyethylene glycol diglycidyl ether (PEG-DGE) and / or Jeffamine D-230, and a lithium salt such as LiTFSI. Of course, it should be understood that other Li+ conductive adhesives can be used to enable the creation of multilayer membranes.

[0062] In one embodiment, rather than using mechanical polishing, laser ablation and / or chemical etching may be used to scrape away the surface of the solid electrolyte membrane 100, exposing the grains of the solid electrolyte 102. Additionally, ion milling or focused ion beam (FIB) may be used to polish the surface.

[0063] We now provide more example information regarding various optional architectures and applications that may or may not implement the above-described methods, depending on the user's preferences. Note that the following information is provided for illustrative purposes and should not be construed as limiting in any way. Any of the following features may be optionally incorporated with or without the exclusion of other features described.

[0064] 2 illustrates a method 200 for making a solid electrolyte membrane, according to one embodiment. Optionally, method 200 may be implemented in conjunction with any one or more of the embodiments described in any preceding and / or following figure(s) and / or the description thereof. However, it should be understood that method 200 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0065] As shown, individual particles of an optimal solid electrolyte are prepared (step 202). In one embodiment, when using LiSiCON as the solid electrolyte material, an aqueous solution containing precursors (Li2CO3, LiNO3, Al2O3, TiO2, GeO2, NH4H2PO4) can be spray-dried into spherical particles with diameters of 1 um to 1 mm (or even less than 1 um) (step 204). It should be understood that the listed precursors should not be construed as being exclusively limited. Other precursors compatible with the desired selected solid electrolyte material may also be used. Furthermore, particle size can directly affect the resistance to ion transport. For example, a thinner film can result in lower resistance to ion transport. Regardless, the film can be tailored to be thick enough to prevent any appreciable penetration of water (or feed solution). The resulting particles are then sintered at high temperatures to densify the particles (step 206). The sintering temperature and time may depend on the selected solid electrolyte material. Increasing the density of the particles may prevent unwanted substances (such as water) from diffusing through the bulk of the aqueous solution while homogenizing the distribution of atoms within the particles (enhancing Li+ conductivity).

[0066] The precursor solution for the solid electrolyte may consist of salts, inorganic or organic compounds containing the elements of the solid electrolyte. The table below shows possible precursors and candidate materials that result in solid electrolytes.

[0067] [Table 1]

[0068] [Table 2]

[0069] where R is any alkyl substituent, including methyl, ethyl, propyl, butyl, isopropyl, and isobutyl. Notable precursors include titanium isopropoxide (TTIP) for Ti and tetraethyl orthosilicate (TEOS) for Si.

[0070] For lithium-selective membranes, the solid electrolyte may consist of any NASICON-type Li+ conductor, such as LATP, LAGP, LAGTP, LATP, LTASP, or LLZP (if first letter of anagram, L=Li; if not first letter of anagram, A=Al, T=Ti, G=Ge, L=La, Z=Zr, S=Si, P=PO4) 3- ). Of the aforementioned electrolytes in the NASICON-type Li+ conductor, any tetravalent metal may be partially or completely replaced with any other tetravalent metal mentioned in the table above, and any trivalent metal (Al) may be partially or completely replaced with any other trivalent metal mentioned in the table above. Additionally, any trivalent or tetravalent metal may be partially or completely eliminated. Other potential solid electrolyte materials may include lithium iron phosphate (LFP), lithium titanium oxide (LTO). Furthermore, the precursors used may depend on the elements used in the solid electrolyte. Of course, for each selected element, suitable precursors may be listed in the tables provided herein.

[0071] Additionally, multiple membranes may be used. For example, as shown in process 800, detailed below, a first solid electrolyte membrane may be used to selectively extract lithium from a feed solution, and a second solid electrolyte membrane may be used to transfer ions from the second electrode to the feed solution (from which the lithium has been extracted). In such embodiments, the composition of the second solid electrolyte membrane may depend on the particular ion utilized at the second electrode. For example, in the case of sodium, the solid electrolyte may be Na 1+x Zr2Si x P 3-x O 12It may consist of any NASICON-type conductor in the form of (0 < x < 3). In the case of the aforementioned NASICON-type conductor, any tetravalent metal (Zr, Si) can be partially or completely replaced by any other equivalent metal in the table provided above. Further, the electrolyte may be doped with any trivalent metal in the table above. In the case of potassium, the solid electrolyte may consist of K2Fe4O7. Thus, the precursors used may depend on the elements used in the solid electrolyte, and for each element selected, suitable precursors may be listed in the table provided herein.

[0072] Next, preferably, in order to remove overly small particles and / or narrow the size distribution of the particle batch, the particles can be filtered based on size (e.g., using a sieve) (step 208). Suitable materials for the solid electrolyte material can include NASICON-type Li+ conductors (also known as LiSICON) including LATP / LAGP / LAGTP, as well as lithium titanate (LTO) and lithium iron phosphate (LFP), but are not limited thereto. Generally, any material that is water-stable and has a high-density crystal structure with a conductivity of at least 10^-6 S / cm for Li+ (or any alkali metal selected) and a selectivity for Li+ (or any ion desired) higher than other ions may be acceptable as a solid electrolyte material.

[0073] In one embodiment, the crystal structure of the solid electrolyte may include a tetrahedral structure (such as ZrO6) and / or an octahedral structure (such as PO4, SiO4). Further, using the process disclosed herein, the microparticles can be sized to the size required for efficient membrane ion transport. For example, the microparticles of the solid electrolyte can be sized to 100 microns (μm) or larger when used in a 100-micron-thick membrane.

[0074] Next, a slurry containing particles, a matrix (such as an epoxy prepolymer), and a thickener (such as SBR, PVDF, PEO, and / or a pre-cured epoxy) is cast onto a substrate (step 210) to form a dense coating in which the particles can be embedded in the matrix. In one embodiment, the prepolymer can also function as a thickener. Furthermore, the substrate can include, but is not limited to, fluorinated ethylene propylene (FEP), polytetrafluoroethane (PTFE), silicone, polyethylene (PE), polypropylene, Kapton, polyethylene terephthalate (PET), and the like. Furthermore, the substrate may be made of one material but can be coated with one of the aforementioned materials (e.g., fluorinated ethylene propylene (FEP), polytetrafluoroethane (PTFE), silicone, polyethylene (PE), polypropylene, Kapton, polyethylene terephthalate (PET), and the like) to impart similar or identical surface properties to the resulting substrate and enable delamination of the resulting coating. The film coating is then cured (step 212). By way of example, curing can be accomplished by thermal curing and / or UV curing. The result of curing may include a densely crosslinked matrix.

[0075] In various embodiments, materials suitable for prepolymers for thermally crosslinked epoxies can include any multifunctional epoxide molecule (such as Epon 828 and / or PEG-DGE) and an amine crosslinker (such as melamine, phenylenediamine, and / or Jeffamine D-230). Materials suitable for UV-cured polymers can include multifunctional acrylates / methacrylates (such as PEGDMA and / or PEGDA) and a photoinitiator (such as Darocur 1173). The crosslinked matrix can have a structure that prevents the diffusion of any substance, most notably water and gas, as a result of its hydrophobic structure and highly crosslinked nature.

[0076] Finally, the film coating, including one or both sides, is then polished (step 214) using a polishing pad. This may be done in a roll-to-roll operation, where the membrane roll with the film coating passes through a series of rotating / sliding polishing pads to scrape the surface of the membrane, thereby removing the outermost regions of the membrane. After polishing, each individual solid electrolyte particle embedded in the membrane will have a large area of ​​exposed surface on both sides of the membrane, which may provide a route for Li+ ions (or any membrane-specific ions) to completely traverse the membrane without having to travel through multiple particles.

[0077] The membranes described herein can be manufactured using a web coater. Regarding the scalability of the production of such membranes, as battery manufacturing capacity increases to meet growing demand, a single conventional roll-to-roll coater (with a footprint small enough to fit in a small office cubicle) can produce enough membrane (such as solid electrolyte membrane 100) to match each additional 2 GWh of lithium battery manufacturing capacity. Additional web coaters may be added to operate in parallel (as lithium battery manufacturing capacity continues to increase over time). Furthermore, these web coaters can be located near battery factories. In this way, solid electrolyte production is space-efficient and scalable to meet anticipated industry demands.

[0078] 3 illustrates a process 300 for mechanically polishing a solid electrolyte film, according to one embodiment. Optionally, process 300 may be implemented in conjunction with any one or more of the embodiments described in any of the preceding and / or following figures and / or figures and / or descriptions thereof. However, it should be understood that process 300 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0079] As shown, the solid electrolyte 302 is embedded within the matrix 304. A mechanical polishing device 308 may be used to polish one or more surfaces of the membrane film (including both the solid electrolyte 302 and the matrix 304). In various embodiments, the solid electrolyte 302 may extend to the surface of the membrane film. In other embodiments, the matrix 304 may extend to the surface of the membrane film. In either case, additional material 306 (either the solid electrolyte 302 and / or the matrix 304) may be present within the membrane film. In various embodiments, polishing may be performed one side at a time (sequentially) or both sides simultaneously (assuming polishing both sides is desired). Furthermore, in one embodiment, a first side may be polished, then the coating may be removed from the release film and transferred to the surface of the electrode (active material coating), with the polished side facing the active material coating, and the resulting stack may then be polished again to expose solid electrolyte particles on the remaining side.

[0080] The membrane film may be polished by passing it through a series of one or more polishing pads that rotate / slide to abrade the surface of the membrane film (310), thereby removing the outermost region of the membrane film.

[0081] After polishing one or more surfaces of the membrane film, the polished membrane 312 includes a first exposed surface 314 of the solid electrolyte and a second exposed surface 316 of the matrix. Thus, each individual solid electrolyte particle embedded in the membrane film has a large area of ​​exposed surface on both sides of the membrane, which may provide a route for Li+ ions to completely traverse the membrane without having to travel through multiple particles.

[0082] 4 illustrates a roll-to-roll process 400 for mechanically polishing a solid electrolyte film, according to one embodiment. Optionally, process 400 may be implemented in conjunction with any one or more of the embodiments described in any of the preceding and / or following figure(s) and / or the description thereof. However, it should be understood that roll-to-roll process 400 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0083] As shown, the membrane film 402 may be polished on one or more sides (shown as double-sided polishing in the roll-to-roll process 400) using mechanical polishing devices 404 (such as polishing pads). The roll-to-roll process 400 illustrates a roll-to-roll operation in which a roll of membrane film 402 is passed through a series of rotating / sliding mechanical polishing devices 404 to abrade the surface of the membrane film 402, thereby removing the outermost regions of the membrane film 402. After passing through the mechanical polishing devices 404, a first exposed surface of the matrix 406 and a second exposed surface of the solid electrolyte 408 may be revealed.

[0084] 5 illustrates an ion-selective solid electrolyte membrane 500, according to one embodiment. Optionally, the ion-selective solid electrolyte membrane 500 may be implemented in conjunction with any one or more of the embodiments described in any preceding and / or following figure(s) and / or the description thereof. However, it should be understood that the ion-selective solid electrolyte membrane 500 may be implemented in conjunction with any desired environment. Furthermore, the foregoing definitions may equally apply to the following description.

[0085] As shown, the ion-selective solid electrolyte membrane 500 is made of lithium Li + 504, Sodium + 506, potassium K + , and / or other metal ions 510. The feed solution 502 contains lithium, Li + 504, Sodium +506, potassium K + , and / or any aqueous solution containing one or more of the other metal ions 510.

[0086] Additionally, the film 512 contains ions, in this exemplary case, lithium Li + 504 can be used to selectively allow other ions to pass through (516) membrane 512. In contrast, membrane 512 can selectively allow other ions, in this example case sodium Na + 506, potassium K + , and / or other metal ions 510 from passing 514 through membrane 512. Stored ions that pass through membrane 512 may be found in filtrate 518.

[0087] It should be appreciated that the global demand for lithium continues to increase (particularly as the demand for vehicle electrification increases). The use of ion-selective solid electrolyte membrane 500 can enable the extraction of lithium from lithium minerals and otherwise unused or discarded sources, including, but not limited to, recycled lithium batteries and seawater (particularly since seawater contains >99% of the Earth's available Li supply). Current systems (such as those from Li brine and / or Li minerals) are unable to recover lithium (and other alkali metals) from unconventional sources and / or have problems (in terms of selectivity, durability, and / or scalability).

[0088] 6 illustrates a voltage drop 600 using a carbon-based membrane, according to one embodiment. Optionally, the voltage drop 600 may be implemented in conjunction with any one or more of the embodiments described in any preceding and / or following figure(s) and / or the description thereof. However, it should be understood that the voltage drop 600 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0089] As shown, a voltage drop 600 may occur using a membrane 604. For example, the membrane 604 may be in contact with a feed solution 602 and an electrode 606. Ions may experience a voltage drop 608 as they pass through the membrane 604. In various embodiments, the membrane 604 may be carbon-based (without solid electrolyte particles). In this particular embodiment, the carbon-based particles may transport lithium ions by capacitive adsorption rather than through the inherent crystalline structure of the material (as is the case with solid electrolyte particles). However, it should be understood that the voltage drop 600 may occur with any type of membrane used (whether carbon-based or solid electrolyte particles).

[0090] In certain embodiments (and as an alternative to membrane 604), the separation membrane may include multiple layers of graphitic carbon. For example, a capacitor-like carbon-based membrane may interact with and contact the feed solution 602. Furthermore, the graphitic carbon membrane may be a second layer within the membrane. It should be understood that any number of layers of graphitic carbon may be used. Based on the interaction with the graphitic carbon, ions passing through the capacitor-like carbon-based membrane and the graphitic carbon membrane may accumulate as solid metals (such as metallic lithium Li). Furthermore, ions may accumulate in the electrode 606 (which may include, but is not limited to, graphite). The electrode 606 may be made of low-porosity graphite prepared by prolonged sintering of a carbonaceous precursor (e.g., a polymer such as polyacrylonitrile (PAN)).

[0091] In one embodiment, membrane 604 and / or the graphitic carbon multilayer film can be configured to selectively extract lithium ions (and / or any pre-formed alkali metal ions) from a precursor / feed solution enriched in the selected ions and other ions, which can include lithium-rich brine, an aqueous solution of ions produced during the acid leaching of lithium minerals, an aqueous solution of ions produced by dissolution (with or without acid) of discarded / recycled batteries, seawater, and / or any other aqueous solution containing the desired ions to be extracted.

[0092] With respect to graphitic carbon multilayer films, the graphitic carbon multilayer film may consist of multiple layers, each of which is made of a different type of carbon (e.g., capacitor-like carbon-based film, graphitic carbon film, etc.).

[0093] Furthermore, with respect to the graphitic carbon film of the graphitic carbon multilayer film, the graphitic carbon film may be comprised of graphitic carbon bound together with a matrix (including a polymeric binder such as polyvinylidene fluoride (PVDF), epoxy, etc.) and / or compressed plates. With respect to the capacitor-like carbon-based film, the capacitor-like carbon-based film may be a separate film layer comprised of carbon particles bound together with a polymeric binder or compressed plates (similar to the graphitic carbon film).

[0094] In one embodiment, regardless of whether membrane 604 or a graphitic carbon multilayer is used, the alkali metal (such as lithium) can be electrochemically reduced to its metallic state (such as Li) as it migrates through the membrane. Furthermore, with respect to membrane 604, the alkali metal can be reduced to its metallic state. Therefore, an active material (such as graphite) can be chosen whose reduction potential is close to that of the metallic alkali metal (such as Li), so that the membrane can be in direct electrical contact with the active material, and the current density can be high enough to initiate the formation of metallic alkali metal (Li) (or the active material can be overcharged). Furthermore, the cell design can include a separator between the active material coating and membrane 604 to prevent direct electrical contact. Furthermore, if plating of metallic Li is desired, an electrode without active material could be created (such that metallic Li could be plated directly on the current collector or any electronically conductive surface within the electrode) and / or the active material can be overcharged so that all sites available for Li insertion into the active material can be occupied (leading to the plating of metallic Li upon further charging). It should be understood that while reduction to the metallic state is feasible, the system may be configured to prioritize energy efficiency (which may in turn require lower current density requirements to reduce energy losses due to ohmic resistance). Thus, the system may be modified to prioritize the desired outcome (such as, but not limited to, energy efficiency, metallic reduction, etc.).

[0095] In one embodiment, the voltage drop may be related to the stability of membrane 604 to water. For this particular application, the voltage drop may be either ionic or electronic in nature. Furthermore, if the voltage drop is electronic, it may allow for safe operation of membrane 604 in contact with water.

[0096] In this manner, the feed solution 602 may function as an electrolyte, and the electrode 606 may function as an anode. Such a phenomenon is indicated by a voltage drop 608. The voltage drop may be due to ohmic resistance, where V=IR. While the resistance R of the membrane layer(s) may be constant based on the design, the voltage drop varies with the applied current I. Because intercalation (lithiation) of lithium ions into graphite occurs at a reduction potential much lower than that of water, a voltage drop may be necessary to prevent the current from reducing water, which would significantly reduce the efficiency of the design. Because the difference in reduction potential between lithium metal and water is 2.21 V, in one embodiment, the membrane may operate at a current I such that it experiences a voltage drop of at least 2.21 V to prevent the electrons from reducing water.

[0097] As illustrated later (in FIG. 7), individual sheets of graphene within carbon particles (either or both of the capacitor-like carbon-based film and the graphitic carbon film of the graphitic carbon multilayer film) can be covalently bonded to one another (as opposed to van der Waals forces). This covalent bonding can significantly increase the amount of energy required to separate the lattices (e.g., covalent bonds cannot tolerate strain). Therefore, sizing the distance between graphene sheets can be tailored to the specific size of ions to be passed through the film.

[0098] In operation, the graphitic carbon particles of the graphitic carbon multilayer film (within either or both of the capacitor-like carbon-based film and the graphitic carbon film) can extract ions from the feed solution 602 by electrochemical intercalation / adsorption. Because electrochemical intercalation of Li requires the lowest strain (10% by volume) of all ions that may be found in the feed solution 602, the selectivity for Li is highest. Furthermore, because other ions would require a significant amount of strain to intercalate, the selectivity for Li over other ions is even further enhanced by increasing the degree of covalent C-C bonding between adjacent sheets of graphene. In this way, the selectivity for Li over other ions (Li) is even greater. +ions, such as Li, can be effectively dropped when passing through the graphitic carbon film of the capacitor-like film and graphitic carbon multilayer film. + As the selected ions (e.g., ions) pass through the membrane 604, they may also experience an effective voltage drop.

[0099] In one embodiment, the carbon particles included in the capacitor-like carbon-based film of the graphitic carbon multilayer film may serve multiple purposes. For example, the carbon particles may act as an electrical buffer between the graphitic carbon film and the feed solution 602 (which is likely an aqueous solution). Additionally, the carbon particles may extract ions from the feed solution 602 and transport such ions to the graphitic carbon film of the graphitic carbon multilayer film.

[0100] Furthermore, an electrochemical buffering effect can be achieved by the hydrophobicity of the material (e.g., carbon) of the capacitor-like carbon-based membrane and by a large electrochemical voltage drop across the capacitor-like carbon-based membrane. Such a voltage drop 608 can prevent water reduction at the interface between the feed solution 602 and the graphitic carbon multilayer capacitor-like carbon-based membrane. This voltage drop is achieved by adjusting the membrane thickness and resistivity as defined by Ohm's law (V=IR, where R=(resistivity)×(thickness / area)).

[0101] Therefore, alkali metal ions can be extracted by electrochemical and capacitive adsorption of the ions on the surface of the carbon particles. By adjusting the porosity and surface area of ​​the carbon particles, the kinetics of ion transport can be tuned. While all ions can be adsorbed on the carbon particles, lighter ions and monovalent ions (e.g., alkali metal ions) can migrate much more rapidly through the membrane 604 (to the electrode 606).

[0102] In various embodiments, the design of membrane 604 can be modified so that alkali ions (e.g., lithium) do not fully reduce to their metallic state (e.g., metallic Li) and / or plate out on the surface of electrode 606.

[0103] In one embodiment, reduction of alkali ions to the metallic stage can be limited by making the graphitic carbon film substantially larger (in terms of film thickness) so that the extracted alkali metal (such as lithium) can be fully contained within (and subsequently removed from) the graphitic carbon film.

[0104] Similarly, the use of membrane 604 may allow for the recovery of the electrical energy used to drive this reaction, reducing the net energy requirements and therefore material costs. In other words, the energy used to drive the transfer of the alkali metal (from the feed solution) to the electrode may then be stored in the form of electrochemical energy that can be released at a later time.

[0105] 7 illustrates a close-up view 700 of graphitic carbon, according to one embodiment. Optionally, close-up view 700 may be implemented in conjunction with any of the before and / or after view(s) and / or any one or more of the embodiments described in the description. However, it should be understood that close-up view 700 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0106] As shown, the graphitic carbon close-up 700 includes graphitic carbon particles 702. Furthermore, such graphitic carbon particles 702 (collectively) may include individual graphene sheets 704, with covalent carbon-carbon bonds 706 connecting the individual graphene sheets 704 to one another.

[0107] In one embodiment, the graphitic carbon film 606 described above may be tailored such that the surface area (of the graphitic carbon particles 702) is minimized and interfacial bonding (e.g., covalent C-C bonds between adjacent sheets of graphene within the lattice) may be maximized.

[0108] By reducing the surface area of ​​the graphitic carbon particles 702, the amount of ions that can be held on the surface of the carbon particles can be significantly reduced, minimizing the amount of undesirable ions that are extracted from the film.

[0109] 8 illustrates a process 800 for recovering energy from lithium extraction, according to one embodiment. Optionally, process 800 may be implemented in conjunction with any one or more of the embodiments described in any preceding and / or following figure(s) and / or their description. However, it should be understood that process 800 may be implemented in conjunction with any desired environment. Additionally, the foregoing definitions may equally apply to the following description.

[0110] As shown, step 802 depicts lithium present in the feed solution. Two membranes may interact with the feed solution: a first membrane as a lithium-selective membrane (consistent with the use of solid electrolyte 102 embedded in matrix 104 as disclosed herein) and a second membrane as a sodium-selective membrane. In one embodiment, the sodium-selective membrane may be embedded in a matrix (like the first membrane) but may use a solid electrolyte tuned for a specific ion (such as sodium). The first membrane may interact with an electrode, and the second membrane may interact with a second electrode (i.e., separate electrodes for lithium ions and sodium ions, respectively). While lithium and sodium are used in the context of process 800, it should be understood that, as disclosed above, the solid electrolyte may be tuned for the separation of any specific ion. Furthermore, although sodium is illustrated, any ion (or ions to be extracted) less reducing than lithium may be used.

[0111] In step 804, a voltage is applied to the process 800, which then allows lithium ions to migrate from the feed solution through the lithium-selective membrane to the lithium electrode. As lithium is removed from the feed solution, sodium ions may be depleted (migrated to the feed solution) from the sodium electrode. As lithium ions are stored in the lithium electrode, the energy input (to move the lithium ions to the lithium electrode) may be stored in the form of electrochemical energy.

[0112] In step 806, the feed solution may be changed to a new electrolyte (such as Na2CO3), and the lithium ions stored in the lithium electrode may migrate back to the new electrolyte (which may then form Li2CO3). The sodium ions that were in the new electrolyte may migrate from the new electrolyte to the sodium electrode (through the sodium-selective membrane).

[0113] Electrochemical energy (stored in the lithium electrode via the lithium ions) can be released with the transfer of lithium ions from the lithium electrode to a new feed solution (new electrolyte). In one embodiment, the energy released by the transfer can be stored via any conventional system (e.g., an external battery, etc.). Such released energy can then be used again to drive process 800 to extract ions, and after extraction, the energy can be recycled (to drive future extractions of lithium ions). In this way, once process 800 is initially established (to achieve the initial extraction), energy can be recycled and then used to drive future extractions / separations.

[0114] More specifically, the energy required for the extraction of lithium from the feed solution into the lithium electrode and for the expulsion of lithium from the lithium electrode into the new electrolyte (final solution) may depend on the current density, with higher current densities corresponding to energy dissipation due to ohmic resistance and the need for higher energy to overcome the difference in the reduction potentials of the electrodes used for the two electrodes (shown as the lithium electrode and the sodium electrode). If the active material for the lithium electrode has a lower reduction potential than the active material for the counter electrode (shown as the sodium electrode), an input of energy may be required to extract lithium ions from the feed solution (shown as sodium ions from the sodium electrode, again corresponding to the expulsion of a second ion from the counter electrode), which can be recovered during the later expulsion of lithium from the lithium electrode into the new electrolyte, which may correspond to the extraction of a second ion (shown as sodium) from the new electrolyte into the sodium electrode. If the active material for the lithium electrode has a higher reduction potential than the active material for the counter electrode (shown as the sodium electrode), an input of energy may be required to eject lithium ions from the feed solution (corresponding to the ejection of second ions from the counter electrode), which can then be recovered when lithium is extracted from the lithium electrode.

[0115] 9 illustrates a cell architecture 900, according to one embodiment. Optionally, cell architecture 900 may be implemented in conjunction with any one or more of the embodiments described in any preceding and / or following figure(s) and / or the description thereof. However, it should be understood that cell architecture 900 may be implemented in conjunction with any desired environment. Furthermore, the foregoing definitions may equally apply to the following description.

[0116] As shown, the cell architecture 900 may include a solid electrolyte membrane 902, which in turn may include solid electrolyte particles 904 embedded in a matrix 906. The solid electrolyte membrane 902 may be separated from an electrode 910 via a separator 908. The electrode 910 may include an electrolyte 912, binder(s) 914, active material particles 916, and a current collector 918. An adhesive 920 may entirely line (on both sides) the solid electrolyte membrane 902, separator 908, and electrode 910.

[0117] With respect to the electrode 910, the current collector 918 can function as an electronically conductive substrate to which the active material coating is bonded for transmitting electricity. Additionally, the current collector can be one of the following (but is not limited to): copper, aluminum, stainless steel, nickel, titanium, or graphene.

[0118] The active material particles 916 may be the location where the alkali metal ions and electrochemical energy are stored. Additionally, the active material particles 916 may act as a host for the extracted lithium ions and store the energy input for extraction in the form of electrochemical energy.

[0119] In various embodiments, suitable electrode materials for lithium electrodes include carbon-based materials (graphite, carbon nanotubes (CNT), graphene, carbon nano-onions (CNO), hard carbon), lithium titanium oxide (LTO), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium manganese phosphate, lithium cobalt phosphate, lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel manganese cobalt oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium titanium sulfate, lithium Lithium intercalation materials such as vanadium phosphate (LVP), lithium ferrous fluoride sulfate (LFPF), lithium conversion materials such as halides of the form MXx where M may be Fe, Co, Ni, Bi, Cu, Ag, and X may be F, Cl, Br, or I, lithium chalcogenides such as S, Se, Te, other non-metals from the group Si, Sn, Ge, Ga, Mg, Al, Zn, In, Au, Ag, Pt, iodine, or oxygen, or metals and metalloids that alloy with lithium such as lithium metal.

[0120] For sodium electrodes (or elements less reducible than the ions to be extracted), it may consist of an active material capable of hosting sodium ions (or any selected ions). In the case of Na or K, the active material may consist of Fe4[Fe(CN)6]3 (Prussian Blue), a Prussian Blue analogue in the form of M1x[M2y(CN)6]3, where M1 and M2 are metals from the group Fe, Ni, Cu, Mn, Co, Ti, Cr, Zn, or carbon-based materials (graphite, carbon nanotubes (CNT), graphene, carbon nano-onions (CNO), hard carbon). In the case of Na, the active material may also include a material that alloys with sodium, such as P or K, or sodium metal. In the case of K, the active material may also include a material that alloys with potassium, such as Na, or potassium metal.

[0121] In one embodiment, the active material particles 916 may also store ions via capacitive / pseudocapacitive mechanisms such as graphene, carbon nanotubes (CNTs), carbon nano-onions (CNOs), Mxene, metal oxides such as ZnO, TiO2, SnO2, RuO2, Co3O4, MnO2, NiO, NiCo2O4, Fe3O4, Fe2O3, and V2O5.

[0122] The binder 914 may adhere the active material particles 916 to the current collector 918 while providing cohesion between the active material particles and other additives. The binder 914 may include (but is not limited to) one or more of the following: poly(vinylidene fluoride) (PVDF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR).

[0123] The electrolyte 912 can function as a medium for transporting alkali metal ions between the active material (including the active material particles 916) and the solid electrolyte membrane 902. The electrolyte can contain one or more salts dissolved in a one or more component solvent system. The salts can include one or more of the following cations: H, Li, Na, K, and Cs, and one or more of the following anions: Cl, Br, I, NO, SO, PO, PF, TFSI, FSI, OTf, and ClO. The solvent can be one or more of the following: water, dimethoxyethane (DME), dioxolane (DOL), tetrahydrofuran (THF), dimethyl carbonate (DMC), propylene carbonate (PC), ethylene carbonate (EC), ethyl methyl carbonate (EC), and ethyl methyl carbonate (EMC).

[0124] Furthermore, separator 908 may optionally function as a reservoir for electrolyte 912 and as an electronic insulating barrier between the active material (such as active material particles 916 ) and solid electrolyte membrane 902 .

[0125] Adhesive 920 may surround the edges of electrode 910 and may act as an impermeable barrier between the inside and outside of electrode 910. The adhesive may consist of (but is not limited to) an epoxy, polyurethane, polyimide, cyanoacrylate, or acrylic adhesive cured by thermal or UV curing.

[0126] Furthermore, a second electrolyte (including a liquid) may be used within electrode 910. The edges of electrode 910 may be protected (edge ​​sealant, glue sealant, etc.) to prevent feed solution from reaching the active material compartments (such as active material particles 916) through these exposed areas.

[0127] It should be understood that the arrangements of components shown in the described figures are exemplary and that other arrangements are possible, and that the various system components (and means) defined by the claims, described below, and illustrated in the various block diagrams represent logical components in some systems configured in accordance with the subject matter disclosed herein.

[0128] For example, one or more of these system components (and means) may be realized in whole or in part by at least some of the components shown in the arrangements illustrated in the described figures. Moreover, some or all of these other components may be combined, some may be omitted entirely, and additional components may be added while still achieving the functionality described herein. Thus, the subject matter described herein may be embodied in many different variations, and all such variations are contemplated to be within the scope of what is claimed.

[0129] In the description above, the subject matter is described with reference to acts and symbolic representations of operations that are performed by one or more devices, unless indicated otherwise.

[0130] The use of the terms "a," "an," and "the" and similar referents in the context of describing the subject matter (particularly in the context of the claims below) should be construed to include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. Furthermore, the foregoing description is for illustrative purposes only and not for limiting purposes, as the scope of protection sought is defined by the claims set forth below and equivalents thereof where entitled. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better describe the subject matter, and does not limit the scope of the subject matter, unless otherwise claimed. In both the claims and the specification, the use of the term "based on" and other similar phrases indicating a condition for producing a result is not intended to exclude other conditions for producing that result. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the claimed invention.

[0131] The embodiments described herein include one or more modes known to the inventors for carrying out the claimed subject matter. Of course, variations on those embodiments will be apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors anticipate that those of ordinary skill in the art will employ such variations as appropriate, and the inventors intend for the claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, this claimed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

1. 1. A method for recycling energy, comprising: transporting lithium ions from a feed solution to a first electrode through a first membrane comprising a first solid electrolyte embedded in a first matrix, wherein the transport of the lithium ions from the feed solution to the first electrode requires an input of energy; transporting second ions from a second electrode to the feed solution through a second membrane comprising a second solid electrolyte embedded in a second matrix, wherein the transport of the second ions from the second electrode to the feed solution occurs simultaneously with the transport of the lithium ions from the feed solution to the first electrode; transporting the lithium ions from the first electrode to an electrolyte solution through the first membrane, wherein the transport of the lithium ions from the first electrode to the electrolyte solution recovers at least a portion of the energy input; and The method comprising:

2. 10. The method of claim 1, wherein the energy input is stored as electrochemical energy of the lithium ions stored in the first electrode, and wherein recovering the at least a portion of the energy input reduces a carbon footprint of a manufacturing facility.

3. 10. The method of claim 1, wherein the feed solution is based on at least one of lithium minerals, lithium-containing brine, recycled lithium batteries, or seawater.

4. 2. The method of claim 1, wherein the voltage drop is proportional to a thickness of at least one of the first film or the second film or to the ohmic resistance of at least one of the first film or the second film.

5. 10. The method of claim 1, wherein each of the lithium ions passes through a single particle of the first solid electrolyte of the first membrane.

6. the first membrane and the second membrane are each water-impermeable; the first membrane is ion-selective for the lithium ions; the second membrane is ion-selective to the second ion; the second ions include at least one of sodium, potassium, or hydrogen; The method of claim 1.

7. 2. The method of claim 1, wherein transporting the lithium ions from the first electrode into the electrolyte solution through the first solid electrolyte occurs simultaneously with uptake of the second ions from the electrolyte solution into the second electrode through the second solid electrolyte.

8. 10. The method of claim 1, wherein the first solid electrolyte is at least one of LATP, LZP, LAGP, LiSICON, or LTO, and the second solid electrolyte is at least one of NaSICON or KFeO.

9. 10. The method of claim 1, wherein the first membrane acts as an electrical buffer between the first electrode and at least one of the feed solution or the electrolyte solution, and the second membrane acts as an electrical buffer between the second electrode and at least one of the feed solution or the electrolyte solution.

10. the first solid electrolyte has a diameter of at least 10 μm (microns); the first matrix and the second matrix are made of the same material; or the first matrix and the second matrix are made of different materials; The method of claim 1 , wherein the at least one of

11. The method of claim 1 , wherein at least one of the first electrode or the second electrode comprises a second electrolyte, a binder, active material particles, and a current collector.

12. 12. The method of claim 11 , wherein the second electrolyte is a liquid and one or more sides of the first electrode and the second electrode are lined with an adhesive configured to prevent the feed solution containing the lithium ions from reaching the active material particles of either the first electrode or the second electrode.

13. The method of claim 1 , wherein the first solid electrolyte is configured to extract the lithium ions.

14. 10. The method of claim 1, wherein the feed solution is a separate input source from the first electrode.

15. 1. A system comprising: a first membrane including a first solid electrolyte embedded in a first matrix, the first membrane configured to transport lithium ions; a first electrode for storing the lithium ions that are first transported from a feed solution through the first membrane, the first transport requiring an input of energy; and a second membrane including a second solid electrolyte embedded in a second matrix, the second membrane configured to transport second ions, the second ions being different from the lithium ions; and a second electrode for storing the second ions; an electrolyte solution for storing the lithium ions that are transported from the first electrode through the first membrane to a second location, the second transport recovering at least a portion of the energy input; and The system comprising:

16. 16. The system of claim 15, wherein the energy input is stored as electrochemical energy of the lithium ions stored in the first electrode, and the recovered at least a portion of the energy input reduces a carbon footprint of a manufacturing facility.

17. 16. The system of claim 15, wherein the feed solution is based on at least one of lithium minerals, lithium-containing brine, recycled lithium batteries, or seawater.

18. The system of claim 15 , wherein the voltage drop is proportional to a thickness of at least one of the first film or the second film.

19. 16. The system of claim 15, wherein the system is configured such that each of the lithium ions passes through a single particle of the first solid electrolyte of the first membrane.

20. the first membrane and the second membrane are each water-impermeable; the first membrane is ion-selective for the lithium ions; the second membrane is ion-selective to the second ion; the second ions include at least one of sodium, potassium, or hydrogen; 16. The system of claim 15.

21. The system comprises: the first transport of lithium ions from the feed solution into the first electrode through the first solid electrolyte occurs simultaneously with the export of second ions from the second electrode into the feed solution through the second solid electrolyte; The second transport of lithium ions from the first electrode through the first solid electrolyte into the electrolyte solution occurs simultaneously with the uptake of second ions from the electrolyte solution into the second electrode through the second solid electrolyte. The system of claim 15 configured to:

22. 16. The system of claim 15, wherein the first solid electrolyte is at least one of LATP, LZP, LAGP, LiSICON, or LTO, and the second solid electrolyte is at least one of NaSICON or K2Fe4O7.

23. 16. The system of claim 15, wherein the system is configured such that the first membrane acts as an electrical buffer between the first electrode and at least one of the feed solution or the electrolyte solution, and the second membrane acts as an electrical buffer between the second electrode and at least one of the feed solution or the electrolyte solution.

24. the first solid electrolyte has a diameter of at least 10 μm (microns); the first matrix and the second matrix are made of the same material; or the first matrix and the second matrix are made of different materials; 16. The system of claim 15, wherein at least one of

25. 16. The system of claim 15, wherein at least one of the first electrode or the second electrode comprises a second electrolyte, a binder, active material particles, and a current collector.

26. 16. The system of claim 15, wherein the second electrolyte is a liquid and one or more sides of the first electrode and the second electrode are lined with an adhesive configured to prevent the feed solution containing the lithium ions from reaching the active material particles of either the first electrode or the second electrode.

27. 16. The system of claim 15, wherein the first solid electrolyte is configured to extract the lithium ions.

28. 16. The system of claim 15, wherein the feed solution is a separate input source from the first electrode.

29. A product, a membrane including a layer including a solid electrolyte embedded within a matrix; the solid electrolyte is configured to extract ions of an alkali metal and is ion-selective for the alkali metal; the layer is water impermeable; The above product.

30. 30. The article of manufacture of claim 29, wherein the alkali metal is lithium.

31. 30. The article of manufacture of claim 29, wherein the alkali metal is at least one of lithium, sodium, or potassium.

32. 30. The article of manufacture of claim 29, wherein the solid electrolyte is one of LATP, LZP, LAGP, LiSICON, LTO, K2Fe4O7, or NaSICON.

33. 30. The article of claim 29, wherein the layer is mechanically polished to expose the solid electrolyte.

34. 30. The product of claim 29, wherein the structure of the matrix is ​​densely crosslinked and hydrophobic.

35. 30. The product of claim 29, wherein the layer acts as an electrical buffer between the feed solution and the electrode.

36. 36. The article of manufacture of claim 35, wherein the layer is configured to extract the ions from the feed solution and transport the ions to the electrode.

37. 30. The article of claim 29, wherein the solid electrolyte has a diameter of at least 10 microns.

38. 30. The article of manufacture of claim 29, wherein a first side of the layer interacts with a feed solution and a second side of the layer interacts with an electrode.

39. 40. The article of manufacture of claim 38, wherein the extracted ions collect on at least one of the electrode, capacitor, pseudocapacitor active material, or conductive surface of the electrode.

40. 39. The article of manufacture of claim 38, wherein the layer is configured such that a voltage drop occurs between the first side and the second side.

41. The voltage drop is is proportional to the thickness of the layer, so as the thickness increases, the voltage drop increases, regulated by increasing the current I across the layer, 41. The article of manufacture of claim 40.

42. 41. The article of claim 40, wherein the voltage drop is a function of the thickness of the layer and the resistivity of the layer.

43. 30. The product of claim 29, wherein the layer interacts with a feed solution containing lithium ions.

44. 44. The product of claim 43, wherein the lithium ions are sourced from at least one of lithium minerals, lithium-containing brine, recycled lithium batteries, or seawater.

45. 30. The article of manufacture of claim 29, wherein said extraction of ions causes a voltage drop.

46. 30. The article of claim 29, wherein the molecules of the matrix are covalently bonded to particles of the solid electrolyte.

47. 30. The article of claim 29, wherein the layer is used as at least one of a polysulfide barrier or an air barrier.

48. 30. The article of claim 29, wherein the ions of the alkali metal pass through a single particle of the solid electrolyte of the layer.

49. 30. The article of claim 29, wherein at least one side of the layer interacts with an electrode, the electrode comprising a second electrolyte, a binder, active material particles, and a current collector.

50. 50. The article of manufacture of claim 49, wherein the second electrolyte is a liquid and one or more sides of the electrode are lined with an adhesive configured to prevent a feed solution containing the ions of the alkali metal from reaching the active material particles of the electrode.

51. 30. The article of claim 29, wherein the ions of the alkali metal pass through a single particle of the solid electrolyte of the layer.

52. 36. The product of claim 35, wherein the feed solution is seawater.

53. 36. The article of manufacture of claim 35, wherein the feed solution is a previously used, exhausted battery.

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