Patent Application
20220093958
The present disclosure relates to rechargeable batteries, and ion-conducting membranes used in these batteries. Certain rechargeable batteries utilize the intercalation of positive and negative electrodes to store ions. The ions shuttle between the electrodes during charge and discharge cycles of the battery. The ion movement between the electrodes may be facilitated with a liquid-based electrolyte. Additionally, replacing the intercalating negative electrode (e.g., graphite and hard carbon) with a metallic electrode (e.g., lithium and sodium) may be advantageous because the specific capacity of the metal electrodes is higher than the intercalating counterpart. This may allow for a reduction in the volume of the negative electrode because the energy delivered per unit volume (i.e., the energy density) is higher than the intercalating electrode. Consequently, there may not be a need to use additives like conductive carbon or a binder.
Embodiments of the present disclosure relate to method of manufacturing ion-conducting membranes. A method includes applying a layer of ion-conducting inorganic particles on an adhesive flexible substrate comprising a crosslinked siloxane polymer. The method also includes employing a physical pressing operation that embeds at least some of the particles into the adhesive substrate. The method also includes coating an electrically insulating polymer over the substrate, thereby forming a composite film that includes the insulating polymer and the particles. The method also includes peeling off the composite film from the adhesive flexible substrate. The method also includes removing a portion of the insulating polymer, thereby exposing particles in the composite film.
Other embodiments of the present disclosure relate to methods of manufacturing rechargeable batteries that include ion-conducting membranes. The method includes providing an anode, providing a cathode, and providing an ion-conducting film between the anode and the cathode. The ion-conducting film is formed by a method including applying a layer of ion-conducting inorganic particles on an adhesive flexible substrate comprising a crosslinked siloxane polymer. The method also includes employing a physical pressing operation that embeds at least some of the particles into the adhesive substrate. The method also includes coating an electrically insulating polymer over the substrate, thereby forming a composite film that includes the insulating polymer and the particles. The method also includes peeling off the composite film from the adhesive flexible substrate. The method also includes removing a portion of the insulating polymer, thereby exposing particles in the composite film.
The above summary is not intended to describe each illustrated embodiment or every implementation of the present disclosure.
The drawings included in the present application are incorporated into, and form part of, the specification. They illustrate embodiments of the present disclosure and, along with the description, explain the principles of the disclosure. The drawings are only illustrative of certain embodiments and do not limit the disclosure.
It should be appreciated that elements in the figures are illustrated for simplicity and clarity. Well-understood elements that may be useful or necessary in a commercially feasible embodiment may not be shown for the sake of simplicity and to aid in the understanding of the illustrated embodiments.
The present disclosure describes a composite ion-conducting membrane for batteries, and a method of preparing the composite ion-conducting membrane.
Various embodiments of the present disclosure are described herein with reference to the related drawings. Alternative embodiments can be devised without departing from the scope of the present disclosure. It is noted that various connections and positional relationships (e.g., over, below, adjacent, etc.) are set forth between elements in the following description and in the drawings. These connections and/or positional relationships, unless specified otherwise, can be direct or indirect, and the present disclosure is not intended to be limiting in this respect. Accordingly, a coupling of entities can refer to either a direct or an indirect coupling, and a positional relationship between entities can be a direct or indirect positional relationship. As an example of an indirect positional relationship, references in the present description to forming layer “A” over layer “B” include situations in which one or more intermediate layers (e.g., layer “C”) is between layer “A” and layer “B” as long as the relevant characteristics and functionalities of layer “A” and layer “B” are not substantially changed by the intermediate layer(s).
The following definitions and abbreviations are to be used for the interpretation of the claims and the specification. As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains” or “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, a mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.
For purposes of the description hereinafter, the terms “upper,” “lower,” “right,” “left,” “vertical,” “horizontal,” “top,” “bottom,” and derivatives thereof shall relate to the described structures and methods, as oriented in the drawing figures. The terms “overlying,” “atop,” “on top,” “positioned on” or “positioned atop” mean that a first element, such as a first structure, is present on a second element, such as a second structure, wherein intervening elements such as an interface structure can be present between the first element and the second element. The term “direct contact” means that a first element, such as a first structure, and a second element, such as a second structure, are connected without any intermediary conducting, insulating or semiconductor layers at the interface of the two elements. It should be noted, the term “selective to,” such as, for example, “a first element selective to a second element,” means that a first element can be etched, and the second element can act as an etch stop.
The use of liquid-based electrolytes in the metallic anode system may promote the formation of needle-like crystals known as dendrites, which may lead to short-circuiting the battery. To suppress dendrite growth on the metallic anode surface, it may be desirable to develop a membrane/separator that has desirable mechanical strength with good ionic conductivity (e.g., higher than 10−5 S/cm or higher than 10−5 S/cm).
One example configuration of an ion-conducting membrane is shown in
One example method of manufacturing an ion-conducting membrane is described in the flow chart of
In operation 204, the particles are spread over the adhesive layer to form a single layer. The particles may be spread to form a regular or irregular array and may form a single layer over all or a portion of the adhesive layer. The particles are arranged in a single layer so that ions may conduct freely therethrough without encountering resistance at interfaces between overlying particles. The ion-conducting particles may optionally be sieved prior to application to the adhesive layer to ensure that the particles are more uniform in size and/or shape.
Additionally, during the tape manufacturing process, the tape may shrink while maintaining an elevated temperature. This shrinkage may disrupt the insulating polymer by displacing the ceramic particles and may result in curling of the membrane. Therefore, in certain examples, in operation 206 (i.e., before spraying an insulating polymer), the tape along with the single-layer ceramic is subjected to an elevated temperature to rearrange the particle before applying an insulating polymer.
In operation 208, the ion-conducting membrane is sprayed with an insulating polymer matrix. The matrix polymer layer may be applied by a wide variety of deposition techniques including, but not limited to, spinning, vapor phase deposition, dip coating, spraying and the like. Following and/or during application, the matrix polymer layer may optionally be further processed to improve its properties for use in subsequent process operations. For example, the matrix polymer may be heated or annealed to remove residual solvent and promote polymer flow, annealed in the presence of a plasticizing solvent in the vapor phase, exposed to radiation for hardening or crosslinking, and the like. For solution processing of the polymer, the polymer may be soluble in a casting solvent, or, if available as insoluble nanoparticles, they should preferably be dispersible in a solvent.
In operation 210, the membrane is released from the adhesive layer by dissolving the adhesive layer (e.g., the tape or PMGI layer) in an appropriate solvent. Example solvents may be ethanol or tetraethylammonium hydroxide for tape and PMGI processes, respectively. It should be appreciated that because the adhesive layer is completely dissolved that the adhesive layer cannot be reused.
The film that is exposed to solvents must undergo further thermal treatment under vacuum to remove the solvent used for removing the adhesive layer, as indicated in operation 212.
In operation 214, a certain portion of the insulating polymer matrix is removed. In certain examples, a portion of the matrix polymer layer is removed to expose a portion of at least some of the conducting particles, such that at least a portion of the particles protrude from the matrix polymer layer and have at least one surface that protrudes from a surface of the matrix polymer layer. The surface of each particle may be substantially free of the polymer making up the polymer layer. The portions of the matrix polymer layer can be removed by any suitable method, for example, soaking in aqueous or organic solvents, polishing, oxygen plasma etching, reactive ion etching, ion milling or any combination thereof. Ion milling may have a potential advantage of directional milling which may be useful for removing polymer from the tops of the particles in conformal coatings, while reducing the etch rate of the polymer making up the matrix polymer layer.
In the example method of manufacturing an ion-conducting membrane tape and PMGI discussed above with respect to
The present embodiments discussed below with respect to
The present embodiments describe a process to fabricate a single particle thick composite ion-conducting membrane that utilizes a reusable sticky substrate, and that does not require using a sacrificial adhesive coating (e.g., the 3M tape or PMGI layer described above). According to the present embodiments, the processing time may be significantly reduced, and the process can be easily scaled up to roll-to-roll manufacturing. The present embodiments utilize a reusable adhesive layer (e.g., a soft elastic substrate that is formed by a crosslinkable siloxane material consisting of simple elements such as silicon, carbon, and oxygen). In certain examples, the crosslinked siloxane polymer comprises a [—SiRR′O-] moiety, wherein R and R′ are each independently selected from the group consisting of a hydrogen, an alkyl, an aryl, an alkylhalide, an arylhalide, and combinations thereof. In other examples, the crosslinked siloxane polymer is PDMS. In certain embodiments, there is no solvent involved in the adhesive removal step (e.g., as in operation 210 of
An example method of manufacturing an ion-conducting membrane is described in the flow chart of
In operation 302, the ion-conducting particles are spread over the free-standing adhesive substrate. The particles may be spread over the free-standing adhesive layer to form a single layer. The particles may be spread to form a regular or irregular array and may form a single layer over all or a portion of the free-standing adhesive substrate. The ion-conducting particles may optionally be sieved prior to application to the adhesive layer to ensure that the particles are more uniform in size and/or shape. In various embodiments, the mean particle size is less than 100 microns, and a mean particle size of less than 80 microns, less than 60 microns, less than 40 microns, or less than 25 microns may also be suitable. In certain embodiments, particles with a mean particle size less than 20 microns may be used. Smaller particles sizes may lead to higher ionic conductance, but average particle sizes of less than 1 micron may induce particle agglomeration and require additional process to produce reliable membranes with single-layered particle distribution. An average thickness of the membrane is dictated by the largest particles, and the size distribution may be less than 10% of the mean, such that the smallest particles may protrude through the opposing surfaces. In certain examples, in operation 302, the ion-conducting particles adhere to and/or become partially embedded in the free-standing adhesive substrate. In certain embodiments, the ion-conducting inorganic particles are selected from the group consisting of a non-oxide inorganic material, a perovskite-type oxide, a garnet-type oxide, a Li3PO4 oxide, a NASICON-type material, a LISICON-type material, lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium aluminum tantalum titanium phosphate (LATTP), and combinations thereof. In certain embodiments, wherein the particles have an average size ranging from 1 to 100 μm.
In operation 304, an electrically insulating polymer matrix is sprayed over the particle array. In certain embodiments, the electrically insulating polymer is selected from the group consisting of an addition polymer, a ring opening metathesis polymer (ROMP), a hydrogenated cyclo-olefin polymer (COP), a cyclo-olefin copolymer (COC), and combinations thereof. The casting solvent for the insulating polymer is evaporated by thermal treatment and then the resulting single-particle thick ceramic-polymer membrane is physically separated from the adhesive soft substrate in operation 306. That is, in certain embodiments, after coating the electrically insulating polymer over the substrate, the method may comprise thermally evaporating volatile species from the electrically insulating polymer. Once the membrane is peeled off, the adhesive substrate is ready for another round of membrane fabrication. In other words, the same adhesive substrate can be used to repeat operations 302, 304 and 306 shown in
In certain embodiments, in operation 308, a certain portion of the insulating polymer matrix is removed. In certain examples, a portion of the matrix polymer layer is removed to expose a portion of at least some of the conducting particles, such that at least a portion of the particles protrude from the matrix polymer layer and have at least one surface that protrudes from a surface of the matrix polymer layer. The surface of each particle may be substantially free of the polymer making up the polymer layer. The portions of the matrix polymer layer can be removed by any suitable method, for example, soaking in aqueous or organic solvents, polishing, oxygen plasma etching, reactive ion etching, ion milling or any combination thereof. Ion milling may have a potential advantage of directional milling which may be useful for removing polymer from the tops of the particles in conformal coatings, while reducing the etch rate of the polymer making up the matrix polymer layer. In certain embodiments, the operation of removing a portion of the insulating polymer to expose particles in the composite film may be performed before the operation of peeling off the composite film from the adhesive flexible substrate.
In certain embodiments, a method of manufacturing a battery utilizing the ion-conducting membrane discussed above is provided. The method may include providing an anode, providing a cathode, and providing an ion-conducting film between the anode and the cathode. In certain embodiments, the anode comprises at least one selected from the group consisting of graphite, silicon, an alkali metal, and an alkaline earth metal. In certain embodiments, the cathode comprises at least one selected from the group consisting of a metal oxide intercalation host, a metal phosphate intercalation host, a metal silicate intercalation host, sulfur, oxygen, iodide, and iodine. In certain embodiments, the method of manufacturing the battery includes providing a liquid electrolyte to fill empty voids in the battery. In certain embodiments, the method of manufacturing the battery includes comprising providing an additional ion-conducting material in between the ion-conducting film and the anode, and in between the ion-conducting film and the cathode.
Referring now to
As shown in
As shown in
Referring to
In certain embodiments, the free-standing adhesive substrate 400 (e.g., PDMS) surface has enough stickiness for the ceramic particles to adhere to. In certain embodiments, the method of manufacturing the ion-conducting membrane may include, after one use of the PDMS substrate for a ceramic-polymer composite membrane, cleaning the surface of the free-standing adhesive substrate 400 with water to prepare for the next set of membranes. The effectiveness of the free-standing adhesive substrate 400 to hold the particles is demonstrated by a uniform and dense coating of the ion-conducting ceramic particles that are stuck on the surface even after reusing the same substrate, for example, ten times or more. Thus, the PDMS substrate in the present embodiments can be re-used multiple times and may obtain reliable ion-conducting membranes in every usage.
As opposed to other techniques of preparing composite electrolytes that involve physical mixing of ceramic particles with a polymer electrolyte to produce an ionically conductive polymer electrolyte, the present embodiments aim at preparing a membrane where ion conduction happens only through the ceramic particle in the membrane. Thus, it may be desirable to obtain a single layer of particles neatly arranged on the PDMS substrate. Therefore, embedding the ion-conducting particles into the free-standing adhesive substrate 400 is an effective to obtain the membrane. When a uniform layer of ceramic particles is deposited on the PDMS substrate, an insulating polymer is sprayed to obtain the single-particle thick membrane. In certain embodiments, this membrane is further treated with oxygen plasma etching to selectively remove part of the insulating polymer matrix that is struck on a top side (i.e., and air side) and a bottom side (i.e., a PDMS side) of the particles so that the membrane is still intact but the surface of the particles on the air side and PDMS side are exposed for ion conduction.
The final membrane having ceramic particles exposed at top and bottom for ion conduction connected by the insulating polymer matrix is shown in
The methods described in the present embodiments may be used to obtain composite membranes consisting of particles of different sizes. A single particle thick membrane prepared by the method of the present embodiments using a PDMS adhesive substrate with particles sizes ranging from 45 to 53 μm is shown in
The electrical properties of the produced single-particle thick ion-conducting membrane were evaluated using impedance spectroscopy measurements. The impedance spectroscopy measurements were performed using lithium electrodes and a standard lithium electrolyte (1 M LiPF6 in ethylene carbonate/dimethyl carbonate (EC/DMC)). The ionic conductivity of the membrane prepared using the present embodiments was measured at 1.0×10−4 S/cm at 25° C.
In one example, polydimethylsiloxane (PDMS) may be prepared as follows. A polymer kit may include a monomer and a curing agent, both liquids, in two separate containers. The monomer and the curing agent are physically mixed in a separate container in a ratio of 10:1. For example, 15 g of monomer is mixed with 1.5 g of curing agent. The mixture is treated for removing the air bubble under vacuum for 1 hour to obtain a clear liquid mixture. The mixture may be poured into a mold or coated over a hard substrate to obtain a soft adhesive film. The adhesive film is hardened by thermal curing at 75° C. for 1 hr. After the thermal treatment, the clear PDMS film can be easily separated from the hard mold to obtain a freestanding film that can be used as an adhesive substrate for ceramic-polymer composite membrane preparation.
The ion-conducting ceramic particles LICGC™ are obtained from Ohara corporation having an ionic conductivity of 1.0×10−4 S/cm. The chemical composition of LICGC™ ceramic particles belongs to the Li2O—Al2O3—SiO2—P2O5—TiO2 system. A single layer of the sieved ion-conducting particles ranging in size from, for example, 55 and 63 μm is spread evenly over the entire surface of the adhesive PDMS substrate by a simple agitation technique that involves creating vibrations. This operation is carried out until the entire film is covered with the ceramic particles. The ceramic particles may be partially embedded into the PDMS substrate by gently pressing them with a silicon rubber roller after covering the particles with a thin polytetrafluoroethylene (PTFE) film. After rolling, any excess, loosely bound particles are dusted out using an air blower. That is, after the pressing operation, in certain embodiments, the method may include blowing air over the adhesive substrate to remove any loose particles. Electronically and ionically insulating polymer matrix may then be coated over the single-layered ceramic particles. In one example, a cyclic olefin copolymer was used, ZEONOR 1430R from Zeon Corporation as the insulating polymer matrix as it shows a high modulus, low moisture absorption rate, and good thermal stability. For example, 1.5 g of ZEONOR 1430R is dissolved in 15.2 g of Decalin to obtain a 9% solution and sprayed over the ceramic particles. The ZEONOR solution is sprayed using the compressed gas at 30 psi. The distance between the spray nozzle and the target is maintained at 5 cm. One cycle of a coat consists of spraying along the horizontal as well as vertical direction of the target area. The directional shift is required for the uniform application of the polymer coat. A 30 second wait period is maintained between coats for the polymer to reach the entire circumference of the ceramic particle and to settle down. To reach the ideal thickness of the polymer coating to firmly hold ceramic particles, multiple coatings can be performed (total of six spray coatings has been employed for the particles sized 55-63 μm). After the spray coating, the ceramic particles are covered with a solution of ZEONOR. The solvent in the ZEONOR solution is thermally evaporated under the fume hood at 75° C. for 1 hr. The resulting membrane thus has a single layer of ceramic particles interlinked by the insulating polymer matrix. The membrane is physically peeled off from the PDMS adhesive substrate. Peeling off a membrane with particle interconnected by polymer is one of the features of the present embodiments.
The membrane is further treated by oxygen plasma to etch away the insulating polymer (called as polymer overburden) on both top (air side) and bottom (PDMS substrate side) of the ceramic particles. Although the polymer overburden is mostly on the air side, some etching might be needed for the PDMS side. The extent of etching depends on the amount of insulating polymer present. The etching should be precisely controlled for leaving enough insulating polymer to hold the particles laterally. In certain examples, an etch time of 6-10 minutes on the air side and a shorter time of about 1-2 minutes on the PDMS side may be employed, although the removal rate depends on the etching conditions. As mentioned above,
The ionic conductivity of the membrane was measured by electrochemical impedance spectroscopy (EIS). Several small signal (V=10 mV) AC impedance measurements were performed on a VMP3 impedance analyzer available from BioLogic Science Instruments, Seyssinet-Pariset, France, using sinusoidal AC waveforms. The frequency of the sinusoidal AC waveforms ranged from about 100 mHz to about 1 MHz. For EIS measurement, the membrane was placed in between two lithium electrodes. To avoid any side reaction of the metallic lithium electrode with the ceramic particles in the membrane, a polymer separator CELGARD 2325 soaked in 1M LiPF6 EC/DMC (1/1 by volume) was placed as a support layer in between the membrane and the lithium electrode. The ionic conductivity of the membrane calculated from the EIS spectra is 1.0×10−4 S/cm at 25° C. that matches well with the industrial specification provided by Ohara Corporation for the particles.
The LICGC™ from Ohara corporation were sieved to obtain particles having sizes ranging from 45 and 53 μm. The single-particle thick membrane was prepared by following the procedure described in Example 2. To reach a desired thickness of the polymer coating to firmly hold ceramic particles, multiple coatings may be performed (a total of six spray coatings were employed for the particles sized 45-53 μm). The resulting membrane is shown in
The LICGC™ from Ohara corporation were sieved to obtain particles size ranging from 32 and 38 μm. The single-particle thick membrane is prepared by following the procedure described in Example 2. To reach the ideal thickness of the polymer coating to firmly hold ceramic particles, multiple coatings can be performed (total of four spray coatings were employed for the particles sized 32-38 μm). The resulting membrane is shown in
The LICGC™ from Ohara corporation were sieved to obtain particles size ranging from 25 and 32 μm. The single-particle thick membrane is prepared by following the procedure described in Example 2. To reach the ideal thickness of the polymer coating to firmly hold ceramic particles, multiple coatings can be performed (total of four spray coatings were employed for the particles sized 25-32 μm). The resulting membrane is shown in
The descriptions of the various embodiments have been presented for purposes of illustration and are not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
