Lithium ion exchange zeolite particles for electrochemical cells and methods of making the same

Abstract

Lithium ion-exchanged zeolite particles and methods of making such lithium ion-exchanged zeolite particles are provided herein. The methods include combining precursor zeolite particles with (NH4)3PO4to form a first mixture of intermediate zeolite particles comprising NH4 + cations. The methods further include adding a lithium salt to the first mixture to form the lithium ion-exchanged zeolite particles, or separating the intermediate zeolite particles from the first mixture and combining the intermediate zeolite particles with the lithium salt to form the lithium ion-exchanged zeolite particles.

Description

Technical Field

[0001] This invention relates to lithium-ion exchange zeolite particles for use in electrochemical batteries and a method for manufacturing the same. Background Technology

[0002] This section provides background information relating to this disclosure, which is not necessarily prior art.

[0003] Electrochemical batteries, such as battery packs, are devices that convert chemical energy into electrical energy through electrochemical reduction-oxidation (redox) reactions. In secondary or rechargeable battery packs, these electrochemical reactions are reversible, allowing the battery pack to undergo multiple charge and discharge cycles.

[0004] High-energy-density electrochemical batteries, such as lithium-ion battery packs, are used in a variety of consumer products and vehicles, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs). Typical lithium-ion, lithium-sulfur, and lithium-metal battery packs include a first electrode, a second electrode, an electrolyte material, and a separator. One electrode acts as the positive electrode or cathode, and the other as the negative electrode or anode. The battery pack cells can be electrically connected in a stack to increase the total output. Conventional rechargeable lithium-ion battery packs operate by reversibly transferring lithium ions back and forth between the negative and positive electrodes. A separator and electrolyte are positioned between the negative and positive electrodes. The electrolyte is adapted to conduct lithium ions and can be in solid (e.g., solid-state diffusion) or liquid form. Each of the negative and positive electrodes is typically carried on or connected to a metal current collector, for example, in the form of a thin layer of electrode material. The current collectors can be interconnected via a disruptive external circuit, through which electrons can be transferred from one electrode to the other during charging and discharging of the battery pack, while lithium ions migrate in the opposite direction through the electrochemical cell.

[0005] Lithium-ion battery packs can reversibly supply power to associated load devices as needed. More specifically, the lithium-ion battery pack can supply power to the load device until the lithium content of the negative electrode is effectively depleted. The battery pack can then be recharged by transferring a suitable direct current in the opposite direction between the electrodes.

[0006] During discharge, the negative electrode may contain a relatively high concentration of intercalated lithium, which is oxidized into lithium ions and electrons. Lithium ions, for example, move from the negative electrode (anode) to the positive electrode (cathode) through the ion-conducting electrolyte solution contained within the pores of the intermediate porous separator. Simultaneously, electrons are transferred from the negative electrode to the positive electrode via an external circuit. Lithium ions can be assimilated into the material of the positive electrode through an electrochemical reduction reaction. After partial or complete discharge of its usable capacity, the battery pack can be recharged by an external power source that reverses the electrochemical reactions that occurred during discharge.

[0007] During recharging, the lithium intercalated in the positive electrode is oxidized into lithium ions and electrons. Lithium ions move from the positive electrode to the negative electrode via the electrolyte through the porous separator, while electrons are transferred to the negative electrode via an external circuit. The lithium cations are reduced to elemental lithium at the negative electrode and stored in the negative electrode material for reuse.

[0008] For example, lithium-ion exchange zeolite particles present in coatings on porous separators can effectively remove trace amounts of water, hydrogen ions, hydrofluoric acid, and dissociated transition metal ions (e.g., Mn) from liquid electrolytes. 2+ and Fe2 + / 3+ Lithium-ion exchange zeolite particles can be used to remove lithium ions, polysulfides, and other target compounds without inhibiting the transport or net flow of lithium ions through them. Removing these target compounds from the liquid electrolyte during battery pack operation can help prevent or mitigate degradation of various battery pack components, thereby improving battery pack life and cycle performance. However, producing such lithium-ion exchange zeolite particles can be challenging, particularly in achieving the exchange between lithium ions with large hydration radii and cations with smaller hydration radii, such as sodium and potassium cations. Therefore, further methods for ion-exchange zeolite particles are needed. Summary of the Invention

[0009] This section provides a general overview of this disclosure and is not a full disclosure of its complete scope or all its features.

[0010] This disclosure relates to a method for preparing lithium-ion exchange zeolite particles. The method includes combining precursor zeolite particles with (NH4)3PO4 to form a first mixture comprising intermediate zeolite particles. The precursor zeolite particles contain components selected from H... + NH4 + Na + K + Mg 2+ Ca + The method may further include adding a lithium salt to a first mixture to form lithium-ion exchanged zeolite particles. Alternatively, the method may include separating intermediate zeolite particles from the first mixture and combining the intermediate zeolite particles with a lithium salt to form lithium-ion exchanged zeolite particles. The lithium-ion exchanged zeolite particles include Li... + and NH4 + cation.

[0011] The lithium-ion exchange zeolite particles comprise cages defined by 8-membered, 9-membered, 10-membered, 12-membered rings, or combinations thereof. The cages may contain Li3PO4.

[0012] The lithium-ion exchange zeolite particles may further include Li3PO4 present on the outer surface of the lithium-ion exchange zeolite particles.

[0013] The lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, or combinations thereof. For example, the zeolite material may be selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

[0014] Precursor zeolite particles may include Na + H + and / or K + Cation and / or intermediate zeolite particles may include NH4 + cation.

[0015] The lithium salt can be selected from lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, lithium sulfate, and combinations thereof.

[0016] In the method, the combination of precursor zeolite particles with (NH4)3PO4, the addition of LiOH to a first mixture to form lithium-ion exchange zeolite particles, and the combination of intermediate zeolite particles with LiOH to form lithium-ion exchange zeolite particles can each be carried out at a temperature of about 18°C ​​to about 120°C.

[0017] The method may further include separating lithium-ion exchange zeolite particles; and / or heating the lithium-ion exchange zeolite particles, for example, at a temperature greater than or equal to about 100°C.

[0018] In other aspects, this disclosure relates to lithium-ion exchange zeolite particles. The lithium-ion exchange zeolite particles comprise cages defined by 8-membered, 9-membered, 10-membered, 12-membered rings, or combinations thereof. The cages comprise Li3PO4. The lithium-ion exchange zeolite particles may further comprise Li + and NH4 + cation.

[0019] The lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and combinations thereof. For example, the zeolite material may be selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

[0020] In still other aspects, the present disclosure relates to an electrochemical cell. The electrochemical cell includes a positive electrode comprising a first electroactive material and a negative electrode spaced apart from the positive electrode, wherein the negative electrode comprises a second electroactive material. The electrochemical cell further includes a porous separator disposed between the opposing surfaces of the negative electrode and the positive electrode, and a liquid electrolyte that wets one or more of the negative electrode, the positive electrode, and the porous separator. The electrochemical cell further includes lithium ion-exchanged zeolite particles comprising cages defined by an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or a combination thereof. The cages include Li₃PO₄. The lithium ion-exchanged zeolite particles may further comprise Li + and NH₄ + cations.

[0021] The lithium ion-exchanged zeolite particles may be present as one or more of the following: (i) a first coating present on the first side, the second side, or both the first and second sides of the porous separator, (ii) a filler in the porous separator; (iii) an additive in the positive electrode, the negative electrode, or both; and (iv) a second coating present on the third side of the negative electrode, the fourth side of the positive electrode, or both the third side of the negative electrode and the fourth side of the positive electrode.

[0022] The lithium ion-exchanged zeolite particles comprise a zeolitic material having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and combinations thereof. For example, the zeolitic material may be selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

[0023] The first electroactive material may be selected from Li (1+x) Mn₂O₄, where 0.1 ≤ x ≤ 1; LiMn (2-x) Ni x O₄, where 0 ≤x ≤ 0.5; LiCoO₂; Li(Ni x Mn y Co z )O₂, where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, and x + y + z = 1; LiNi (1-x-y) Co x M y O₂, where 0<x<0.2, y<0.2, and M is Al, Mg or Ti; LiFePO₄, LiMn 2-x Fe x PO₄, where 0 < x < 0.3; LiNiCoAlO₂; LiMPO₄, where M is at least one of Fe, Ni, Co and Mn; Li(Ni x Mny Co z Al p )O2, where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, 0 ≤ P ≤ 1, x + y + z+p = 1 (NCMA); LiNiMnCoO2; Li2Fe x M 1-x PO4, where M is Mn and / or Ni, 0 ≤ x ≤ 1; LiMn2O4; LiFeSiO4; LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC622), LiMnO2 (LMO), activated carbon, sulfur and combinations thereof.

[0024] The second electroactive material includes lithium, lithium-silicon alloy, lithium-aluminum alloy, lithium-indium alloy, lithium-tin alloy, graphite, activated carbon, carbon black, hard carbon, soft carbon, graphene, silicon, tin oxide, aluminum, indium, zinc, germanium, silicon oxide, titanium oxide, lithium titanate, or combinations thereof.

[0025] Porous insulating materials include composite materials, polymer materials, nonwoven materials, or combinations thereof.

[0026] The present invention discloses the following technical solutions: 1. A method for preparing lithium-ion exchange zeolite particles, the method comprising: (a) Combining precursor zeolite particles with (NH4)3PO4 to form a first mixture comprising intermediate zeolite particles, wherein the precursor zeolite particles comprise a group selected from H + NH4 + Na + K + Mg 2+ Ca + and cations in combination thereof; and (b) Perform one of the following: (i) Adding a lithium salt to the first mixture to form the lithium-ion exchange zeolite particles, or (ii) separating the intermediate zeolite particles from the first mixture and combining the intermediate zeolite particles with the lithium salt to form the lithium-ion exchange zeolite particles; and The lithium-ion exchange zeolite particles contained Li + and NH4 + cation.

[0027] 2. The method according to technical solution 1, wherein the lithium-ion exchange zeolite particles comprise cages defined by 8-membered rings, 9-membered rings, 10-membered rings, 12-membered rings or combinations thereof, and wherein the cages contain Li3PO4.

[0028] 3. The method according to technical solution 2, wherein the lithium ion exchange zeolite particles further comprise Li3PO4 present on the outer surface of the lithium ion exchange zeolite particles.

[0029] 4. The method according to technical solution 1, wherein the lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA and combinations thereof.

[0030] 5. The method according to technical solution 1, wherein the lithium-ion exchange zeolite particles comprise zeolite materials selected from zeolite A, zeolite Y, zeolite L, ZSM-5 and combinations thereof.

[0031] 6. The method according to technical solution 1, wherein the precursor zeolite particles contain Na + H + and / or K + The cations and / or the intermediate zeolite particles contain NH4 + cation.

[0032] 7. The method according to technical solution 1, wherein the lithium salt is selected from lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, lithium sulfate, and combinations thereof.

[0033] 8. The method according to technical solution 1, wherein the combination of the precursor zeolite particles with (NH4)3PO4, the addition of LiOH to the first mixture to form the lithium-ion exchange zeolite particles, and the combination of the intermediate zeolite particles with LiOH to form the lithium-ion exchange zeolite particles are each carried out at a temperature of about 18°C ​​to about 120°C.

[0034] 9. The method according to technical solution 1 further includes performing one or more of the following: (c) Separating the lithium-ion exchange zeolite particles; and (d) Heating the lithium-ion exchange zeolite particles.

[0035] 10. The method according to technical solution 9, wherein the heating is performed at a temperature greater than or equal to about 100°C.

[0036] 11. A lithium-ion exchange zeolite particle, comprising: A cage defined by an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or a combination thereof, wherein said cage comprises Li3PO4; and Li + and NH4 +cation.

[0037] 12. The lithium-ion exchange zeolite particles according to technical solution 11, wherein the lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA and combinations thereof.

[0038] 13. The lithium-ion exchange zeolite particles according to technical solution 11, wherein the lithium-ion exchange zeolite particles comprise zeolite materials selected from zeolite A, zeolite Y, zeolite L, ZSM-5 and combinations thereof.

[0039] 14. An electrochemical cell comprising: A positive electrode containing a first electroactive material; A negative electrode spaced apart from the positive electrode, wherein the negative electrode comprises a second electroactive material; A porous insulating member is disposed between the opposing surfaces of the negative electrode and the positive electrode; A liquid electrolyte wetting one or more of the negative electrode, the positive electrode, and the porous separator; and Lithium-ion exchanged zeolite particles, comprising: A cage defined by an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or a combination thereof, wherein the cage comprises Li3PO4; and Li + and NH4 + cation.

[0040] 15. The electrochemical battery according to technical solution 14, wherein the lithium-ion exchange zeolite particles are present as one or more of the following: (i) A first coating present on a first side, a second side, or both of the first and second sides of the porous spacer; (ii) The packing material in the porous separator; (iii) the additive in the positive electrode, the negative electrode, or both; and (iv) A second coating present on the third side of the negative electrode, the fourth side of the positive electrode, or both the third side of the negative electrode and the fourth side of the positive electrode.

[0041] 16. The electrochemical battery according to technical solution 14, wherein the lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA and combinations thereof.

[0042] 17. The electrochemical cell according to claim 14, wherein the lithium ion-exchanged zeolite particles comprise a zeolite material selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

[0043] 18. The electrochemical cell according to claim 14, wherein the first electroactive material is selected from Li (1+x) Mn₂O₄, where 0.1 ≤ x ≤ 1; LiMn (2-x) Ni x O₄, where 0 ≤ x ≤ 0.5; LiCoO₂; Li(Ni x Mn y Co z )O₂, where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, and x + y + z = 1; LiNi (1-x-y) Co x M y O₂, where 0<x<0.2, y<0.2, and M is Al, Mg or Ti; LiFePO₄, LiMn 2-x Fe x PO₄, where 0 < x < 0.3; LiNiCoAlO₂; LiMPO₄, where M is at least one of Fe, Ni, Co and Mn; Li(Ni x Mn y Co z Al p )O₂, where 0 ≤ x ≤ 1, 0 ≤y ≤ 1, 0 ≤ z ≤ 1, 0 ≤ P ≤ 1, x + y + z +p = 1 (NCMA); LiNiMnCoO₂; Li₂Fe x M 1-x PO₄, where M is Mn and / or Ni, 0 ≤ x ≤ 1; LiMn₂O₄; LiFeSiO₄; LiNi 0.6 Mn 0.2 Co 0.2 O₂ (NMC622), LiMnO₂ (LMO), activated carbon, sulfur, and combinations thereof.

[0044] 19. The electrochemical cell according to claim 14, wherein the second electroactive material comprises lithium, lithium-silicon alloy, lithium-aluminum alloy, lithium-indium alloy, lithium-tin alloy, graphite, activated carbon, carbon black, hard carbon, soft carbon, graphene, silicon, tin oxide, aluminum, indium, zinc, germanium, silicon oxide, titanium oxide, lithium titanate, or a combination thereof.

[0045] 20. The electrochemical battery according to technical solution 14, wherein the porous separator comprises a composite material, a polymer material, a nonwoven material, or a combination thereof.

[0046] Further applicable fields will become apparent from the description provided herein. The descriptions and specific examples in this invention are intended for illustrative purposes only and are not intended to limit the scope of this disclosure. Attached Figure Description

[0047] The accompanying drawings described herein are for illustrative purposes only for selected embodiments and not all possible implementations, and are not intended to limit the scope of this disclosure.

[0048] Figure 1A This is a diagram of an exemplary lithium-ion exchange zeolite particle according to the present disclosure; Figure 1B This is an illustration of an alternative exemplary lithium-ion exchange zeolite particle according to the present disclosure; Figure 2A A flowchart of an exemplary method for preparing lithium-ion exchange zeolite particles according to the present disclosure; Figure 2B A flowchart of an exemplary method for preparing lithium-ion exchanged zeolite particles according to this disclosure is provided. Figure 3 This is a schematic diagram of an exemplary electrochemical battery pack according to the present disclosure; Figure 4 This is a schematic diagram of another exemplary electrochemical battery pack according to this disclosure; Figure 5 This is a schematic diagram of another exemplary electrochemical battery pack according to this disclosure; Figure 6 This is an X-ray diffraction (XRD) pattern of lithium-ion exchange zeolite particles.

[0049] Several views are shown in the accompanying drawings, with corresponding reference numerals indicating the corresponding parts. Detailed Implementation

[0050] The provision of exemplary embodiments makes this disclosure complete and ensures that its scope is fully communicated to those skilled in the art. Numerous specific details, such as examples of specific compositions, components, apparatuses, and methods, are set forth to provide a full understanding of embodiments of this disclosure. It will be apparent to those skilled in the art that specific details are not required, exemplary embodiments may be presented in many different forms, and none of them should be construed as limiting the scope of this disclosure. In some exemplary embodiments, well-known methods, well-known apparatus structures, and well-known techniques are not described in detail.

[0051] The terminology used herein is for the purpose of describing particular exemplary embodiments only and is not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” are intended to include the plural forms as used herein. The terms “comprising,” “including,” “covering,” and “having” are concurrent and thus specify the presence of the stated features, elements, compositions, steps, integers, operations, and / or components, but do not exclude the presence or inclusion of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Although the open-ended term “comprising” should be understood as a non-limiting term used to describe and claim the various embodiments described herein, in some respects it may be understood alternatively to more restrictive and limiting terms such as “consisting of” or “substantially consisting of.” Thus, for any given embodiment recounting a composition, material, component, element, feature, integer, operation, and / or method step, this disclosure also specifically includes embodiments consisting of or substantially consisting of such recounted compositions, materials, components, elements, features, integers, operations, and / or method steps. In the case of “consisting of…”, the alternative embodiments exclude any additional compositions, materials, components, elements, features, integers, operating and / or method steps. In the case of “essentially composed of…”, any additional compositions, materials, components, elements, features, integers, operating and / or method steps that substantially affect the essential and novel characteristics are excluded from such embodiments. However, any compositions, materials, components, elements, features, integers, operating and / or method steps that do not substantially affect the essential and novel characteristics may be included in the embodiments.

[0052] Any methods, procedures, and operations described herein should not be construed as requiring them to be performed in a specific order as discussed or illustrated, unless explicitly stated otherwise. It should also be understood that additional or alternative steps may be used unless otherwise stated.

[0053] When a component, element, or layer is mentioned as being “on,” “engaged,” “connected,” or “coupled” to another component or layer, it may be directly engaged, connected, or coupled to the other component, element, or layer, or an intermediary element or layer may be present. Conversely, when an element is mentioned as being “directly on,” “directly engaged,” “directly connected,” or “directly coupled” to another component or layer, an intermediary element or layer may not be present. Other terms used to describe relationships between elements should be interpreted similarly (e.g., “between” versus “directly between,” “adjacent” versus “directly adjacent,” etc.). As used herein, the term “and / or” includes any and all combinations of one or more of the related enumerations.

[0054] Although the terms first, second, third, etc., may be used herein to describe various steps, elements, components, regions, layers, and / or sections, these steps, elements, components, regions, layers, and / or sections should not be limited by these terms unless otherwise stated. These terms may be used only to distinguish one step, element, component, region, layer, or section from another. Unless the context clearly indicates otherwise, terms such as “first,” “second,” and other numerical terms used herein do not imply order or sequence. Therefore, the first step, element, component, region, layer, or section discussed below may be referred to as the second step, element, component, region, layer, or section without departing from the teachings of the exemplary embodiments.

[0055] For ease of description, spatially or temporally relative terms such as “before,” “after,” “inner,” “outer,” “below,” “below,” “lower,” “above,” “upper,” etc., may be used herein to describe the relationship of one element or feature as shown in the accompanying drawings to other elements or features(s). In addition to the orientations shown in the accompanying drawings, spatially or temporally relative terms may be intended to cover different orientations of the apparatus or system during use or operation.

[0056] Throughout this disclosure, numerical values ​​represent approximate measurements or range limits to cover slight deviations from a given value and embodiments that substantially have the mentioned value as well as embodiments that precisely have the mentioned value. Except in the detailed description of the working examples provided at the end, all numerical values ​​of parameters (e.g., quantities or conditions) in this specification (including the appended claims) should be understood to be modified in all cases by the term “about,” regardless of whether “about” actually precedes the numerical value. “About” means that the numerical value allows for a certain degree of slight imprecision (approaching the exact value to a certain extent; substantially or reasonably approximating the value; almost). If the imprecision provided by “about” is not otherwise understood in this ordinary sense in the art, then “about” as used herein refers to at least a deviation that can be caused by ordinary methods of measuring and using such parameters. For example, “about” may include deviations of less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to 0.5%, and in some respects optionally less than or equal to 0.1%.

[0057] In addition, the disclosure of the range includes disclosure of all values ​​throughout the range and disclosure of further subdivisions of the range, including disclosure of the endpoints and subranges given by the range.

[0058] Exemplary embodiments will now be described more fully with reference to the accompanying drawings.

[0059] I. Lithium-ion exchanged zeolite particles and their manufacturing methods This document provides lithium-ion exchanged zeolite particles. These lithium-ion exchanged zeolite particles may comprise or consist essentially of particles of one or more natural or synthetic zeolite materials. As used herein, “zeolite” is defined as a synthetic or natural crystalline material having a porous framework structure constructed of tetrahedral atoms (e.g., silicon, aluminum, phosphorus) connected by bridging oxygen atoms. Zeolites may comprise a three-dimensional framework of AlO2 and SiO2 tetrahedral units and extra-framework cations. Each AlO2 unit introduces a negative charge into the framework, which is canceled out by the extra-framework cations. The extra-framework cations may be organic or inorganic in nature. As used herein, the term “lithium-ion exchanged zeolite particle” refers to a zeolite that has undergone ion exchange with lithium ions such that multiple lithium ions exist within the zeolite as free ions and / or as extra-framework ions.

[0060] In various aspects, lithium-ion exchanged zeolite particles can contain a three-dimensional framework of AlO2 and SiO2 tetrahedral units and an extra-framework lithium cation (Li). + The amount of extraframework lithium cations present in lithium-ion exchange zeolite particles can be at least partially determined by the Si:Al ratio of a particular zeolite material and the cation exchange capacity (CEC) of that zeolite material. In lithium-ion exchange zeolite particles, lithium cations (Li... + The cations that can constitute the framework of the zeolite particles are greater than or equal to about 90 atomic percent (at.%), greater than or equal to about 95 atomic percent, greater than or equal to 99 atomic percent, or about 100 atomic percent. In some embodiments, the zeolite may be in a dehydrated form.

[0061] The zeolite framework has cage-like or channel-like voids or pores between tetrahedra, defined by rings of interconnected oxygen (O), silicon (Si), phosphorus (P), and / or aluminum (Al) atoms. Zeolite particles may have an average pore size of less than or equal to about 1.5 nm, less than or equal to about 1 nm, less than or equal to about 0.75 nm, less than or equal to about 0.5 nm, less than or equal to about 0.25 nm, less than or equal to about 0.1 nm, or about 0.05 nm. Additionally or alternatively, zeolite particles may have an average pore size greater than or equal to about 0.1 nm to less than or equal to about 1.5 nm, greater than or equal to about 0.1 nm to less than or equal to about 1 nm, or greater than or equal to about 0.35 nm to less than or equal to about 0.7 nm. Zeolite materials having pore openings of the width or diameter described above may include zeolite materials having pore openings defined by 8-membered, 9-membered, 10-membered, and / or 12-membered rings.

[0062] Examples of known zeolite frameworks are given in the “Atlas of Zeolite Frameworks”, published under the name of the “Structure Commission of the International Zeolite Association”, 6th revision, Ch. Baerlocher, LB McCusker, DH Olson et al., Elsevier, New York (2007), and on the corresponding website http: / / www.iza-structure.org / databases / . Under this definition, a zeolite can be an aluminosilicate having a zeolite framework type and a crystalline structure containing heteroatoms other than silicon and aluminum. Such heteroatoms can include any heteroatoms generally known to be suitable for inclusion in a zeolite framework, such as gallium, boron, germanium, phosphorus, zinc, antimony, tin, and / or other transition metals that can substitute for silicon and / or aluminum in a zeolite framework.

[0063] In some embodiments, the lithium-ion exchange zeolite particles, for example prior to operation of the electrochemical cell, may contain one or more of the following extra-framework cations: Na, less than or equal to about 10 atomic%, less than or equal to about 5 atomic%, less than or equal to about 1 atomic%, less than or equal to about 0.5 atomic%, or less than or equal to about 0.1 atomic%. + K + Mg 2+ Ca + H + and NH4 + In some embodiments, the lithium-ion exchange zeolite particles may contain less than or equal to about 1 atomic percent or less than or equal to about 0.1 at% Na. + H + Ca + K + and / or NH4 + One or more of the following. In some embodiments, the lithium-ion exchange zeolite particles contain NH4+. + The amount may be greater than one or more of the following cations: Na + K + Mg 2+ and Ca + Additionally or alternatively, lithium-ion exchange zeolite particles may substantially be free of one or more of the following: Na + K + Mg 2+ and Ca + cation.

[0064] like Figure 1AThe lithium-ion exchange zeolite particles 100 described herein, as provided herein, may include Li + Cations 115 and NH4 + Cation 120, for example, as an extra-framework cation. Additionally, the lithium-ion exchange zeolite particles may also include a Li3PO4 complex 125. (e.g.) Figure 1A As shown, Li3PO4 complex 125 may be present within cage 112 of lithium-ion exchange zeolite particles 100. In other words, cage 112 may include or contain one or more Li3PO4 complexes 125. Additionally or alternatively, as... Figure 1B As described, Li3PO4 complex 125 can also exist on the outer surface of lithium ion exchange zeolite particles 101.

[0065] In any embodiment, the lithium-ion exchange zeolite particles may have an average particle size of less than or equal to about 20 μm, less than or equal to about 15 μm, less than or equal to about 10 μm, less than or equal to about 5 μm, less than or equal to about 1 μm, less than or equal to about 100 nm, less than or equal to about 50 nm, or about 10 nm. Additionally or alternatively, the lithium-ion exchange zeolite particles may have an average particle size of greater than or equal to about 10 nm to less than or equal to about 20 μm, greater than or equal to about 10 nm to less than or equal to about 10 μm, greater than or equal to about 10 nm to less than or equal to about 5 μm, or greater than or equal to about 10 nm to less than or equal to about 1 μm.

[0066] Zeolite crystal structures comprise interstitial spaces (or cages) at the molecular size. Therefore, zeolites can be used as adsorbents to selectively adsorb molecules by retaining them within their interstitial spaces. Inlets to the interstitial spaces within the zeolite are provided by pore openings (or channels) in the zeolite lattice, defined by rings of interconnected oxygen (O), silicon (Si), and / or aluminum (Al) atoms. The size and shape of these pore openings limit the size and shape of molecules that can be adsorbed by the zeolite and are determined at least in part by the number of tetrahedral units (or alternative oxygen atoms) constituting the rings and the type of extra-framework cations present within the zeolite. Thus, lithium-exchange zeolite particles can have an average pore size capable of achieving one or more of the following: (i) selectively adsorbing water molecules (e.g., trace amounts) from liquid electrolytes without adsorbing organic solvent molecules or lithium salt ions from the electrolyte solution; and (ii) allowing substantially only Li-12 molecules to migrate while blocking polysulfide migration. +Ions pass through a separator, such as in a lithium-sulfur battery pack. In some embodiments, lithium-ion exchange zeolite particles may have an average pore size greater than the ionic radius of water (H₂O) but smaller than the ionic radius of organic solvent molecules in the electrolyte solution. Specifically, lithium-ion exchange zeolite particles may have an average pore size of less than or equal to about 1.5 nm, less than or equal to about 1 nm, less than or equal to about 0.75 nm, less than or equal to about 0.5 nm, less than or equal to about 0.25 nm, less than or equal to about 0.1 nm, or about 0.05 nm. Additionally or alternatively, lithium-ion exchange zeolite particles may have an average pore size greater than or equal to about 0.05 nm to less than or equal to about 1.5 nm, greater than or equal to about 0.05 nm to less than or equal to about 1 nm, greater than or equal to about 0.1 nm to less than or equal to about 1 nm, or greater than or equal to about 0.25 nm to less than or equal to about 0.75 nm. Zeolite materials having pore openings of the width or diameter described above may include zeolite materials having pore openings defined by 8-membered rings, 9-membered rings, 10-membered rings and / or 12-membered rings.

[0067] In some embodiments, the lithium-ion exchange zeolite particles may comprise particles of zeolite material having a SiO2:Al2O3 ratio of less than or equal to about 50, less than or equal to about 40, less than or equal to about 30, less than or equal to about 20, or about 10. The lithium-ion exchange zeolite particles may comprise particles of zeolite material having a SiO2:Al2O3 ratio of greater than or equal to about 10 to less than or equal to about 50, greater than or equal to about 10 to less than or equal to about 40, greater than or equal to about 10 to less than or equal to about 20, greater than or equal to about 20 to less than or equal to about 50, about 20 to about 40, or about 30 to about 50. In some embodiments, lithium-ion exchange zeolite particles having more SiO2 than Al2O3, for example, having a SiO2:Al2O3 ratio greater than about 10, are preferred, for example, to improve stability. In other embodiments, lithium-ion exchange zeolite particles with more SiO2 than Al2O3, such as having a SiO2:Al2O3 ratio of less than about 10, are provided, for example, to improve the hydrofluoric acid (HF) removal function of the porous separator to protect the positive electrode.

[0068] Lithium-ion exchange zeolite particles may contain zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and combinations thereof. For example, lithium-ion exchange zeolite particles may contain zeolite materials selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

[0069] This document provides a method for preparing lithium-ion exchanged zeolite particles. Zeolite particles prior to lithium ion exchange are referred to herein as "precursor zeolite particles." Precursor zeolite particles may have a framework selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and combinations thereof. For example, precursor zeolite particles may comprise zeolite materials selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof. Furthermore, the precursor zeolite particles and the lithium-ion exchanged zeolite particles formed therefrom may have substantially the same pore size, substantially the same particle size, and substantially the same SiO2:Al2O3 ratio as described herein. For example, ZSM-5 particles (precursor zeolite particles) with an average pore size of about 0.5 nm, an average particle size of 100 nm, and a SiO2:Al2O3 ratio of about 20 can undergo ion exchange to form lithium-ion exchanged ZSM-5 particles with essentially the same pore size, particle size, and SiO2:Al2O3 ratio as the initial ZSM-5 particles. In this paper, it is assumed that after ion exchange of the precursor zeolite particles, the pore size, particle size, and SiO2:Al2O3 ratio of the resulting lithium-ion exchanged zeolite particles may change to some extent (e.g., about 1-5%) compared to the precursor zeolite particles.

[0070] The precursor zeolite particles may have one or more hydrogen-containing or alkali metal or alkaline earth metal ions as initial exchangeable cations. Specifically, the precursor zeolite particles may have one or more ions selected from hydrogen, ammonium, lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium as initial exchangeable cations. In some embodiments, the precursor zeolite particles may contain one or more of the following cations: H... + NH4 + Na + K + Mg 2+ and / or Ca + .

[0071] This method may include obtaining a suitable amount of precursor zeolite particles, which are in powder form and have exchangeable extraframework cations. For example, such as... Figure 2A As shown, the method may include step 205: for example, combining precursor zeolite particles with (NH4)3PO4 in a first container at a sufficient temperature and for a sufficient duration to allow at least some of the exchangeable extraframework cations (e.g., Na+) within the zeolite precursor particles to be incorporated. + H + K + ) by NH4 + Ion substitution or exchange to produce, for example, NH4+ +The first mixture of intermediate zeolite particles of cations. (NH4)3PO4 can be present in aqueous or non-aqueous solutions (i.e., solvent solutions), and the precursor zeolite particles can be mixed with (NH4)3PO4.

[0072] Step 205 can be performed at a temperature greater than or equal to about 18°C, greater than or equal to about 20°C, greater than or equal to about 25°C, greater than or equal to about 30°C, greater than or equal to about 50°C, greater than or equal to about 80°C, greater than or equal to about 100°C, greater than or equal to about 120°C, or about 150°C; about 18°C ​​to about 150°C, about 18°C ​​to about 120°C, about 25°C to about 120°C, about 50°C to about 100°C, or about 80°C to about 120°C. Additionally or alternatively, step 205 may be performed for approximately 5 minutes, approximately 15 minutes, approximately 30 minutes, approximately 60 minutes, approximately 6 hours, approximately 12 hours, approximately 18 hours, approximately 24 hours, or approximately 48 hours; or approximately 5 minutes to approximately 48 hours, approximately 5 minutes to approximately 24 hours, approximately 30 minutes to approximately 48 hours, approximately 30 minutes to approximately 24 hours, approximately 60 minutes to approximately 48 hours, approximately 60 minutes to approximately 24 hours, approximately 6 hours to approximately 24 hours, approximately 12 hours to approximately 24 hours, approximately 18 hours to approximately 24 hours, or approximately 24 hours to approximately 48 hours.

[0073] In any embodiment, the method may include step 210, wherein a lithium salt may be added to a first mixture, for example, in a first container at a sufficient temperature and for a sufficient duration, to allow at least some of the exchangeable extraframework cations (e.g., NH4) within the intermediate zeolite particles to react. + Na + H + K + ) by Li + Ion substitution or exchange is used to produce lithium-ion exchanged zeolite particles as described herein. The lithium salt may be present in an aqueous or non-aqueous solution (i.e., a solvent solution), and the intermediate zeolite particles may be mixed with the lithium salt. The lithium salt may include lithium hydroxide (LiOH), lithium carbonate (Li₂CO₃), lithium chloride (LiCl), lithium nitrate (LiNO₃), lithium sulfate (Li₂SO₄), or combinations thereof. In one embodiment, the lithium salt may be LiOH. The concentration of the lithium salt in the solution may be from 0.1 M to 2 M and can be adjusted during the lithium-ion exchange process to ensure that a sufficient amount of initial exchangeable cations in the intermediate zeolite particles are replaced by lithium ions, such as NH₄⁺. + Cations are treated by Li + Cationic substitution. The addition of lithium salt to the first mixture can be represented by the following exemplary reaction equation (1): 3 LiOH + (NH4)3PO4 = Li3PO4 ↓ + 3NH3 ↑ + 3 H2O (1). The Li3PO4 formed during the reaction can be present within the cages of the lithium-ion exchange zeolite particles as described above. Additionally or alternatively, the Li3PO4 formed during the reaction can be present on the outer surface of the lithium-ion exchange zeolite particles as described above. It is considered herein that the concentrations of (NH4)3PO4 and lithium salts (e.g., LiOH) can be adjusted based on the amount of cations in the precursor zeolite material to ensure that Li3PO4 forms within the cages of the zeolite particles.

[0074] Step 210 may be performed at a temperature greater than or equal to about 18°C, greater than or equal to about 20°C, greater than or equal to about 25°C, greater than or equal to about 30°C, greater than or equal to about 50°C, greater than or equal to about 80°C, greater than or equal to about 100°C, greater than or equal to about 120°C, or about 150°C; about 18°C ​​to about 150°C, about 18°C ​​to about 120°C, about 25°C to about 120°C, about 50°C to about 100°C, or about 80°C to about 120°C. Additionally or alternatively, step 210 may be performed for approximately 5 minutes, approximately 15 minutes, approximately 30 minutes, approximately 60 minutes, approximately 6 hours, approximately 12 hours, approximately 18 hours, approximately 24 hours, or approximately 48 hours; or approximately 5 minutes to approximately 48 hours, approximately 5 minutes to approximately 24 hours, approximately 30 minutes to approximately 48 hours, approximately 30 minutes to approximately 24 hours, approximately 60 minutes to approximately 48 hours, approximately 60 minutes to approximately 24 hours, approximately 6 hours to approximately 24 hours, approximately 12 hours to approximately 24 hours, approximately 18 hours to approximately 24 hours, or approximately 24 hours to approximately 48 hours.

[0075] It has been discovered that by first using NH4 + Cation exchange precursor zeolite particles contain extra-framework cations, such as Na+, with small hydration radii. + H + K + (For example, in step 205), NH4 + The cation can then more easily and readily react with Li. + Cation exchange (e.g., in step 210). Undesirable cations, such as Na+, are removed from the zeolite particles. + and K + It is beneficial because these unwanted cations can contaminate the electrolyte of the battery pack. In addition, the incorporation of Li3PO4 into zeolite particles is advantageous because Li3PO4 has flame-retardant properties and can help prevent ignition during thermal runaway events in the battery pack.

[0076] Additionally or alternatively, the method may further include an optional step 215, which involves separating lithium-ion exchanged zeolite particles from the solvent or water after ion exchange. The lithium-ion exchanged zeolite particles can be separated by any suitable method, such as centrifugation or filtration. The lithium-ion exchanged zeolite particles can be cleaned or washed to remove residual ions and solvent—for example, by washing with deionized water. Additionally or alternatively, the method may include an optional step 220, which involves heating the separated lithium-ion exchanged zeolite particles at a suitable temperature for a sufficient amount of time to remove adsorbed water. The lithium-ion exchanged zeolite particles can be calcined in a dry environment or in a vacuum to accelerate the dehydration process. For example, the lithium-ion exchanged zeolite particles can be calcined in an environment with a relative humidity of less than 20% or in a drier environment. Step 220 may be performed at a temperature greater than or equal to about 100°C, greater than or equal to about 200°C, greater than or equal to about 300°C, greater than or equal to about 400°C, greater than or equal to about 500°C, or about 600°C; or about 100°C to about 600°C, about 200°C to about 600°C, about 300°C to about 600°C, about 400°C to about 600°C, or about 200°C to about 600°C. Additionally or alternatively, step 220 may last for approximately 5 minutes, approximately 15 minutes, approximately 30 minutes, approximately 60 minutes, approximately 2 hours, approximately 3 hours, approximately 4 hours, approximately 6 hours, approximately 8 hours, approximately 10 hours, approximately 16 hours, approximately 20 hours, or approximately 24 hours; or approximately 5 minutes to approximately 24 hours, approximately 5 minutes to approximately 16 hours, approximately 5 minutes to approximately 10 hours, approximately 5 minutes to approximately 4 hours, approximately 30 minutes to approximately 24 hours, approximately 30 minutes to approximately 8 hours, approximately 30 minutes to approximately 4 hours, approximately 60 minutes to approximately 24 hours, approximately 60 minutes to approximately 6 hours, approximately 60 minutes to approximately 5 hours, approximately 60 minutes to approximately 4 hours, approximately 2 hours to approximately 24 hours, approximately 2 hours to approximately 10 hours, approximately 2 hours to approximately 5 hours, approximately 2 hours to approximately 4 hours, approximately 4 hours to approximately 24 hours, or approximately 4 hours to approximately 8 hours. In one embodiment, lithium-ion exchange zeolite particles can be calcined by heating at a temperature of about 400-600°C for 1 to 5 hours. For example, lithium-ion exchange zeolite particles can be calcined by heating at a temperature of about 400°C for about 4 hours.

[0077] Calcinated lithium-ion exchange particles readily adsorb atmospheric moisture. Therefore, to prevent water from being introduced into the electrochemical cell along with the lithium-ion exchange zeolite particles, care should be taken to avoid exposing the particles to atmospheric moisture after the calcination step and before and during battery assembly. For example, the particles can be removed from step 220 and stored in a dry environment before incorporating them into the electrochemical cell. If the lithium-ion exchange zeolite particles are exposed to water, including atmospheric moisture, at any point before electrochemical cell assembly, an additional heat treatment step can be performed to remove trace amounts of water from the particles. This additional heat treatment step can be performed at a temperature greater than about 100°C for a sufficient time to remove trace amounts of water from the lithium-ion exchange zeolite particles.

[0078] In a further embodiment, an alternative method for preparing lithium-ion exchange zeolite particles is provided. For example, such as... Figure 2B As described herein, the method may include step 225: for example, combining precursor zeolite particles with (NH4)3PO4 in a first container at a sufficient temperature for a sufficient duration to allow at least some of the exchangeable extraframework cations (e.g., Na+) within the zeolite precursor particles to... + H + K + ) by NH4 + Ion substitution or exchange to produce, for example, NH4+ + A first mixture of cationic intermediate zeolite particles. Step 225 may be performed as described herein with respect to step 205.

[0079] The method may further include step 230: separating intermediate zeolite particles from a solvent or aqueous solution containing (NH4)3PO4. The intermediate zeolite particles can be separated by any suitable method, such as centrifugation or filtration. The intermediate zeolite particles can be cleaned or washed by removing residual ions and solvent—for example, by washing with deionized water. Additionally, in step 235, the separated intermediate zeolite particles may be combined with a lithium salt as described herein to form lithium-ion exchange zeolite particles as described herein. Step 235 may be performed as described herein with respect to step 210.

[0080] Additionally or alternatively, the method may further include step 240, which includes separating lithium-ion exchanged zeolite particles from the solvent or water after ion exchange. Step 240 may be performed as described herein with respect to step 215. Additionally or alternatively, the method may include optional step 245, which includes heating the lithium-ion exchanged zeolite particles at a suitable temperature for a sufficient amount of time to remove adsorbed water therefrom. Step 245 may be performed herein with respect to step 220.

[0081] II. Electrochemical Cells Lithium-ion electrochemical batteries typically include a negative electrode, a positive electrode, an electrolyte for conducting lithium ions between the negative and positive electrodes, and a porous separator between the negative and positive electrodes to physically and electrically isolate the electrodes from each other while allowing free ion flow. When assembled in an electrochemical battery, such as a lithium-ion battery pack, the porous separator is wetted with a liquid electrolyte. It has been found that lithium-ion exchange zeolite particles, such as those present in the electroactive material of the positive electrode and / or in the coating on the porous separator, can actively remove trace amounts of water, hydrogen ions, hydrofluoric acid, and dissociated transition metal ions (e.g., Mn) from the liquid electrolyte. 2+ and Fe 2+ / 3+ The electrolyte removes lithium ions, polysulfides, and other target compounds without inhibiting the transport or net flow of lithium ions through it. Removing these target compounds from the liquid electrolyte during battery pack operation can help prevent or mitigate degradation of various battery pack components, thereby improving battery pack life and cycle performance.

[0082] This document provides for use in battery packs, such as lithium-ion battery packs, or as electrochemical cells as capacitors. For example, exemplary and schematic illustrations of electrochemical cell 20 (also referred to as lithium-ion battery pack or battery pack 20) ​​are provided. Figure 3 As shown in the figure. The electrochemical cell 20 includes a negative electrode 22 (also referred to as a negative electrode layer 22), a first current collector 32 (also referred to as a negative electrode current collector 32) disposed at or near the negative electrode 22, a positive electrode 24 (also referred to as a positive electrode layer 24), a second current collector 34 (also referred to as a positive electrode current collector 34) disposed at or near the positive electrode 24, and a spacer 26 disposed between the positive electrode 24 and the first current collector 32. The space between the negative electrode 22 and the positive electrode 24 (e.g., the spacer 26) may be filled with an electrolyte 30. If pores exist in the negative electrode 22 and / or the positive electrode 24, the pores may also be filled with the electrolyte 30. The electrolyte 30 may impregnate, wet, or moisten the surfaces of each of the negative electrode 22, the positive electrode 24, and the porous spacer 26 and fill their pores.

[0083] The first current collector 32 and the second current collector 34 collect and move free electrons to and from the external circuit 40, respectively. The interruptible external circuit 40 and the load device 42 connect the first current collector 32 and the second current collector 34. Each of the negative electrode 22, the positive electrode 24, and the separator 26 may further contain an electrolyte 30 capable of conducting lithium ions. By being sandwiched between the negative electrode 22 and the positive electrode 24 to prevent physical contact and thus short circuits, the separator 26 acts as both an electrical insulator and a mechanical support. In addition to providing a physical barrier between the electrodes 22 and 24, the separator 26 provides a path of minimal resistance for the internal passage of lithium ions (and associated anions) to facilitate the operation of the battery pack 20. The separator 26 also contains an electrolyte solution in an open network during lithium-ion cycling to facilitate the operation of the battery pack 20.

[0084] When the negative electrode 22 contains a relatively larger amount of intercalated lithium, the battery pack 20 can generate current during discharge through a reversible electrochemical reaction that occurs when the external circuit 40 is closed (to connect the negative electrode 22 and the positive electrode 24). The chemical potential difference between the positive electrode 24 and the negative electrode 22 drives electrons generated at the negative electrode 22 by the oxidation of intercalated lithium to the positive electrode 24 via the external circuit 40. Simultaneously, lithium ions generated at the negative electrode are transferred through the electrolyte 30 and the separator 26 to the positive electrode 24. Electrons flow through the external circuit 40 and lithium ions migrate through the separator 26 in the electrolyte 30 to form intercalated lithium at the positive electrode 24. The current through the external circuit 40 can be utilized and directed by the load device 42 until the intercalated lithium in the negative electrode 22 is depleted and the capacity of the lithium-ion battery pack 20 decreases.

[0085] The lithium-ion battery pack 20 can be recharged or re-energized / re-energized at any time by connecting an external power source to it to reverse the electrochemical reactions that occur during battery pack discharge. The connection of the external power source to the lithium-ion battery pack 20 promotes the originally non-spontaneous oxidation of intercalated lithium at the positive electrode 24 to generate electrons and lithium ions. Electrons flowing back to the negative electrode 22 via the external circuit 40 and lithium ions carried by the electrolyte 30 through the separator 26 back to the negative electrode 22 recombine at the negative electrode 22, replenishing the intercalated lithium for consumption during the next battery pack discharge event. Thus, a complete discharge event followed by a complete charge event is considered a cycle in which lithium ions circulate between the positive electrode 24 and the negative electrode 22. External power sources that can be used to charge the lithium-ion battery pack 20 can vary depending on the size, construction, and specific end use of the lithium-ion battery pack 20. Some notable and exemplary external power sources include, but are not limited to, AC wall sockets and vehicle alternators.

[0086] In many battery pack configurations, each of the negative electrode current collector 32, negative electrode 22, separator 26, positive electrode 24, and positive electrode current collector 34 is fabricated as a relatively thin layer (e.g., a few micrometers or millimeters thick or less) and assembled in an electrically parallel arrangement of connected layers to provide a suitable energy pack. The negative electrode current collector 32 and the positive electrode current collector 34 collect and move free electrons to the external circuit 40 and collect and move free electrons from the external circuit 40, respectively.

[0087] In addition, the battery pack 20 may include a variety of other components, though not depicted herein, that are known to those skilled in the art. For example, as a non-limiting example, the lithium-ion battery pack 20 may include a housing, gaskets, end caps, tabs, battery terminals, and any other conventional components or materials that may be located within or near the battery pack 20, including those located between or near the negative electrode 22, the positive electrode 24, and / or the separator 26. Figure 3 The battery pack 20 shown includes a liquid electrolyte 30 and illustrates a representative concept for battery pack operation.

[0088] As described above, the size and shape of the lithium-ion battery pack 20 can vary depending on the specific application it is designed for. Battery-powered vehicles and portable consumer electronics are two examples where the battery pack 20 is most likely designed with different sizes, capacities, and power output specifications. If required by the load device 42, the battery pack 20 can also be connected in series or parallel with other similar lithium-ion batteries or battery packs to produce greater voltage output and power density.

[0089] Therefore, the battery pack 20 can generate current to a load device 42 that can be operatively connected to an external circuit 40. The load device 42 can be fully or partially powered by the current flowing through the external circuit 40 when the lithium-ion battery pack 20 is discharging. While the load device 42 can be any number of known electric devices, several specific examples of power-consuming load devices include, as non-limiting examples, electric motors in hybrid or fully electric vehicles, laptops, tablets, mobile phones, and cordless power tools or appliances. The load device 42 can also be a power generation device that charges the battery pack 20 for the purpose of energy storage.

[0090] This technology relates to improved electrochemical batteries, particularly lithium-ion battery packs. Such batteries are used in various vehicle or automotive transportation applications (e.g., motorcycles, boats, tractors, buses, motorbikes, mobile homes, campervans, and tanks). However, this technology can be used in a wide variety of other industries and applications, as non-limiting examples, including aerospace components, consumer products, devices, buildings (e.g., residences, offices, sheds, and warehouses), office equipment and furniture, and industrial equipment machinery, agricultural or farm equipment, or heavy machinery.

[0091] A. Positive electrode The positive electrode 24 may be formed of a first electroactive material that can sufficiently perform lithium intercalation and deintercalation while serving as the positive terminal of the lithium-ion battery pack 20. The positive electrode 24 may further comprise a polymeric binder material to structurally reinforce the lithium-based active material and the conductive material. One exemplary common class of known materials that can be used to form the positive electrode 24 is layered lithium transition metal oxides. For example, in certain embodiments, the positive electrode 24 may comprise Li (1+x) Mn2O4, where 0.1 ≤ x ≤ 1; LiMn (2-x) Ni x O4, where 0 ≤ x ≤ 0.5; LiCoO2; Li(Ni x Mn y Co z )O2, where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, and x + y + z = 1; LiNi (1-x-y) Co x M y O2, where 0<x<0.2, y<0.2, and M is Al, Mg or Ti; LiFePO4, LiMn 2-x Fe x PO4, where 0 < x < 0.3; LiNiCoAlO2; LiMPO4, where M is at least one of Fe, Ni, Co and Mn; Li(Ni x Mn y Co z Al p )O2, where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, 0 ≤ P ≤ 1, x + y + z + p = 1 (NCMA); LiNiMnCoO2; Li2Fe x M 1-x PO4 (M = Mn and / or Ni, 0 ≤ x ≤ 1); LiMn2O4; LiFeSiO4; LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC622), LiMnO2 (LMO), activated carbon, sulfur (e.g., greater than 60 wt.% based on the total weight of the positive electrode), or a combination thereof. Additionally or alternatively, the positive electrode 24 may comprise lithium ion-exchange zeolite particles as described herein, for example as an additive.

[0092] In this document, the first electroactive material is considered to be in particle form and may have a circular or axial geometry. The term "axial geometry" refers to a particle that typically has a rod-like, fibrous, or other cylindrical shape with a distinctly long or slender axis. Generally, the aspect ratio (AR) of a cylindrical shape (e.g., a fiber or rod) is defined as AR = L / D, where L is the length of the longest axis and D is the diameter of the cylinder or fiber. Exemplary axial geometry electroactive material particles suitable for this disclosure may have a high aspect ratio, for example, from about 10 to about 5,000. In some variations, the first electroactive material particles having an axial geometry include fibers, wires, sheets, whiskers, filaments, tubes, rods, etc.

[0093] The term "circular geometry" is generally used for particles with a low aspect ratio, such as close to 1 (e.g., less than 10). It should be noted that particle geometry may differ from a true circle and may include, for example, rectangles or ellipses, including elongated or oblate spheroids, aggregated particles, polygonal (e.g., hexagonal) particles, or other shapes that typically have a low aspect ratio. An oblate spheroid may have a disk-like shape with a relatively high aspect ratio. Therefore, particles with approximately circular geometry are not limited to relatively low aspect ratios and spherical shapes.

[0094] Additionally or alternatively, the positive electrode 24 may optionally comprise a conductive material and / or a polymer binder. Examples of conductive materials include, but are not limited to, carbon black, graphite, acetylene black (such as KETCHEN). TM Black or Denka TM The conductive materials include black carbon nanotubes, carbon fibers, carbon nanofibers, graphene, graphene nanosheets, graphene oxide, nitrogen-containing carbon, metal powders (e.g., copper, nickel, steel, or iron), liquid metals (e.g., Ga, GaInSn), conductive polymers (e.g., including polyaniline, polythiophene, polyacetylene, polypyrrole, etc.), and combinations thereof. As used herein, the term "graphene nanosheet" refers to a nanosheet or stack of graphene layers. Such conductive materials in particle form can have circular or axial geometries as described above.

[0095] Examples of suitable polymeric adhesives include, but are not limited to, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber or carboxymethyl cellulose (CMC), nitrile butadiene rubber (NBR), styrene-butadiene rubber (SBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), poly(acrylate) PAA, polyimide, polyamide, sodium alginate, lithium alginate, and combinations thereof. In some embodiments, the polymeric adhesive may be a polymer based on a non-aqueous solvent or a polymer based on an aqueous solvent. In particular, the polymeric adhesive may be a polymer based on a non-aqueous solvent, which may exhibit less capacity decay, provide a more robust mechanical network and improved mechanical properties to more effectively cope with silicon particle expansion, and have good chemical and heat resistance. For example, the polymeric adhesive may include polyimide, polyamide, polyacrylonitrile, polyacrylic acid, salts of polyacrylic acid (e.g., potassium, sodium, lithium), polyacrylamide, polyvinyl alcohol, carboxymethyl cellulose, or combinations thereof. The first electroactive material may be blended with a conductive material and / or at least one polymeric adhesive. For example, a first electroactive material and an optional conductive material can be slurry-cast and applied to the current collector together with such a binder. The polymer binder can play multiple roles in the electrode, including: (i) enabling electronic and ionic conductivity of the composite electrode, (ii) providing electrode integrity, such as the integrity of the electrode and its components, and its adhesion to the current collector, and (iii) participating in the formation of the solid electrolyte interface (SEI), which plays an important role since the kinetics of lithium intercalation depend primarily on the SEI.

[0096] In any embodiment, the first electroactive material may be present in the positive electrode in an amount greater than or equal to about 50% by weight, greater than or equal to about 60% by weight, greater than or equal to about 70% by weight, greater than or equal to about 80% by weight, greater than or equal to about 90% by weight, greater than or equal to about 95% by weight, or about 99% by weight, based on the total weight of the positive electrode; or about 50% by weight to about 99% by weight, about 70% by weight to about 99% by weight, or about 90% by weight to about 99% by weight.

[0097] Additionally or alternatively, the conductive material and polymeric binder may each be present in the positive electrode in an amount of about 0.5% to about 20% by weight, about 1% to about 15% by weight, or about 1% to about 10% by weight, based on the total weight of the positive electrode.

[0098] B. Negative electrode The negative electrode 22 comprises a second electroactive material as a lithium matrix material capable of serving as the negative terminal of a lithium-ion battery pack. The second electroactive material may include lithium (e.g., metallic lithium), lithium alloys, such as, but not limited to, lithium-silicon alloys, lithium-aluminum alloys, lithium-indium alloys, lithium-tin alloys, or combinations thereof. The negative electrode 22 may optionally further comprise one or more of graphite, activated carbon, carbon black, hard carbon, soft carbon, graphene, silicon, tin oxide, aluminum, indium, zinc, germanium, silicon oxide, titanium oxide, lithium titanate, and combinations thereof, such as silicon mixed with graphite. Non-limiting examples of silicon-containing electroactive materials include silicon (amorphous or crystalline), or silicon-containing binary and ternary alloys, such as Si-Sn, SiSnFe, SiSnAl, SiFeCo, etc. In other variations, the negative electrode 22 may be a metal film or foil, such as a lithium metal film or a lithium-containing foil. The second electroactive material may be in particle form and may have the circular or axial geometry described above. Additionally or alternatively, the negative electrode 22 may contain lithium-ion exchange zeolite particles as described herein, for example, as an additive.

[0099] Additionally, the negative electrode 22 may optionally include conductive materials as described herein and / or polymeric binders as described herein to improve the structural integrity of the electrode. For example, the second electroactive material and the electronically conductive or conductive material may be slurry-cast together with binders such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber or carboxymethyl cellulose (CMC), nitrile rubber (NBR), styrene-butadiene rubber (SBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), poly(acrylate) PAA, polyimide, polyamide, sodium alginate, or lithium alginate, and applied to the current collector. Examples of conductive materials include, but are not limited to, carbon black, graphite, acetylene black (such as KETCHEN), etc. TM Black or Denka TM (Black), carbon nanotubes, carbon fibers, carbon nanofibers, graphene, graphene nanosheets, graphene oxide, nitrogen-containing carbon, metal powders (e.g., copper, nickel, steel or iron), liquid metals (e.g., Ga, GaInSn), conductive polymers (e.g., including polyaniline, polythiophene, polyacetylene, polypyrrole, etc.) and combinations thereof.

[0100] In various respects, the second electroactive material may be present in the negative electrode in an amount of about 70% to about 99% by weight, about 80% to about 98% by weight, about 90% to about 99% by weight, or about 95% to about 98% by weight, based on the total weight of the negative electrode. Additionally or alternatively, the conductive material and the polymeric binder may each be present independently in the negative electrode in an amount of about 0.5% to about 15% by weight, about 1% to about 10% by weight, or about 1% to about 5% by weight, based on the total weight of the negative electrode.

[0101] C. Current collector The first current collector 32 and the second current collector 34 may each comprise a metal containing copper, aluminum, nickel, or an alloy thereof, stainless steel, or other suitable conductive material known to those skilled in the art. Additionally or alternatively, the first current collector 32 and the second current collector 34 may each be formed of or further comprise a carbon or carbon-metal (e.g., silver (Ag), aluminum (Al), zinc (Zn)) composite coating, for example having a thickness of about 500 nm to about 2 µm. In some aspects, the first current collector 32 and / or the second current collector 34 may be in the form of a foil, a slit mesh, and / or a woven mesh.

[0102] D. Porous spacers In any embodiment, the porous separator 26 may comprise any organic or inorganic material that can physically and electrically isolate the positive and negative electrodes from each other while allowing lithium ions to flow freely therebetween. For example, the porous separator 26 may comprise composite or nonwoven materials, such as sheets, webs, or mats made of oriented or randomly oriented fibers, including but not limited to cotton, nylon, polyester, glass, and combinations thereof. As another example, the separator 26 may comprise porous (e.g., microporous) polymeric materials, such as polyolefin-based microporous membranes (membrane or film). The porous separator 26 may comprise a single polyolefin or a combination of polyolefins, such as polyethylene (PE), polypropylene (PP), polyamide (PA), poly(tetrafluoroethylene) (PTFE), polyvinylidene fluoride (PVdF), and / or poly(vinyl chloride) (PVC). The polyolefin may be a homopolymer (derived from a single monomer component) or a hybrid (derived from more than one monomer component), and may be linear or branched. If the hybrid polymer is derived from two monomer components, the polyolefin can take any copolymer chain arrangement, including those of block copolymers or random copolymers. Similarly, if the polyolefin is a hybrid polymer derived from more than two monomer components, it can also be a block copolymer or a random copolymer. In some embodiments, the porous separator 26 may comprise a laminate of one or more polymer materials, such as a laminate of PE and PP. Commercially available polyolefin porous separator substrates may include CELGARD, available from Celgard LLC. ® 2500 (single-layer polypropylene spacer) and CELGARD ® 2325 (Three-layer polypropylene / polyethylene / polypropylene separator). Additionally or alternatively, the porous separator 26 may contain lithium-ion exchange zeolite particles as described herein, for example, as a filler.

[0103] In other respects, the porous spacer 26 may be a fibrous membrane having a large number of pores extending between opposing surfaces and may have an average thickness of, for example, less than 1 mm. However, as another example, multiple discrete layers of similar or different polyolefins may be assembled to form the porous spacer 26. In addition to polyolefins, the porous spacer 26 may also contain other polymers, such as, but not limited to, polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyamides, polyimides, poly(amide-imide) copolymers, polyetherimides, and / or cellulose, or any other material suitable for creating the desired porous structure. Polyolefin layers and any other optional polymer layers may be further included as fibrous layers in the porous spacer 26 to help provide the porous spacer 26 with appropriate structural and porosity properties. The porous spacer 26 may have a thickness of about 4 μm to about 25 μm.

[0104] E. (One or more) coatings In any embodiment, the porous separator may include a first coating comprising lithium-ion exchange zeolite particles as described herein. For example, as Figure 4 As shown, in the battery pack 21, the porous separator 26 may have a first side 50 and an opposite second side 55. A first coating 60 containing lithium-ion exchange zeolite particles may be present on one or both sides 50, 55 of the separator 26. In some embodiments, such as Figure 4 As shown, the first side 50 and second side 55 of the spacer 26 may be coated with a first coating 60. In the assembly, the first coating 60 present on the first side 50 faces and presses against the negative electrode 22, and the first coating 60 present on the second side 55 faces and presses against the positive electrode 24. However, in other embodiments, the first side 50 of the spacer 26 may be coated with the first coating 60 and the second side 55 of the spacer 26 may be uncoated, such that in the assembly, the second side 55 of the spacer 26 faces and presses against the positive electrode 24. In other embodiments, the second side 55 of the spacer 26 may be coated with the first coating 60 and the first side 50 of the spacer 26 may be uncoated, such that in the assembly, the first side 50 of the spacer 26 faces and presses against the negative electrode 22. The first coating 60 may additionally comprise a polymeric adhesive material.

[0105] The first coating 60 may be formed continuously or discontinuously on the first and / or second sides 50, 55 of the spacer 26. For example, the first coating 60 may be formed on the first side 50 of the spacer 26 such that the first coating 60 covers the entire surface area or only a portion of the surface area of ​​the first side 50 of the spacer 26. Similarly, the first coating 60 may be formed on the second side 55 of the spacer 26 such that the first coating 60 covers the entire surface area or only a portion of the surface area of ​​the second side 55 of the spacer 26. The first coating 60 may extend across the first and second sides 50, 55 of the spacer 26 and, in some cases, may partially extend into the micropores of the spacer 26.

[0106] Additionally or alternatively, the positive electrode, negative electrode, or both may include a second coating comprising lithium-ion exchange zeolite particles as described herein. For example, as... Figure 5 As shown, in battery pack 22, negative electrode 22 may have a third side 74, and positive electrode 24 may have a fourth side 76. A second coating 70 containing lithium-ion exchange zeolite particles may be present on one or both sides 74, 76 of electrodes 22, 24. In some embodiments, such as Figure 5 As shown, the third side 74 and the fourth side 76 may be coated with a second coating 70. In the assembly, the second coating 70 present on the third side 74 faces and presses against the spacer 26, and the second coating 70 present on the fourth side 76 faces and presses against the spacer 26. However, in other embodiments, the third side 74 of the negative electrode 22 may be coated with the second coating 70 and the fourth side 76 of the positive electrode 24 may be uncoated, such that in the assembly, the fourth side 76 of the positive electrode 24 faces and presses against the spacer 26. In other embodiments, the fourth side 76 of the positive electrode 24 may be coated with the second coating 70 and the third side 74 of the negative electrode 22 may be uncoated, such that in the assembly, the third side 74 of the negative electrode 22 faces and presses against the spacer 26. The second coating 70 may additionally comprise a polymeric adhesive material.

[0107] The second coating 70 can be formed continuously or discontinuously on each of the sides 74, 76. For example, the second coating 70 can be formed on the third side 74 of the negative electrode 22 such that the second coating 70 covers the entire surface area or only a portion of the surface area of ​​the third side 74 of the negative electrode 22. Similarly, the second coating 70 can be formed on the fourth side 76 of the positive electrode 24 such that the second coating 70 covers the entire surface area or only a portion of the surface area of ​​the fourth side 76 of the positive electrode 24. The second coating 70 can extend throughout the third and fourth sides 74, 76, and in some cases can partially extend into the micropores of the electrodes 22, 24.

[0108] In any embodiment, the first coating 60 and / or the second coating 70 may have a thickness of less than or equal to about 25 μm, less than or equal to about 20 μm, less than or equal to about 10 μm, less than or equal to about 5 μm, less than or equal to about 1 μm, or about 50 nm. Alternatively or additionally, the first coating 60 and / or the second coating 70 may have a thickness of about 50 nm to about 20 μm, about 50 nm to about 10 μm, or about 50 nm to about 5 μm. The thickness of the first coating 60 may be less than the thickness of the spacer 26. For example, the thickness of the first coating 60 may be 50% or less of the thickness of the spacer 26.

[0109] Lithium-ion exchange zeolite particles, serving as additives in electrodes 22 and 24 and / or as fillers in separator 26, within the first coating 60 and second coating 70, can be arranged within the lithium-ion transport path through electrochemical cells 20, 21, and 22. During operation of electrochemical cells 20, 21, and 22, lithium ions can travel back and forth between the negative electrode 22 and the positive electrode 24 of electrochemical cells 20, 21, and 22, and the lithium-ion exchange zeolite particles can be arranged such that, during this back-and-forth movement, lithium ions inevitably encounter one or more of the lithium-ion exchange zeolite particles. Lithium ions can come into contact with, surround, or travel through the lithium-ion exchange zeolite particles during their movement through electrochemical cells 20, 21, and 22. The lithium-ion exchange zeolite particles can be formulated or selected to adsorb, remove, intercept certain target compounds within electrochemical cells 20, 21, and 22, or otherwise inhibit their movement, without adversely affecting the transport or net flow rate of lithium ions through electrochemical cells 20, 21, and 22. For example, lithium-ion exchange zeolite particles can be formulated or selected based on the aforementioned pore size, average particle size, and / or cation content to intercept or suppress water molecules, polysulfide molecules, hydrogen ions, HF, and transition metal ions, such as Mn, within electrochemical cells 20, 21, and 22. 2+ and Fe 2+ / 3+ Ion movement. Target compounds can be trapped within lithium-ion exchange zeolite particles physically, chemically, or both physically and chemically.

[0110] Therefore, including lithium-ion exchange zeolite particles in batteries 20, 21, and 22 can help prevent a phenomenon known as “voltage droop,” reduce capacity decay and impedance, improve coulombic efficiency, help maintain a uniform current distribution along the electrode / electrolyte interface, mitigate corrosion, and prevent leakage in batteries 20, 21, and 22.

[0111] Unwilling to be bound by theory, it is believed that lithium-ion exchange zeolite particles can advantageously help improve the cycle performance of electrochemical cells 20, 21, and 22, for example, by trapping trace amounts of water, removing hydrofluoric acid (HF), and / or blocking polysulfide migration. Immobilizing trace water molecules within electrochemical cells 20, 21, and 22 can help prevent the decomposition of the liquid electrolyte 30, which in turn can help prevent the decomposition of the lithium-based intercalation matrix material of the positive electrode 24. Hydrofluoric acid is highly corrosive and can be generated in electrochemical cells 20, 21, and 22 during the decomposition of the electrolyte, particularly through the reaction of LiPF6 with water according to the following reaction equation (2): LiPF6 + H2O ↔ LiF + POF3 + 2HF (2) The HF thus generated can increase the acidity of the liquid electrolyte 30, which can lead to corrosion of the lithium-based intercalation matrix material of the positive electrode 24 and / or the current collectors 32, 34. Therefore, by acting as an HF scavenger, the lithium-ion exchange zeolite particles in the batteries 20, 21, 22 can help mitigate the corrosion and degradation of various components of the batteries 20, 21, 22.

[0112] Furthermore, it is believed that the lithium-ion exchange zeolite particles in batteries 20, 21, and 22 can retain transition metal ions, such as Mn. 2+ and Fe 2+ / 3+ The presence of transition metal ions in the liquid electrolyte 30 can help improve the cycle performance of electrochemical cells 20, 21, and 22. These transition metal ions may be present in the liquid electrolyte 30 due to the decomposition of the lithium-based intercalation matrix material of the positive electrode 24 and / or due to the presence of transition metal impurities in the positive electrode 24. Furthermore, the lithium-ion exchange zeolite particles within cells 20, 21, and 22 can help improve the robustness of cells 20, 21, and 22, for example, by improving the mechanical properties and thermal stability of the separator 26.

[0113] F. Electrolytes The positive electrode 24, negative electrode 22, and separator 26 may each contain an electrolyte solution or system 30 within their pores, capable of conducting lithium ions between the negative electrode 22 and the positive electrode 24. Any suitable electrolyte 30 capable of conducting lithium ions between the negative electrode 22 and the positive electrode 24, whether in solid, liquid, or gel form, can be used in the lithium-ion battery packs 20 and 21. In some aspects, the electrolyte 30 may be a non-aqueous liquid electrolyte solution comprising a lithium salt dissolved in an organic solvent or a mixture of organic solvents. Many conventional non-aqueous liquid electrolyte solutions 30 can be used in the lithium-ion battery packs 20 and 21.

[0114] In some aspects, electrolyte 30 may be a non-aqueous liquid electrolyte solution comprising one or more lithium salts dissolved in an organic solvent or a mixture of organic solvents. For example, a non-limiting list of lithium salts soluble in organic solvents to form a non-aqueous liquid electrolyte solution includes lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalate)borate (LiB(C2O4)2) (LiBOB), and lithium difluorooxalate borate (LiBF2(C2O4)2) (LiBF4). Lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethane)sulfonylimide (LiN(CF3SO2)2), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2) (LiSFI), lithium bis(trifluoromethanesulfonyl)imide (Li(G3)(TFSI)), lithium bis(trifluoromethanesulfonyl)imide (LiTFSA) (bis(trifluoromethanesulfonyl)azanide) and combinations thereof.

[0115] These and other similar lithium salts can be dissolved in a variety of non-aqueous, aprotic organic solvents, including but not limited to, various alkyl carbonates such as cyclic carbonates (e.g., ethylene carbonate (EC), propylene carbonate (PC), butyl carbonate (BC), fluoroethylene carbonate (FEC)), linear carbonates (e.g., dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC)), aliphatic carboxylic acid esters (e.g., methyl formate, methyl acetate, methyl propionate), γ-lactones (e.g., γ-butyrolactone, γ-valerolactone), chain ethers (e.g., 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g., tetrahydrofuran, 2-methyltetrahydrofuran), and 1,3-dioxolane. One or more salts may be present in the electrolyte at a concentration greater than or equal to about 1 M, greater than or equal to about 2 M, greater than or equal to about 3 M, or about 4 M, or about 1 M to about 4 M, about 1 M to 2 M, about 2 M to about 4 M, or about 3 M to about 4 M (number of moles of salt per liter of solvent).

[0116] Additionally or alternatively, the electrolyte may include additives that can, for example, improve the temperature and voltage stability of electrochemical battery materials (e.g., electrolyte 30, negative electrode 22, and positive electrode 24). Examples of suitable additives include, but are not limited to, ethylene carbonate, vinyl ethylene carbonate, propane sulfonate, and combinations thereof. Other additives may include diluents that do not coordinate with lithium ions but can reduce viscosity, such as bis(2,2,2-trifluoroethyl) ether (BTFE), and flame retardants, such as triethyl phosphate. Example

[0117] Example 1 Lithium-ion exchanged zeolite particles were prepared using two methods. The first method involved zeolite precursor particles and Li... + Conventional direct ion exchange between cations. A second method is the ion exchange method according to this disclosure. Unless otherwise specified, zeolite powder (CBV 600; zeolite Y) with a Na₂O weight ratio of 0.2%, obtained from Zeolyst International, is used as the zeolite precursor particles. LiOH and (NH₄)₃PO₄ are obtained from Sigma-Aldrich. Li + or NH4 + Concentration of cations (mol L) -1 ) Controlled to Na in zeolite + Approximately 10 times that of cations.

[0118] In the first method, zeolite precursor particles were combined with an aqueous solution containing LiOH at 80°C for 24 hours to form lithium-ion exchange particles. These particles were then separated by vacuum filtration, washed twice with deionized water, and finally dried overnight in a vacuum furnace at 100°C to obtain comparative zeolite particles A. In the second method, zeolite precursor particles were combined with an aqueous solution containing (NH4)3PO4 at 80°C for 24 hours to form a first mixture. LiOH was added to the first mixture at 80°C for 24 hours to form lithium-ion exchange particles. These particles were then separated by vacuum filtration, washed twice with deionized water, and finally dried overnight in a vacuum furnace at 100°C to obtain zeolite particles 1. The amounts of cations present in comparative zeolite particles A and zeolite particles 1 are shown in Table 1 below.

[0119] Table 1 sample <![CDATA[Na + (atomic percentage) <![CDATA[Li + (atomic percentage) N (atomic %) Comparison of zeolite particles A 0.1440 0.445 < 0.5 Zeolite particles 1 0.0517 0.567 < 0.5 .

[0120] As shown in Table 1, the second method results in more Li in zeolite particles 1. + Cations and less Na +Cations. X-ray diffraction (XRD) analysis was also performed on zeolite particles 1 and Li3PO4 (10) was confirmed to be present in zeolite particles 1 (20). Figure 6 The XRD pattern of zeolite particle 1 is shown.

[0121] For illustrative and descriptive purposes, the foregoing description of embodiments has been provided. It is not intended to be exhaustive or limiting of this disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but are interchangeable and may be used in selected embodiments where applicable, even if not specifically shown or described. They may also be varied in many ways. Such variations should not be considered a departure from this disclosure, and all such modifications are intended to be included within the scope of this disclosure.

Claims

1. A method for preparing lithium-ion exchange zeolite particles, the method comprising: (a) Combining precursor zeolite particles with (NH4)3PO4 to form a first mixture comprising intermediate zeolite particles, wherein the precursor zeolite particles comprise a group selected from H + NH4 + Na + K + Mg 2+ Ca + and cations in combination thereof; and (b) Perform one of the following: (i) Adding a lithium salt to the first mixture to form the lithium-ion exchange zeolite particles, or (ii) Separating the intermediate zeolite particles from the first mixture and combining the intermediate zeolite particles with the lithium salt to form the lithium-ion exchange zeolite particles; and The lithium-ion exchange zeolite particles contained Li + and NH4 + cation.

2. The method of claim 1, wherein the lithium-ion exchange zeolite particles comprise cages defined by 8-membered rings, 9-membered rings, 10-membered rings, 12-membered rings or combinations thereof, and wherein the cages contain Li3PO4.

3. The method according to claim 2, wherein the lithium-ion exchange zeolite particles further comprise Li3PO4 present on the outer surface of the lithium-ion exchange zeolite particles.

4. The method of claim 1, wherein the lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and combinations thereof.

5. The method according to claim 1, wherein the lithium-ion exchange zeolite particles comprise zeolite materials selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

6. The method of claim 1, wherein the precursor zeolite particles comprise Na + H + and / or K + The cations and / or the intermediate zeolite particles contain NH4 + cation.

7. The method according to claim 1, wherein the lithium salt is selected from lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, lithium sulfate, and combinations thereof.

8. The method according to claim 1, wherein the combination of the precursor zeolite particles with (NH4)3PO4, the addition of LiOH to the first mixture to form the lithium-ion exchange zeolite particles, and the combination of the intermediate zeolite particles with LiOH to form the lithium-ion exchange zeolite particles are each carried out at a temperature of 18°C ​​to 120°C.

9. The method of claim 1, further comprising performing one or more of the following: (c) Separating the lithium-ion exchange zeolite particles; and (d) Heating the lithium-ion exchange zeolite particles.

10. The method of claim 9, wherein the heating is performed at a temperature greater than or equal to 100°C.

11. A lithium-ion exchange zeolite particle, comprising: A cage defined by an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or a combination thereof, wherein said cage comprises Li3PO4; and Li + and NH4 + cation.

12. The lithium-ion exchange zeolite particles of claim 11, wherein the lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and combinations thereof.

13. The lithium-ion exchange zeolite particles according to claim 11, wherein the lithium-ion exchange zeolite particles comprise zeolite materials selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

14. An electrochemical battery comprising: A positive electrode containing a first electroactive material; A negative electrode spaced apart from the positive electrode, wherein the negative electrode comprises a second electroactive material; A porous insulating member is disposed between the opposing surfaces of the negative electrode and the positive electrode; A liquid electrolyte wetting one or more of the negative electrode, the positive electrode, and the porous separator; and Lithium-ion exchanged zeolite particles, comprising: A cage defined by an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or a combination thereof, wherein the cage comprises Li3PO4; and Li + and NH4 + cation.

15. The electrochemical cell according to claim 14, wherein the lithium-ion exchange zeolite particles are present as one or more of the following: (i) A first coating present on a first side, a second side, or both of the first and second sides of the porous spacer; (ii) The packing material in the porous separator; (iii) The additive in the positive electrode, the negative electrode, or both; and (iv) A second coating present on the third side of the negative electrode, the fourth side of the positive electrode, or both the third side of the negative electrode and the fourth side of the positive electrode.

16. The electrochemical battery of claim 14, wherein the lithium-ion exchange zeolite particles comprise zeolite materials having a framework type selected from NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and combinations thereof.

17. The electrochemical battery according to claim 14, wherein the lithium-ion exchange zeolite particles comprise zeolite materials selected from zeolite A, zeolite Y, zeolite L, ZSM-5, and combinations thereof.

18. The electrochemical cell according to claim 14, wherein the first electroactive material is selected from Li (1+x) Mn2O4, wherein 0.1 ≤ x ≤ 1; LiMn (2-x) Ni x O4, wherein 0 ≤ x ≤ 0.5; LiCoO2; Li(Ni x Mn y Co z )O2, wherein 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, and x + y + z = 1; LiNi (1-x-y) Co x M y O2, wherein 0<x<0.2, y<0.2, and M is Al, Mg or Ti; LiFePO4, LiMn 2-x Fe x PO4, wherein 0 < x < 0.3; LiNiCoAlO2; LiMPO4, wherein M is at least one of Fe, Ni, Co and Mn; Li(Ni x Mn y Co z Al p )O2, wherein 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, 0 ≤ P ≤ 1, x + y + z + p = 1 (NCMA); LiNiMnCoO2; Li2Fe x M 1-x PO4, wherein M is Mn and / or Ni, 0 ≤ x ≤ 1; LiMn2O4; LiFeSiO4; LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC622), LiMnO2 (LMO), activated carbon, sulfur, and combinations thereof.

19. The electrochemical battery according to claim 14, wherein the second electroactive material comprises lithium, lithium-silicon alloy, lithium-aluminum alloy, lithium-indium alloy, lithium-tin alloy, graphite, activated carbon, carbon black, hard carbon, soft carbon, graphene, silicon, tin oxide, aluminum, indium, zinc, germanium, silicon oxide, titanium oxide, lithium titanate, or combinations thereof.

20. The electrochemical cell of claim 14, wherein the porous separator comprises a composite material, a polymer material, a nonwoven material, or a combination thereof.

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