System and method for a rechargeable energy source system including a delithiated cathode

Abstract

In some embodiments, the present disclosure provides a rechargeable energy source system. The rechargeable energy source system provides at least about 0.4 g / cm³ 3 The negative electrode may include a layer of lithium metal having a density and an impurity level of less than approximately 50 ppm by mass. The rechargeable energy source system may include a positive electrode synthesized to be substantially lithium-free. The positive electrode may have a capacity of at least 250 mAh / g and a gravimetric energy density of at least 800 Wh / kg.

Description

[Technical Field]

[0001] cross reference This application claims the benefit of U.S. Provisional Application No. 63 / 509,109, filed on June 20, 2023, which is incorporated herein by reference in its entirety.

[0002] Statement regarding federally funded research This disclosure was made with government support under DE-AC02-05CH11231, granted by the Department of Energy. The government has certain rights to this disclosure. [Background technology]

[0003] The redox material can be used as the positive electrode in a rechargeable energy source system. [Overview of the project] [Means for solving the problem]

[0004] In some embodiments, the Disclosure provides an electrochemical system comprising a negative electrode including a layer of lithium metal having a density of at least about 0.4 g / cm³; and a positive electrode substantially free of lithium when the rechargeable energy source system is charged, wherein the positive electrode has a capacity of at least 300 mAh / g and a gravimetric energy density of at least 800 Wh / kg.

[0005] In some embodiments, the Disclosure provides an electrochemical system comprising a negative electrode including a layer of lithium metal having a density of at least about 0.4 g / cm³; and a positive electrode substantially free of lithium when the rechargeable energy source system is in a charged state, wherein the positive electrode has a capacity of at least 250 mAh / g and is configured to exhibit a volume change of less than 15% between a discharged state and a charged state.

[0006] In some embodiments, the positive electrode is configured to maintain a volume change over at least 100 charge / discharge cycles of the electrochemical system.

[0007] In some embodiments, the positive electrode contains vanadium atoms. In some embodiments, the positive electrode contains V x O y In some embodiments, the positive electrode contains V x O y F z In some embodiments, the positive electrode contains V6O5F 19 V3OF 11 VO2F, VOF3, VPO4F, LiV3OF 11 Mn3V(PO4)6, V6O5F 19 V2(PO4)3, LiVOF4, LiV(OF)2, LiV(OF)2, MnVP2(O4F)2, V4O7F5, LiV3CoO 10 VPO5, VFeP2(O4F)2, TiVO4, LiTiV3O 10 VFeP2(HO5)2, Li2VOF5, MnV4O 12 VBO4, LiV2P2(O4F)2, LiV3CrO8, V4(OF3)3, LiV4O8, V(CO3)2, LiV5O 10 VCuO4, or at least one of VCo3O8. In some embodiments, the positive electrode contains FePO4, NiMnCoO2, or TiS2.

[0008] In some embodiments, the rechargeable energy source system contains an excess of lithium, and the excess lithium constitutes less than 10% of the net amount of lithium transferred between the negative and positive electrodes during the discharge or charge of the rechargeable energy source system. In some embodiments, the positive electrode is configured to exhibit a volume change of less than 10% over at least 100 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the energy capacity loss of the rechargeable energy source system is less than 1% over at least 100 charge / discharge cycles. In some embodiments, the energy capacity loss of the rechargeable energy source system is less than 1% over at least 300 charge / discharge cycles. In some embodiments, the N / P ratio is less than 0.1 when the rechargeable energy source system is completely discharged. In some embodiments, the N / P ratio is about 0 when the rechargeable energy source system is completely discharged.

[0009] In some embodiments, lithium from the negative electrode is added to the positive electrode via an intercalation or conversion mechanism.

[0010] In some embodiments, the lithium metal layer includes a thickness of less than 100 μm. In some embodiments, the positive electrode contains less than 10% by mass of lithium.

[0011] In some embodiments, the Disclosure provides an electrochemical system in which at least 90% of the total lithium is oxidized to Li+ during discharge and reduction, the potential difference between the negative and positive electrodes of the rechargeable energy source system is at least 2.5 volts, the expansion of the positive electrode volume due to discharge of the rechargeable energy source system is less than 15%, and the positive electrode capacity is at least 250 mAh / g.

[0012] In some embodiments, the Disclosure relates to a negative electrode comprising a layer of lithium metal, wherein in the discharge state of a rechargeable energy source system, the negative electrode comprises less than 10% of the total lithium in the rechargeable energy source system, and V x O yThe present invention provides an electrochemical system comprising a positive electrode containing less than 10% of the total lithium in the rechargeable energy source system, which is structurally stable in the charged state of the rechargeable energy source system, the difference in volume of the positive electrode between the discharged state and the charged state of the rechargeable energy source system is less than 10%, the potential difference between the negative electrode and the positive electrode excluding overvoltage is at least 2.5V, and the energy density of the rechargeable energy source system is at least 225Wh / kg.

[0013] In some embodiments, the disclosure provides a rechargeable energy source system including an electrochemical system disclosed herein.

[0014] In some embodiments, the present disclosure relates to a method for fabricating electrodes, comprising one or more V x O y F z The present invention provides a method comprising: mixing a precursor into a mixture; heating the mixture to at least 350°C or up to 550°C for at least 2 hours or up to 12 hours to generate a solid phase; coating the solid phase with carbon; mixing the solid phase with a binder; and casting the solid phase onto a current collector.

[0015] In some embodiments, one or more V x O y F z The precursor is V i F j , V k O l or both. In some embodiments, one or more V x O y F z The precursors include VF4, V2O5, or both.

[0016] In some embodiments, the method further includes calendering a solid phase on a current collector. In some embodiments, the solid phase includes a powder.

[0017] In some aspects, this disclosure provides for at least about 0.4 g / cm³ 3The present invention provides a rechargeable energy source system comprising a negative electrode containing a layer of lithium metal having a density and an impurity level of less than approximately 50 ppm by mass; and a positive electrode substantially free of lithium when the rechargeable energy source system is in a charged state, wherein the positive electrode has a capacity of at least 250 mAh / g and a gravimetric energy density of at least 800 Wh / kg.

[0018] In some embodiments, the positive electrode contains a vanadium atom. In some embodiments, the positive electrode is V x O y This includes. In some embodiments, the positive electrode is V x O y F z Includes. In some embodiments, the positive electrode is V6O5F 19 V3OF 11 , VO2F, VOF3, VPO4F, LiV3OF 11 Mn3V(PO4)6, V6O5F 19 , V2(PO4)3, LiVOF4, LiV(OF)2, LiV(OF)2, MnVP2(O4F)2, V4O7F5, LiV3CoO 10 , VPO5, VFeP2(O4F)2, TiVO4, LiTiV3O 10 , VFeP2(HO5)2, Li2VOF5, MnV4O 12 , VBO4, LiV2P2(O4F)2, LiV3CrO8, V4(OF3)3, LiV4O8, V(CO3)2, LiV5O 10 It includes at least one of VCuO4 or VCo3O8. In some embodiments, the positive electrode includes FePO4, NiMnCoO2, or TiS2.

[0019] In some embodiments, the rechargeable energy source system contains an excess of lithium, and the excess lithium constitutes less than 10% of the net amount of lithium transferred between the negative and positive electrodes during the discharge or charge of the rechargeable energy source system. In some embodiments, the positive electrode is configured to exhibit a volume change of less than 10% over at least 100 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the energy capacity loss of the rechargeable energy source system is less than 1% over at least 100 charge / discharge cycles. In some embodiments, the N / P ratio is less than 0.1 when the rechargeable energy source system is fully discharged. In some embodiments, the N / P ratio is about 0 when the rechargeable energy source system is fully discharged. In some embodiments, lithium from the negative electrode is added to the positive electrode via an intercalation or conversion mechanism. In some embodiments, the lithium metal layer includes a thickness of less than 100 μm. In some embodiments, the positive electrode contains less than 10 mass% lithium.

[0020] In some embodiments, the Disclosure provides a rechargeable energy source system in which a reduction reaction is carried out in at least 90% of the total lithium during charging and discharging, the potential difference between the negative and positive electrodes of the rechargeable energy source system is at least 2.5 volts, and the volume expansion of the positive electrode due to discharge of the rechargeable energy source system is less than 15%.

[0021] In some embodiments, the Disclosure relates to a negative electrode comprising a layer of lithium metal, wherein in the discharge state of a rechargeable energy source system, the negative electrode comprises less than 10% of the total lithium in the rechargeable energy source system, and V x O yThe present invention provides a rechargeable energy source system comprising a positive electrode containing less than 10% of the total lithium in the rechargeable energy source system while being structurally stable in the charged state of the rechargeable energy source system, wherein the volume difference of the positive electrode between the discharged state and the charged state of the rechargeable energy source system is less than 10%, the potential difference between the negative electrode and the positive electrode excluding overvoltage is at least 2.5V, and the energy density of the rechargeable energy source system is at least 350Wh / kg.

[0022] Reference All publications, patents, and patent applications referenced herein are incorporated by reference to the same extent as each individual publication, patent, or patent application is specifically and individually indicated as being incorporated by reference. To the extent that any publications and patents or patent applications incorporated by reference conflict with any disclosures contained herein, this specification is intended to supersede and / or take precedence over such conflicting material.

[0023] Novel features of this disclosure are described in detail in the appended claims. A better understanding of the features and advantages of this disclosure will be obtained by referring to the following detailed description illustrating exemplary embodiments in which the principles of this disclosure are utilized, and to the appended drawings. [Brief explanation of the drawing]

[0024] [Figure 1A] This diagram shows a rechargeable energy source in a charged state according to several embodiments, with arrows indicating the direction of lithium transport during discharge. [Figure 1B] This diagram shows a rechargeable energy source in a discharged state according to several embodiments, with arrows indicating the direction of lithium transport during charging. [Modes for carrying out the invention]

[0025] In some embodiments, the present disclosure provides a rechargeable energy source system. In some embodiments, the rechargeable energy source system includes a negative electrode. In some embodiments, the rechargeable energy source system includes a positive electrode.

[0026] As used herein, “cathode” may refer to the electrode where the reduction half-reaction occurs. As used herein, “anode” may refer to the electrode where the oxidation half-reaction occurs. As used herein, “redox reaction” may refer to the sum of two half-reactions. As used herein, “negative electrode” may refer to the electrode containing lithium metal. As used herein, “positive electrode” may refer to the electrode containing redox material.

[0027] In some embodiments, rechargeable energy storage systems utilize redox reactions in which charge carriers move between materials in an electrochemical process. In some embodiments, the charge carriers may be electrons or ions. Redox reactions can occur reversibly.

[0028] As used herein, “galvanic cell” may refer to a forward or discharge reaction that outputs energy. As used herein, “electrolytic cell” may refer to a reverse or charging reaction that consumes energy. In some embodiments, during charging, one electrode undergoes an oxidation half-reaction. In some embodiments, during discharge, the electrode undergoes a reduction half-reaction.

[0029] As used herein, “lithiation,” “forward reaction,” or “discharge reaction” may refer to the movement of lithium ions toward the negative electrode. In some embodiments, lithiation functions by an intercalation mechanism, a conversion mechanism, or both. As used herein, “intercalation mechanism” may refer to a mechanism by which lithium ions occupy pores in the scaffolding material. As used herein, “conversion mechanism” may refer to a mechanism by which lithium ions enter metal vacancies in the electrode. The conversion mechanism may include diffusion-based conversion, alloy-based conversion, or both.

[0030] In some embodiments, the present disclosure provides an electrochemical system. In some embodiments, the electrochemical system includes a negative electrode. In some embodiments, the electrochemical system includes a positive electrode.

[0031] In the design of rechargeable energy source systems, the selection of the cathode material offers several factors to consider. A cathode material may offer better energy density if (i) it can hold and release a large number of itinerant ions (Li+ in lithium batteries), and / or (ii) the potential difference between the cathode and anode materials is large. While not bound by any particular theory, the theoretical energy density of some rechargeable energy source systems can be calculated as the product of (i) the number of itinerant ions (Li+ in this system) involved in the Faraday (charge transfer) reaction at the electrode and (ii) the electrochemical potential associated with the Faraday reaction. Another factor to consider is the change in the specific volume of the cathode between the charged and discharged states of the rechargeable energy source system. A smaller change in specific volume can provide better structural stability to the cathode.

[0032] The cathode material may have atoms that can interconvert between two valence states. For example, the present disclosure provides specific embodiments of a cathode material synthesized to contain vanadium atoms and substantially no lithium. One such material is V6O5F 19And this is Li5V6O5F when saturated with lithium. 19 The chemical formula may include: If the cathode material interconverts between its two valence states during charging and discharging of a rechargeable energy source system, the material can theoretically utilize all of the lithium it receives. Increased utilization can reduce excess lithium. Reducing excess lithium can reduce the amount of lithium used in a rechargeable energy source system, thereby reducing cost and footprint. For example, V6O5F 19 +5 Li + ⇔Li5V6O5F 19 Interconversion between the two can provide a greater electrochemical potential to the reaction in relation to the change in the oxidation state of vanadium atoms in the material. Vanadium is an element that can exist in multiple oxidation states, e.g., +2, +3, +4, and +5. This reaction can increase the theoretical potential of the Faraday reaction, thereby increasing the amount of released (or stored) energy per lithium atom. In some embodiments, lithium can be added to the cathode material via a conversion mechanism. In some embodiments, lithium can also be added to the cathode via an intercalation mechanism.

[0033] The chemical and physical stability of the cathode material can improve the safety of rechargeable energy source systems and reduce capacity or energy density loss over time. Large volume changes in the cathode material may (but not necessarily) be associated with instability. V6O5F 19 +5 Li + ⇔Li5V6O5F 19 In this case, the theoretically expected volume change is 3%. Reducing the volume change is expected to provide better stability for the cathode material by reducing the initiation of new cracks and the extension of existing cracks.

[0034] In some embodiments, the present disclosure provides an electrochemical system. In some embodiments, the electrochemical system provides at least about 0.4 g / cm³ 3The system includes a negative electrode comprising a layer of lithium metal having a density of . In some embodiments, the electrochemical system includes a positive electrode that is substantially lithium-free when the rechargeable energy source system is in a charged state. In some embodiments, the positive electrode has a capacity of at least 300 mAh / g. In some embodiments, the positive electrode has a capacity of at least 250 mAh / g. In some embodiments, the positive electrode has a gravimetric energy density of at least 800 Wh / kg. In some embodiments, the positive electrode is configured to exhibit a volume change of less than about 15% between a discharged state and a charged state. In some embodiments, the positive electrode is configured to maintain the volume change over at least 100 charge / discharge cycles of the electrochemical system.

[0035] In some embodiments, lithium from the negative electrode is added to the positive electrode via an intercalation or conversion mechanism. In some embodiments, the positive electrode contains vanadium atoms. In some embodiments, the positive electrode is V x O y This includes. In some embodiments, the positive electrode is V x O y F z Includes. In some embodiments, the positive electrode is V6O5F 19 V3OF 11 , VO2F, VOF3, VPO4F, LiV3OF 11 Mn3V(PO4)6, V6O5F 19 , V2(PO4)3, LiVOF4, LiV(OF)2, LiV(OF)2, MnVP2(O4F)2, V4O7F5, LiV3CoO 10 , VPO5, VFeP2(O4F)2, TiVO4, LiTiV3O 10 , VFeP2(HO5)2, Li2VOF5, MnV4O 12 , VBO4, LiV2P2(O4F)2, LiV3CrO8, V4(OF3)3, LiV4O8, V(CO3)2, LiV5O 10 It includes at least one of VCuO4 or VCo3O8. In some embodiments, the positive electrode includes FePO4, NiMnCoO2, or TiS2.

[0036] In some embodiments, the rechargeable energy source system contains an excess of lithium, and the excess lithium constitutes less than 10% of the net amount of lithium transferred between the negative and positive electrodes during the discharge or charge of the rechargeable energy source system. In some embodiments, the positive electrode is configured to exhibit a volume change of less than 10% over at least 100 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the energy capacity loss of the rechargeable energy source system is less than 1% over at least 100 charge / discharge cycles. In some embodiments, the energy capacity loss of the rechargeable energy source system is less than 1% over at least 300 charge / discharge cycles. In some embodiments, the N / P ratio is less than 0.1 when the rechargeable energy source system is completely discharged. In some embodiments, the N / P ratio is about 0 when the rechargeable energy source system is completely discharged.

[0037] In some embodiments, the lithium metal layer includes a thickness of less than 100 μm. In some embodiments, the positive electrode contains less than 10% by mass of lithium.

[0038] In some embodiments, the Disclosure provides an electrochemical system in which at least 90% of the total lithium is oxidized to Li+ during discharge and reduction, the potential difference between the negative and positive electrodes of the rechargeable energy source system is at least 2.5 volts, the expansion of the positive electrode volume due to discharge of the rechargeable energy source system is less than 15%, and the positive electrode capacity is at least 250 mAh / g.

[0039] In some embodiments, the Disclosure relates to a negative electrode comprising a layer of lithium metal, wherein in the discharge state of a rechargeable energy source system, the negative electrode comprises less than 10% of the total lithium in the rechargeable energy source system, and V x O yThe present invention provides an electrochemical system comprising a positive electrode containing less than 10% of the total lithium in the rechargeable energy source system, which is structurally stable in the charged state of the rechargeable energy source system, the difference in volume of the positive electrode between the discharged state and the charged state of the rechargeable energy source system is less than 10%, the potential difference between the negative electrode and the positive electrode excluding overvoltage is at least 2.5V, and the energy density of the rechargeable energy source system is at least 225Wh / kg.

[0040] In some embodiments, the disclosure provides a rechargeable energy source system including an electrochemical system disclosed herein.

[0041] In some embodiments, the present disclosure provides a method for fabricating electrodes. In some embodiments, the method involves one or more V x O y F zThe method includes mixing a precursor into a mixture. In some embodiments, the method includes heating the mixture to at least 350°C or up to 550°C for at least 2 hours or up to 12 hours to produce a solid phase. In some embodiments, the method includes heating the mixture to at least 375, 400, 425, 450, 475, 500, 525, or 525°C. In some embodiments, the method includes heating the mixture to a maximum of 375, 400, 425, 450, 475, 500, 525, or 525°C. In some embodiments, the method includes heating the mixture for at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours. In some embodiments, the method includes heating the mixture for a maximum of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours. In some embodiments, the method includes coating the solid phase with a conductive material. In some embodiments, the conductive material includes carbon. In some embodiments, the method includes mixing a solid phase with a binder. In some embodiments, the binder includes a polymer. In some embodiments, the polymer includes polyvinylidene fluoride. In some embodiments, the method includes casting the solid phase onto a current collector. In some embodiments, one or more V x O y F z The precursor is V i F j , V k O l or both. In some embodiments, one or more V x O y F z The precursor comprises VF4, V2O5, or both. In some embodiments, the method further comprises calendering a solid phase on a current collector. In some embodiments, the solid phase comprises a powder.

[0042] positive electrode In some embodiments, the present disclosure provides a cathode. The cathode may include a redox material. The redox material may be synthesized to be substantially lithium-free. The redox material may be in contact with a substrate.

[0043] The redox material may include a lithium intercalate material. The redox material may include a multi-electron intercalate material. The redox material may include a transition metal in which the change in oxidation state between the charged and discharged states is at least 2. The redox material may be configured to receive lithium via an intercalation mechanism, a conversion mechanism, or both.

[0044] This specification provides various redox materials. Redox materials can be integrated into rechargeable energy source systems. Table 1 provides a list of several redox materials for cathodes according to several embodiments (volts: V; milliampere-hours: mAh; grams: g; watt-hours: Wh; kilograms: kg). [Table 1]

[0045] Redox materials can contain atoms with multiple oxidation states. Redox materials can contain atoms of titanium, vanadium, chromium, manganese, iron, cobalt, copper, germanium, arsenic, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, tin, antimony, or any combination thereof. Redox materials can contain vanadium atoms.

[0046] The redox material may contain transition metals. The redox material may contain at least one of the following atoms: vanadium, cobalt, nickel, cobalt-aluminum alloy, manganese, niobium, molybdenum, technetium, tungsten, rhenium, rhodium, ruthenium, iridium, palladium, or platinum. The redox material may contain vanadium atoms. The redox material may contain oxides. The redox material may contain V x O y It can include redox material V x O y F zIt can include. "X", "Y", and "Z" can be integers. "X", "Y", and "Z" can be real numbers that can represent variations from the exact stoichiometric ratio. The redox material is V6O5F 19 、V3OF 11 、VO2F, VOF3, VPO4F, LiV3OF 11 、Mn3V(PO4)6, V6O5F 19 、V2(PO4)3, LiVOF4, LiV(OF)2, LiV(OF)2, MnVP2(O4F)2, V4O7F5, LiV3CoO 10 、VPO5, VFeP2(O4F)2, TiVO4, LiTiV3O 10 、VFeP2(HO5)2, Li2VOF5, MnV4O 12 、VBO4, LiV2P2(O4F)2, LiV3CrO8, V4(OF3)3, LiV4O8, V(CO3)2, LiV5O 10 、VCuO4, VCo3O8, or at least one of any combination thereof. The redox material can include FePO4, NiMnCoO2, or TiS2.

[0047] The redox material can include metal sulfides. The redox material can include titanium disulfide. The redox material can include metal oxides. The positive electrode can include Li x MO2, where M is a metal. The redox material can include vanadium atoms. The redox material can include vanadium, cobalt, nickel, cobalt - aluminum alloy, manganese, niobium, molybdenum, technetium, tungsten, rhenium, rhodium, ruthenium, iridium, palladium, platinum atoms, or any combination thereof. The redox material can include polyatomic anions. The polyatomic anion can include PO4.

[0048] The redox material can include additives. The redox material can include phosphate-based materials such as FePO4, VPO4F, V2(PO4)2F3, FePO4F, and V2(PO4)3; oxides such as CoO2, V2O5, orthorhombic MnO2, layered iron oxide FeO2, chromium oxide CrO2, layered Ni 0.5 Mn 0.5 O2, and V6O 15 nanorods; layered sulfides such as TiS2; perovskite transition metal fluorides, or mixtures thereof. The redox material can include a conductive filler such as graphene. The redox material can include a binder that can be a polymer such as polyvinylidene fluoride.

[0049] The redox material can include less than 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% by mass of lithium. The redox material can include more than 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% by mass of lithium. For example, the redox material can include less than 10% by mass of lithium. The amount of lithium can be measured in the delithiated state.

[0050] In some embodiments, the positive electrode can be selected based on factors including, but not limited to, high conductivity (both ionic and electronic), low toxicity, high crustal abundance, low oxygen generation, an upper limit voltage less than 4.5, and a low voltage cut-off higher than 50% of the upper cut-off window.

[0051] In some embodiments, the positive electrode includes a capacity of at least 275, 280, 290, 300, or 305 mAh / g. In some embodiments, the positive electrode includes a capacity of at most 275, 280, 290, 300, or 305 mAh / g.

[0052] Structure Redox materials can take various forms. For example, redox materials can take the form of sheets, ribbons, or particles. Redox materials can take the form of microstructures. Redox materials can take the form of nanostructures. Microstructures or nanostructures can take the form of substantially spherical, cylindrical, or layered forms, or any combination thereof. Such structures may be deposited on the surface of a substrate.

[0053] additives The redox material may contain a binder. The binder can bond the redox material to the current collector. The binder may be conductive. The binder may contain polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers (including ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber ("SBR"), acrylic SBR, epoxy resins, and nylon). The binder may contain carbon black or steam-pulverized carbon fibers. The binder may contain polyvinylidene fluoride (PVDF), sodium alginate, and sodium carboxymethylcellulose. The binder may contain PVDF, polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and polyimide. The binder may contain graphene or carbon nanotubes.

[0054] The redox material may include a surface coating. The surface coating may include oxides, hydroxides, oxyhydroxides, oxycarbonates, or hydroxycarbonates. The surface coating may be amorphous or crystalline. The surface coating may include magnesium (Mg), aluminum (Al), cobalt (Co), potassium (K), sodium (Na), calcium (Ca), silicon (Si), titanium (Ti), vanadium (V), tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr) atoms, or any combination thereof. The surface coating may be formed using spray coating, dipping, or any other suitable method.

[0055] The redox material may contain a polymer binder. The polymer binder may contain a block copolymer. The block copolymer can provide hydrophobic domains on the electrode surface. The hydrophobic polymer film can bond to the hydrophobic domains on the surface of the redox material.

[0056] Base material The substrate may include a current collector. The current collector may include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, or silver, and aluminum-cadmium alloys. The current collector may take various forms, including films, sheets, foils, nets, porous structures, foams, and nonwoven fabrics. The current collector may include carbon, carbon paper, carbon cloth, or metal or precious metal mesh or foil. The current collector may have fine irregularities on its surface to enhance the adhesion strength of the current collector to the redox material. The current collector may have a thickness of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 μm. The current collector can have a maximum thickness of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 μm.

[0057] characteristics The positive electrode can be configured to have a stable capacity. Over numerous cycles, the positive electrode can resist the loss of redox material. For example, if a lithium-containing redox material fragment is released, uncontrolled crack formation and propagation can lead to the loss of redox material. The fragment may become electrically insulated from the rest of the positive electrode, and the lithium contained within may not be able to participate in the redox reaction and contribute to the capacity and energy density of the electrochemical system. The stable volume of the redox material with respect to its charge state, temperature, and pressure can reflect the physical stability of the positive electrode.

[0058] The positive electrode capacity may be at least 50, 100, 150, 200, 250, 300, 350, 400, 450, or 500 mAh / g. The positive electrode capacity may be up to 50, 100, 150, 200, 250, 300, 350, 400, 450, or 500 mAh / g. For example, the positive electrode capacity may be at least 250 mAh / g. The positive electrode energy density may be at least 200, 400, 600, 800, 1000, 1200, 1400, or 1600 Wh / kg. The positive electrode energy density may be up to 200, 400, 600, 800, 1000, 1200, 1400, or 1600 Wh / kg. For example, the positive electrode energy density may be at least 800 Wh / kg.

[0059] In some embodiments, the redox material exhibits a volume change of less than approximately 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 4%, 3%, 2%, or 1% after a predetermined number of cycles. In some embodiments, the redox material exhibits a volume change of more than approximately 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 4%, 3%, 2%, or 1% after a predetermined number of cycles. The predetermined number of cycles may be at least 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, or 5000 cycles. The specified number of cycles may be a maximum of 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, or 5000 cycles. Cycling may be performed at 2V-4.5V, 3V-4.5V, or 2V-3V. Cycling can be performed at C rates of at least C / 20:C / 20, C / 10:C / 10, C / 5:C / 5, C / 2:C / 2, 1C:1C, or 2C:2C. Cycling can be performed at C rates of up to C / 20:C / 20, C / 10:C / 10, C / 5:C / 5, C / 2:C / 2, 1C:1C, or 2C:2C. Cycling is permitted with a C-rate of at least C / 2:C / 5, 1C:C / 5, 2C:C / 5, C / 2:C / 2, 1C:C / 2, 2C:C / 2, C / 2:1C, 1C:1C, 2C:1C, C / 2:2C, 1C:2C, or 2C:2C. Cycling is permitted with a C-rate of at most C / 2:C / 5, 1C:C / 5, 2C:C / 5, C / 2:C / 2, 1C:C / 2, 2C:C / 2, C / 2:1C, 1C:1C, 2C:1C, C / 2:2C, 1C:2C, or 2C:2C.

[0060] In some embodiments, the positive electrode energy capacity loss may be about 30%, 25%, 20%, 15%, 10%, 5%, 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02%, or less than 0.01% over a predetermined number of cycles. In some embodiments, the positive electrode energy capacity loss may be about 30%, 25%, 20%, 15%, 10%, 5%, 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02%, or greater than 0.01% over a predetermined number of cycles. The predetermined number may be at least 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 1000, or 5000 cycles. The specified number of cycles may be a maximum of 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 1000, or 5000 cycles. Cycling may be 2V-4.5V, 3V-4.5V, or 2V-3V. Cycling can be performed at C rates of at least C / 20:C / 20, C / 10:C / 10, C / 5:C / 5, C / 2:C / 2, 1C:1C, or 2C:2C. Cycling can be performed at C rates of up to C / 20:C / 20, C / 10:C / 10, C / 5:C / 5, C / 2:C / 2, 1C:1C, or 2C:2C. Cycling is permitted with a C-rate of at least C / 2:C / 5, 1C:C / 5, 2C:C / 5, C / 2:C / 2, 1C:C / 2, 2C:C / 2, C / 2:1C, 1C:1C, 2C:1C, C / 2:2C, 1C:2C, or 2C:2C. Cycling is permitted with a C-rate of at most C / 2:C / 5, 1C:C / 5, 2C:C / 5, C / 2:C / 2, 1C:C / 2, 2C:C / 2, C / 2:1C, 1C:1C, 2C:1C, C / 2:2C, 1C:2C, or 2C:2C.

[0061] In some embodiments, the positive electrode has a Coulomb efficiency of at least 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, or 99.9% over a predetermined number of cycles. In some embodiments, the positive electrode has a Coulomb efficiency of up to 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, or 99.9% over a predetermined number of cycles. The predetermined number of cycles may be at least 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 1000, or 5000 cycles. The predetermined number of cycles may be at most 50, 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 1000, or 5000 cycles. Cycling may be 2V-4.5V, 3V-4.5V, or 2V-3V. Cycling may be performed at C rates of at least C / 20:C / 20, C / 10:C / 10, C / 5:C / 5, C / 2:C / 2, 1C:1C, or 2C:2C. Cycling can be done with a maximum C-rate of C / 20:C / 20, C / 10:C / 10, C / 5:C / 5, C / 2:C / 2, 1C:1C, or 2C:2C. Cycling can be done with a minimum C-rate of C / 2:C / 5, 1C:C / 5, 2C:C / 5, C / 2:C / 2, 1C:C / 2, 2C:C / 2, C / 2:1C, 1C:1C, 2C:1C, C / 2:2C, 1C:2C, or 2C:2C. Cycling can be done with a maximum C-rate of C / 2:C / 5, 1C:C / 5, 2C:C / 5, C / 2:C / 2, 1C:C / 2, 2C:C / 2, C / 2:1C, 1C:1C, 2C:1C, C / 2:2C, 1C:2C, or 2C:2C.

[0062] In some embodiments, the positive electrode has a capacity of at least 250 mAh / g. In some embodiments, the positive electrode has a capacity of at least 100, 150, 200, 250, 300, or 350 mAh / g. In some embodiments, the positive electrode has a capacity of up to 500 mAh / g. In some embodiments, the positive electrode has a capacity of up to 450, 400, 350, 300, 250, 200, or 150 mAh / g.

[0063] In some embodiments, the positive electrode has a gravimetric energy density of at least 800 Wh / kg. In some embodiments, the positive electrode has a gravimetric energy density of at least 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, or 1300 Wh / kg. In some embodiments, the positive electrode has a gravimetric energy density of up to 1500 Wh / kg. In some embodiments, the positive electrode has a gravimetric energy density of up to 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, or 1450 Wh / kg.

[0064] In some embodiments, the positive electrode includes atoms having multiple oxidation states. In some embodiments, the positive electrode includes atoms of titanium, vanadium, chromium, manganese, iron, cobalt, copper, germanium, arsenic, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, tin, antimony, or any combination thereof. In some embodiments, the positive electrode includes a vanadium atom.

[0065] In some embodiments, the positive electrode contains an oxide. In some embodiments, the positive electrode is V x O y This includes. In some embodiments, the positive electrode is V x O y F zThis includes the following: "X", "Y", and "Z" can be integers. "X", "Y", and "Z" can be real numbers that can represent variations from the exact stoichiometric ratio. In some embodiments, the positive electrode is V6O5F 19 V3OF 11 , VO2F, VOF3, VPO4F, LiV3OF 11 Mn3V(PO4)6, V6O5F 19 , V2(PO4)3, LiVOF4, LiV(OF)2, LiV(OF)2, MnVP2(O4F)2, V4O7F5, LiV3CoO 10 , VPO5, VFeP2(O4F)2, TiVO4, LiTiV3O 10 , VFeP2(HO5)2, Li2VOF5, MnV4O 12 , VBO4, LiV2P2(O4F)2, LiV3CrO8, V4(OF3)3, LiV4O8, V(CO3)2, LiV5O 10 It includes at least one of VCuO4 or VCo3O8. In some embodiments, the positive electrode includes FePO4, NiMnCoO2, or TiS2.

[0066] A rechargeable energy source system may include a negative electrode. The negative electrode may include lithium metal. The lithium metal may be contained in a layer. The layer of lithium metal may be substantially pure or high density. For example, the layer of lithium metal may contain at least 0.4 g / cm³ 3 The density may include the following: In some embodiments, the lithium metal layer may have a density of at least 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, or 0.52 g / cm³. 3 The density can include 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, or 0.53 g / cm³. 3The density may include the following: The density can be measured, for example, at room temperature. In some embodiments, the lithium metal layer may contain less than 50 ppm of impurities. The lithium metal layer may contain less than 45, 40, 35, 30, 25, 20, 15, 10, or 5 ppm of impurities. The lithium metal layer may contain more than 0, 5, 10, 15, 20, 25, 30, 35, 40, or 45 ppm of impurities. The impurities can be determined by mass or moles. The impurities may be metallic impurities.

[0067] A rechargeable energy source system may be an "anodeless" system. As used herein, an "anodeless" system may refer to a rechargeable energy storage system that is anode-free in a fully discharged state but includes a current collector. An "anodeless" system may include a current collector, but may also include a small amount of anode material (e.g., a small amount of residual lithium that can be identified using surface inspection techniques) when fully discharged.

[0068] In some embodiments, the anodic reaction in an anodeless system occurs within the electrolyte rather than on or within the substrate. For example, in a wet "anode-free" lithium metal battery system, the negative electrode contains metallic lithium, and the positive electrode functions within the electrolyte. The potential of the positive electrode reaction can be collected by an electrochemically inert metal current collector. The electrolyte can function as both the electrolyte and the site of the positive electrode reaction. The electrolyte and the positive electrode may be referred to as "phase integration" or "mutual solvation."

[0069] The N / P ratio can be a measure of the capacity ratio between the negative and positive electrodes in a rechargeable energy system. In some embodiments, a rechargeable energy source system includes an N / P ratio of less than 0.1 when the rechargeable energy source system is completely discharged. In some embodiments, a rechargeable energy source system includes N / P ratios of 0.2, 0.15, 0.1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, 1e when the rechargeable energy source system is completely discharged. -3 , 1e -4 , 1e -5 , or 1e -6 Includes an N / P ratio of less than 0.15, 0.1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, 1e -3 , 1e -4 , 1e -5 , or 1e -6This includes an N / P ratio greater than 0. In some embodiments, the rechargeable energy source system includes an N / P ratio of about 0 when the rechargeable energy source system is completely discharged. In some embodiments, the positive electrode contains less than 10 mass% lithium in the rechargeable energy source system. In some embodiments, the positive electrode contains less than 20 mass%, 15 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.8 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.4 mass%, 0.3 mass%, 0.2 mass%, or less than 0.1 mass% lithium in the rechargeable energy source system when charged. In some embodiments, the positive electrode contains more than 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.8% by mass, 0.7% by mass, 0.6% by mass, 0.5% by mass, 0.4% by mass, 0.3% by mass, 0.2% by mass, 0.1% by mass, or 0% by mass in the rechargeable energy source system when charged. When charged, the negative electrode may include a layer of lithium metal with a thickness of less than 100 μm. When charged, the negative electrode may include a layer of lithium metal with a thickness of less than 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10 μm. During charging, the negative electrode may include a layer of lithium metal with a thickness exceeding 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, or 400 μm.

[0070] A rechargeable energy source system may contain some excess lithium, or it may not contain any excess lithium. Excess lithium may be a small portion of the net lithium transferred between the negative and positive electrodes during the discharge or charge of the rechargeable energy source system. Excess lithium may be a small portion of the net lithium transferred between two opposing electrodes during the discharge or charge of the rechargeable energy source system. Excess lithium may be less than 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%. Excess lithium may be greater than 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%.

[0071] The positive electrode can be configured to have a stable capacity. Over a large number of cycles, the positive electrode can resist the loss of active material. For example, if a lithium-containing positive electrode fragment is released, uncontrolled crack formation and extension can lead to the loss of active material. The fragment may become electrically insulated from the rest of the positive electrode, and the lithium contained within it may not be able to participate in redox reactions, contributing to the capacity and energy density of the electrochemical system. The volume stability of the positive electrode may reflect the physical stability of the positive electrode. In some embodiments, the positive electrode may be configured to exhibit a volume change of less than about 10% over at least 100 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the positive electrode may be configured to exhibit a volume change of less than 30%, 25%, 20%, 15%, 10%, 5%, 4%, 3%, 2%, or 1% over at least 100 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the positive electrode may be configured to exhibit a volume change of at least 0% over at least 100 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the positive electrode may be configured to exhibit a volume change of more than 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%, or 25% over at least 100 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the positive electrode may be configured to exhibit a volume change of less than about 20% over at least 1000 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the positive electrode may be configured to exhibit a volume change of less than about 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5% over at least 1000 charge / discharge cycles of the rechargeable energy source system. In some embodiments, the positive electrode may be configured to exhibit a volume change of more than about 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, or 45% over at least 1000 charge / discharge cycles of the rechargeable energy source system.In some embodiments, the energy capacity loss of a rechargeable energy source system may be less than about 1% over at least 100 charge / discharge cycles. In some embodiments, the energy capacity loss of a rechargeable energy source system may be less than about 30%, 25%, 20%, 15%, 10%, 5%, 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02%, or 0.01% over at least 100 charge / discharge cycles. In some embodiments, the energy capacity loss of a rechargeable energy source system may be greater than about 0.01% over at least 100 charge / discharge cycles. In some embodiments, the energy capacity loss of a rechargeable energy source system may be about 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%, or more than 25% over at least 100 charge / discharge cycles.

[0072] electrolyte In some embodiments, the electrolyte includes an aqueous electrolyte. In some embodiments, the electrolyte includes a non-aqueous electrolyte. In some embodiments, the electrolyte includes a polymer electrolyte. In some embodiments, the electrolyte includes an organic electrolyte. In some embodiments, the electrolyte includes a lithium salt. In some embodiments, the electrolyte includes an ionic liquid. In some embodiments, the electrolyte includes a deep eutectic solvent. The electrolyte may be used in the manufacture of lithium metal electrodes. The electrolyte may be used in rechargeable energy source systems.

[0073] In some embodiments, the electrolyte is non-flammable or fire-resistant. In some embodiments, the electrolyte is substantially non-volatile at room temperature and room pressure. In some embodiments, the electrolyte is non-flammable at room temperature and room pressure. In some embodiments, the electrolyte is self-extinguishing. In some embodiments, the electrolyte contains additives, such as nitrogen, sulfur, phosphorus, or silicon compounds.

[0074] In some embodiments, the electrolyte includes a decomposition voltage of at least 2, 3, 4, 5, or 6 V. In some embodiments, the electrolyte includes a decomposition voltage of up to 2, 3, 4, 5, or 6 V. In some embodiments, the electrolyte includes a dielectric constant of at least 2, 5, 10, 20, 30, 40, 50, 60, 70, or 80. In some embodiments, the electrolyte includes a dielectric constant of up to 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90. The electrolyte can include a variety of viscosities. Polymer or polymer solution electrolytes can include high viscosities because viscosity can increase exponentially with the molecular weight of the polymer above the critical molecular weight (e.g., entanglement molecular weight). In some embodiments, the electrolyte includes a viscosity of at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 mPa·s. In some embodiments, the electrolyte contains a viscosity of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 kPa·s. In some embodiments, the electrolyte contains a viscosity of up to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 mPa·s. In some embodiments, the electrolyte contains a viscosity of up to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 Pa·s.In some embodiments, the electrolyte contains a viscosity of up to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 kPa·s.

[0075] Various organic electrolytes can be used. In some embodiments, the organic electrolyte may include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, 1,3-dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, oxolan-2-one, and any combination thereof. In some embodiments, the electrolyte may include organic carbonate compounds, ester compounds, ether compounds, ketone compounds, alcohol compounds, aprotic bipolar solvents, or combinations thereof. The carbonate compound may be an open-chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate derivative thereof, or a combination thereof.

[0076] In some embodiments, the linear carbonate compound may be diethyl carbonate ("DEC"), dimethyl carbonate ("DMC"), dipropyl carbonate ("DPC"), methylpropyl carbonate ("MPC"), ethylpropyl carbonate ("EPC"), methylethyl carbonate ("MEC"), and combinations thereof. In some embodiments, the cyclic carbonate compound may be ethylene carbonate ("EC"), propylene carbonate ("PC"), butylene carbonate ("BC"), fluoroethylene carbonate ("FEC"), vinylethylene carbonate ("VEC"), and combinations thereof. In some embodiments, the fluorocarbonate compound may be fluoroethylene carbonate ("FEC"), 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,4,5-trifluoroethylene carbonate, 4,4,5,5-tetrafluoroethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methylethylene carbonate, 4,4,5-trifluoro-5-methylethylene carbonate, trifluoromethylethylene carbonate, and combinations thereof. In some embodiments, the carbonate compound may include a combination of cyclic carbonates and linear carbonates, taking into account the dielectric constant and viscosity of the electrolyte. In some embodiments, the carbonate compound may be a mixture of the linear carbonates and / or cyclic carbonate compounds described above and the fluorocarbonate compound. In some embodiments, fluorocarbonate compounds can increase the solubility of lithium salts, thereby improving the ionic conductivity of the electrolyte and promoting the formation of thin films on the negative electrode. In some embodiments, ester compounds include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate ("MP"), ethyl propionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and methyl formate.In some embodiments, the ether compounds are dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran. An example of a ketone compound is cyclohexanone. In some embodiments, the alcohol compound may be ethyl alcohol or isopropyl alcohol. In some embodiments, the aprotic solvent may be nitriles (e.g., R-CN, where R is a C2-C20 linear, branched, or cyclic hydrocarbon moiety that may include a double bond, aromatic ring, or ether bond), amides (e.g., formamide and dimethylformamide), dioxolanes (e.g., 1,2-dioxolane and 1,3-dioxolane), methyl sulfoxides, sulfolanes (e.g., sulfolane and methylsulfolane), 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidinone, nitromethane, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and triesters. In some embodiments, the electrolyte may include an aromatic hydrocarbon organic solvent in a carbonate solvent.In some embodiments, the aromatic hydrocarbon organic solvent is benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 2,3-difluorotoluene, 2,4-difluorotoluene, 2,5-difluorotoluene, 2,6-difluorotoluene, 3,4-difluorotoluene, 3,5-difluorotoluene, 2,3,4-trifluorotoluene, 2,3,5-trifluorotoluene, 2,3,6-trifluorotoluene, 3,4,5-trifluorotoluene 2,4,5-trifluorotoluene, 2,4,6-trifluorotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2,3-dichlorotoluene, 2,4-dichlorotoluene, 2,5-dichlorotoluene, 2,6-dichlorotoluene, 2,3,4-trichlorotoluene, 2,3,5-trichlorotoluene, 2,3,6-trichlorotoluene, 3,4,5-trichlorotoluene, 2,4,5-trichlorotoluene, 2,4,6-trichlorotoluene, 2-iodotoluene, 3-iodotoluene This may include diiodotoluene, 4-iodotoluene, 2,3-diiodotoluene, 2,4-diiodotoluene, 2,5-diiodotoluene, 2,6-diiodotoluene, 3,4-diiodotoluene, 3,5-diiodotoluene, 2,3,4-triiodotoluene, 2,3,5-triiodotoluene, 2,3,6-triiodotoluene, 3,4,5-triiodotoluene, 2,4,5-triiodotoluene, 2,4,6-triiodotoluene, o-xylene, m-xylene, p-xylene, and combinations thereof.

[0077] Various polymer electrolytes can be used. Polymer electrolytes may include poly(ethylene oxide), poly(vinyl alcohol), poly(methyl methacrylate), poly(caprolactone), poly(chitosan), poly(vinylpyrrolidone), poly(vinyl chloride), poly(vinyl fluoride), poly(imide), or any combination thereof, which are inherently lithium ion conductors or can be doped with one or more lithium salts to make the polymer lithium conductive.

[0078] You can use any of the various ionic liquids listed in the National Institute of Standards and Technology's (NIST) Ionic Liquid Database (ILThermo).

[0079] Various lithium salts can be used. These lithium salts may include lithium 12-hydroxystearate, lithium acetate, lithium amide, lithium aspartate, lithium azide, lithium bis(trifluoromethanesulfonyl)imide, lithium borohydride, lithium bromide, lithium carbonate, lithium chlorate, lithium chloride, lithium citrate, lithium cyanide, lithium diphenylphosphine, lithium hexafluorogermanate, lithium hexafluorophosphate, lithium hypochlorite, lithium hypofluorite, lithium metaborate, lithium methoxide, lithium naphthalene, lithium niobate, lithium nitrate, lithium nitrite, lithium oxalate, lithium perchlorate, lithium stearate, lithium succinate, lithium sulfate, lithium sulfide, lithium superoxide, lithium tantalate, lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate, lithium triflate, lithium tungstate, or any combination thereof. In some embodiments, the electrolyte may include a lithium salt containing an organic anion selected from the group consisting of trifluoromethanesulfonyl-imide (TFSI), N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyruTFSI), trifluoromethanesulfonyl-imide, bis(trifluoromethanesulfonyl)imide (LiTFSI), and l-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI). In some embodiments, the cathode solution 290 may contain an ionic liquid forming salt dissolved in 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME). In some embodiments, the electrolyte may include Li2SO4, Li2CO3, LiPF6, LiBF4, LiBH4, LiBO, LiDFOB, LiClO4, LiTFSI, and combinations thereof.In some embodiments, the electrolyte is LiPF6, LiBF4, LiBH4, LiBO, LiDFOB, LiSbF6, LiAsF6, LiSbF6, LiCF3SO3, Li(CF3SO2)3C, Li(CF3SO2)2N, LiC4F9SO3, LiClO4, LiAlO4, LiAlCl4, LiAlF4, LiBPh4, LiBioCl. 10 , CH3SO3Li, C4F3SO3Li, (CF3SO2)2NLi, LiN(C x F 2x+1 SO2)(C x F 2y+1 The following can be included: SO2) (wherein x and y are natural numbers), CF3CO2Li, LiCl, LiBr, LiI, LIBOB (lithium bisoxalate borate), lithium lower aliphatic carboxylate, lithium terphenylborate, lithium imide, and any combination thereof. In some embodiments, the concentration of the lithium salt may be in the range of about 0.1 mol ("M") to about 2.0 M. In some embodiments, the concentration of the lithium salt is at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, or 3 M. In some embodiments, the lithium salt concentration is up to 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, or 3M.

[0080] The electrolyte may include a lithium-conducting polymer. The lithium-conducting polymer may be a copolymer. In some embodiments, the polymer may include a block copolymer or a random copolymer. In some embodiments, a portion of the block copolymer is in contact with the lithium metal, and this portion is substantially inactive with the lithium metal. The block copolymer can be, for example, annealed to separate microphases and provide an exposed hydrophobic surface that is substantially inactive with the lithium metal. Alternatively, the block copolymer may further include percolating hydrophilic domains that provide pathways for lithium ions to pass from one side of the block copolymer to the other. In some embodiments, the block copolymer includes diblock copolymers, triblock copolymers, triblockterpolymers, multiblock copolymers, and grafted copolymers. In some embodiments, the block copolymer may include PDMS-PEG (e.g., poly(polydimethylsiloxane methacrylate)-b-poly(poly(ethylene glycol) methacrylate)). In some embodiments, the block copolymer may include POEM-b-PLMA, POEM-P(PDMSMA), PBA-b-PPEGMA, or any combination thereof.In some embodiments, the copolymer may include poly(butyl acrylate) (PBA), poly(butyl methacrylate) (PBMA), poly(lauryl methacrylate) (PLMA), poly(ethylene) (PE), poly(ethylene-alt-propylene) (PEP), poly(urethane) (PU), poly(butadiene) (PB), poly(polyvinylidene methacrylate) (PPVDFMA), poly(polytetrafluoroethylene methacrylate) (PPTFEMA), poly(perfluoropolyether) (PFPE), poly(perfluoropolyether methacrylate) (PFPEMA), poly(perfluoropolyether acrylate) (PFPEA), poly(poly(ethylene glycol) methacrylate) (PPEGMA), poly(poly(ethylene glycol) acrylate) (PPEGA), poly(perfluoropolyether methacrylate) (PFPEMA), poly(perfluoropolyether acrylate) (PFPEA), or any combination thereof.

[0081] Hydrophobic polymers may include, for example, cyclic olefin copolymers, fluorinated ethylene propylene, ethylene-methyl acrylate copolymers, polymonochlorotrifluoroethylene, perfluoroalkoxy polymers, polymethylpentene, polypropylene, polyphenylene sulfide, polystyrene, polytetrafluoroethylene, polyvinyl chloride, polyethylene, ethylene vinyl acetate, or any combination thereof.

[0082] In some embodiments, the electrolyte may be a highly conductive electrolyte having a lithium transport fraction greater than 0.3, low flammability, and weak solvation ability to minimize charge transfer resistance. In some embodiments, fluorinated compounds tend to create an inorganic-rich SEI layer that promotes higher Coulomb efficiency.

[0083] Separator A separator can be provided between the negative electrode and the positive electrode. The separator can be in contact with the lithium metal layer. The separator can be in contact with the positive electrode.

[0084] The separator may include a polymer or ceramic film. The separator may be moistened with an electrolyte. The separator may include a surface that is substantially inactive with lithium metal.

[0085] The separator may include a polypropylene surface. The separator may include a single layer or multiple layers. The separator may include glass fiber, polyester, Teflon, polyethylene, polypropylene, polyvinylidene fluoride ("PVDF"), polytetrafluoroethylene ("PTFE"), or a combination thereof. The separator may include at least three layers. The at least three layers may, in order, be polypropylene, polyethylene, and polypropylene.

[0086] The separator can have a porosity of at least 10, 20, 30, 40, 50, 60, 70, or 80%. The separator can have a porosity of up to 10, 20, 30, 40, 50, 60, 70, or 80%. The separator can have a porosity of at least 55%. The separator can have a porosity of up to 55%. The separator can have a porosity of approximately 55%.

[0087] The separator can have a thickness of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 μm. The separator can have a maximum thickness of 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 μm. The separator can have a thickness of 5 to 50 μm.

[0088] The separator can selectively conduct lithium ions between the negative and positive electrodes. It can substantially prevent or inhibit the movement of organic solvents, lithium salt anions, water, or contaminants between the negative and positive electrodes. The separator may be a hydrophobic polymer. The separator may contain lithium ion conductive channels.

[0089] [Examples] The following embodiments are provided to further illustrate some embodiments of the present disclosure, but are not intended to limit the scope of the present disclosure. Their exemplary nature will make it clear that other procedures, methodologies, or techniques known to those skilled in the art may be used instead.

[0090] [Example 1] Rechargeable energy source system including lithium-free cathode This embodiment provides a predictive example of a rechargeable energy source system that includes a delithiated cathode.

[0091] A rechargeable energy source system is manufactured that includes a negative electrode and a delithiated positive electrode. The negative electrode contains a layer of lithium metal, and the positive electrode is one of the positive electrode materials listed in Table 1 (e.g., V x O yThe material is included. The potential difference between the negative and positive electrodes, excluding overvoltage, is at least 2.5V, or one of the values ​​shown in Table 1. The lithium content and the amount of positive electrode material are balanced so that, in the discharged state of the rechargeable energy source system, the negative electrode contains less than 10%, 5%, or 1% of the total lithium in the rechargeable energy source system. At the same time, in the charged state of the rechargeable energy source system, the positive electrode contains less than 10%, 5%, or 1% of the total lithium in the rechargeable energy source system while being structurally stable. The positive electrode is structurally stable in that the volume difference between the discharged and charged states of the rechargeable energy source system is 10%, 5%, or 3% or less. Thus, the amount of stress that the charge-discharge cycling of the rechargeable energy source system imposes on its components is negligible or acceptable, and the positive electrode material does not develop cracks that would lead to loss of active material. Charge-discharge cycling experiments are performed under various conditions in which the rechargeable energy source system is expected to operate, for example, in portable electronic devices (e.g., telephones), electric vehicles, and energy storage from wind turbines. The energy density of the rechargeable energy source system is at least 350 Wh / kg, with the cathode material appropriately selected from Table 1. During charging and discharging, the rechargeable energy source system utilizes at least 90% of the total lithium in the system for redox reactions. The potential difference between the negative and positive electrodes of the rechargeable energy source system is at least 2.5 volts. The volume expansion of the positive electrode due to discharge of the rechargeable energy source system is less than 15%.

[0092] [Example 2] V x O y F z synthesis This example is V x O y F z This provides a predictive method for producing [a specific compound]. In the formula, Mx - 2y - z = 0, where M is the oxidation state of V in the range of +3 to +5. For example, V6O5F 19 In this case, x=6, y=5, z=19, and M=+4.83.

[0093] VF4 and V2O5 precursors are mixed in stoichiometric amounts, sometimes with a slight (<10%) excess of VF4 to compensate for losses due to gas generation. The mixture is placed in an alumina crucible or sealed in a quartz crucible and calcined at a temperature in the range of 350–550°C for a time in the range of 2–12 hours. Approximately 6 hours at 400°C is preferred. The synthesis is carried out in an inert Ar atmosphere. After synthesis, the powder is carbon-coated using carbothermal reduction, then mixed with a suitable binder (i.e., PVDF), cast onto a current collector (i.e., aluminum), calendered to the appropriate thickness, and used as an electrode.

[0094] While preferred embodiments of the Disclosure have been shown and described herein, it will be apparent to those skilled in the art that such embodiments are provided only as examples. Those skilled in the art will be able to conceive of numerous variations, modifications, and substitutions without departing from the Disclosure. It should be understood that various alternative forms to the embodiments of the Disclosure described herein may be used in the practice of the Disclosure. The following claims define the scope of the Disclosure, and the methods and structures within these claims, as well as their equivalents, are intended to be encompassed thereby.

Claims

1. (a) at least about 0.4 g / cm³ ３ A negative electrode comprising a layer of lithium metal having a density of; and (b) A rechargeable energy source system includes a positive electrode that is substantially free of lithium when it is charged, The positive electrode has a capacity of at least 300 mAh / g and a gravimetric energy density of at least 800 Wh / kg. Electrochemical systems.

2. (a) at least about 0.4 g / cm³ ３ A negative electrode comprising a layer of lithium metal having a density of; and (b) The rechargeable energy source system includes a positive electrode that is substantially free of lithium when charged, The positive electrode has a capacity of at least 250 mAh / g, and is configured to exhibit a volume change of less than approximately 15% between the discharged state and the charged state. Electrochemical systems.

3. The electrochemical system according to claim 1 or 2, wherein the positive electrode is configured to maintain the volume change over at least 100 charge / discharge cycles of the electrochemical system.

4. The electrochemical system according to any one of claims 1 to 3, wherein the positive electrode contains a vanadium atom.

5. The positive electrode is V ｘ O ｙ The electrochemical system according to claim 4, including the following:

6. The positive electrode is V ｘ O ｙ F ｚ The electrochemical system according to claim 5, including the following:

7. The positive electrode is V ６ O ５ F １９ 、V ３ OF １１ 、VO ２ F、VOF ３ 、VPO ４ F、LiV ３ OF １１ 、Mn ３ V(PO ４ ) ６ 、V ６ O ５ F １９ 、V ２ (PO ４ ) ３ 、LiVOF ４ 、LiV(OF) ２ 、LiV(OF) ２ 、MnVP ２ (O ４ F) ２ 、V ４ O7F ５ 、LiV ３ CoO １０ 、VPO ５ 、VFeP ２ (O ４ F) ２ 、TiVO ４ 、LiTiV ３ O １０ 、VFeP ２ (HO ５ ) ２ 、Li ２ VOF ５ 、MnV ４ O １２ 、VBO ４ 、LiV ２ P ２ (O ４ F) ２ 、LiV ３ CrO ８ 、V ４ (OF ３ ) ３ 、LiV ４ O ８ 、V(CO ３ ) ２ 、LiV ５ O １０ 、VCuO ４ 、Or VCo ３ O ８ The electrochemical system according to claim 4, comprising at least one of the following.

8. The positive electrode is FePO ４ NiMnCoO ２ , or TiS ２ An electrochemical system according to any one of claims 1 to 7, including the above.

9. The electrochemical system according to any one of claims 1 to 8, wherein the rechargeable energy source system contains an excess of lithium, and the excess lithium comprises less than 10% of the net amount of lithium transferred between the negative electrode and the positive electrode during the discharge or charge of the rechargeable energy source system.

10. The electrochemical system according to any one of claims 1 to 9, wherein the positive electrode is configured to exhibit a volume change of less than about 10% over at least 100 charge / discharge cycles of the rechargeable energy source system.

11. The electrochemical system according to any one of claims 1 to 10, wherein the energy capacity loss of the rechargeable energy source system is less than about 1% over at least 100 charge / discharge cycles.

12. The electrochemical system according to claim 11, wherein the energy capacity loss of the rechargeable energy source system is less than about 1% over at least 300 charge / discharge cycles.

13. The electrochemical system according to any one of claims 1 to 12, wherein the N / P ratio is less than 0.1 when the rechargeable energy source system is completely discharged.

14. The electrochemical system according to any one of claims 1 to 13, wherein the N / P ratio is about 0 when the rechargeable energy source system is completely discharged.

15. The electrochemical system according to any one of claims 1 to 14, wherein the lithium from the negative electrode is added to the positive electrode via an intercalation mechanism or a conversion mechanism.

16. The electrochemical system according to any one of claims 1 to 15, wherein the lithium metal layer includes a thickness of less than 100 μm.

17. The electrochemical system according to any one of claims 1 to 16, wherein the positive electrode contains less than 10% by mass of lithium.

18. An electrochemical system in which at least 90% of the total lithium is oxidized to Li+ during discharge and reduction, and the potential difference between the negative and positive electrodes of the rechargeable energy source system is at least 2.5 volts, wherein the volume expansion of the positive electrode due to discharge of the rechargeable energy source system is less than 15%, and the capacity of the positive electrode is at least 250 mAh / g.

19. a. A negative electrode comprising a layer of lithium metal, wherein, in the discharge state of the rechargeable energy source system, the negative electrode comprises less than 10% of the total lithium in the rechargeable energy source system, b. V ｘ O ｙ A positive electrode comprising, which is structurally stable in the charged state of the rechargeable energy source system and contains less than 10% of the total lithium in the rechargeable energy source system, The difference in volume of the positive electrode between the discharged state and the charged state of the rechargeable energy source system is less than 10%. The potential difference between the negative electrode and the positive electrode, excluding overvoltage, is at least 2.5V. The energy density of the rechargeable energy source system is at least 225 Wh / kg. Electrochemical systems.

20. A rechargeable energy source system comprising the electrochemical system described in any one of claims 1 to 19.

21. A method for fabricating electrodes, (a) One or more V ｘ O ｙ F ｚ Mixing a precursor into a mixture; (b) A step of heating the mixture to at least 350°C or at least 550°C for at least 2 hours or up to 12 hours to produce a solid phase; (c) Coating the solid phase with carbon; (d) Mixing the solid phase with the binder; and (e) A method comprising casting the solid phase onto a current collector.

22. The one or more V ｘ O ｙ F ｚ The precursor is V ｉ F ｊ , V ｋ O ｌ The method according to claim 21, comprising either or both.

23. the one or more V ｘ O ｙ F ｚ where the precursor comprises VF ４ , V ２ O ５ or both, the method according to claim 22

24. The method according to any one of claims 21 to 23, further comprising calendering the solid phase on the current collector.

25. The method according to any one of claims 21 to 24, wherein the solid phase includes a powder.

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