Systems and methods for rechargeable energy systems with redox active positive electrodes

Abstract

In some aspects, the disclosure provides a rechargeable energy system. The system may include a positive electrode containing a redox material and having a specific capacity of at least 300 mAh / g. The system may include a negative electrode including a lithium metal layer having a purity level greater than about 90% and a thickness ranging from about 1 [mu] m to about 20 [mu] m. The positive electrode may be configured to maintain a specific capacity between 1.6 and 4.5 volts for at least 100 charge / discharge cycles at a charge / discharge rate of C / 10 or greater.

Description

Cross-referencing

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 517,553, filed August 3, 2023, which is incorporated herein by reference in its entirety. Background Technology

[0002] The large-scale implementation of renewable energy, the increasing popularity of portable electronic devices, and the next generation of electric vehicles have created additional demand for advanced energy storage systems for transportation, commercial, industrial, residential, and consumer applications. Summary of the Invention

[0003] In some aspects, this disclosure provides a rechargeable energy system comprising: a positive electrode containing a redox material and having a specific capacity of at least 300 mAh / g; and a negative electrode containing a lithium metal layer having a purity level greater than about 90%.

[0004] In some aspects, this disclosure provides a rechargeable energy system comprising: a positive electrode containing a redox material having a specific capacity of at least 300 mAh / g; and a negative electrode containing a lithium metal layer having a thickness ranging from about 1 μm to about 20 μm.

[0005] In some aspects, this disclosure provides a rechargeable energy system comprising: a positive electrode containing a redox material; and a negative electrode containing a lithium metal layer having an impurity level of less than about 100 ppm by mass; wherein the positive electrode is configured to maintain a specific capacity for at least 100 charge / discharge cycles between 1.6 and 4.5 volts at a charge / discharge rate of C / 10 or higher.

[0006] In some implementations, the positive electrode is configured to maintain the specific capacity for at least 100 charge / discharge cycles at a charge / discharge rate of C / 5 or higher.

[0007] In some implementations, the redox material is configured to intercalate lithium.

[0008] In some implementations, the redox material comprises a multi-electron intercalation material.

[0009] In some implementations, the positive electrode contains at least 70% by weight of a redox material.

[0010] In some implementations, the positive electrode comprises a polymer binder.

[0011] In some implementations, the polymer adhesive comprises a block copolymer.

[0012] In some implementations, the block copolymer provides hydrophobic water on the positive electrode surface.

[0013] In some embodiments, the system further includes a hydrophobic polymer film that binds to the hydrophobic water surface on the positive electrode.

[0014] In some implementations, the reducing agent comprises a transition metal reducing agent.

[0015] In some embodiments, the transition metal redox material comprises at least one of the following: vanadium, cobalt, nickel, cobalt-aluminum alloy, manganese, niobium, molybdenum, technetium, tungsten, rhenium, rhodium, ruthenium, iridium, palladium, or platinum.

[0016] In some implementations, the redox raw material contains polyatomic anions.

[0017] In some implementations, the polyatomic anion includes PO4.

[0018] In some implementations, the redox raw material comprises VOPO4.

[0019] In some implementations, VOPO4 includes α(I)-VOPO4, α(II)-VOPO4, β-VOPO4, ε-VOPO4, δ-VOPO4, ω-VOPO4, or γ-VOPO4.

[0020] In some implementations, the redox raw material comprises V2O5.

[0021] In some implementations, the lithium metal layer contains less than 0.1 wt% or at% nitrogen, oxygen, or both.

[0022] In some implementations, the lithium metal layer contains less than 0.1 wt% or at% boron.

[0023] In some implementations, the lithium metal layer contains less than 0.1 wt% or at% magnesium, aluminum, or both.

[0024] In some implementations, the lithium metal layer contains less than 0.1 wt% or at% of non-conductive impurities.

[0025] In some implementations, the lithium metal layer contains less than 0.1 wt% lithium alloy.

[0026] In some implementations, the lithium metal layer contains fewer than one non-lithium undersurface structure / mm. 3 .

[0027] In some implementations, the lithium metal layer comprises less than one non-lithium crystal subsurface structure / mm. 3 . Incorporation

[0028] All publications, patents, and patent applications mentioned in this specification are incorporated herein by reference to the extent that each publication, patent, or patent application is specifically and individually cited and incorporated herein by reference. To the extent that any publication, patent, or patent application incorporated by reference conflicts with any disclosure contained herein, this specification is intended to supersede and / or give precedence to any such conflicting material. Attached Figure Description

[0029] The novel features of this disclosure are set forth 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 and accompanying drawings, which illustrate embodiments in which the principles of this disclosure are utilized, in which: Figure 1A The image shows a scanning electron microscope (SEM) image of ε-VOPO4 before cycling. Figure 1B The energy-dispersive X-ray spectrum (EDS) image of ε-VOPO4 before cycling is shown.

[0030] Figure 2A The cycle life and capacity of battery A are displayed. Figure 2B The specific capacity and voltage of battery A are displayed.

[0031] Figures 3A-3D show the experimental results for battery B.

[0032] Figure 4A- Figure 4E The experimental results for battery C are shown.

[0033] Figures 5A-5D show the experimental results for battery D. Detailed Implementation

[0034] In some aspects, this application provides a rechargeable energy system. The rechargeable energy system may contain a reducing agent. The reducing agent may include a specific capacity of at least 300 mAh / g. The rechargeable energy system may include a negative electrode containing a lithium metal layer. The lithium metal layer may include a purity level greater than about 90% by weight. The lithium metal layer may include a thickness ranging from about 1 μm to about 20 μm. The lithium metal layer may include an impurity level of less than about 100 ppm by mass. The positive electrode may be configured to maintain a specific capacity for at least 100 charge / discharge cycles between 1.6 and 4.5 volts at a charge / discharge rate of C / 10 or higher. The positive electrode may be configured to maintain a specific capacity for at least 100 charge / discharge cycles at a charge / discharge rate of C / 5 or higher.

[0035] The reducing agent can be configured to intercalate lithium. The reducing agent can comprise a multi-electron intercalation material. The positive electrode can comprise at least 70% reducing agent by mass. The positive electrode can comprise a polymer binder. The polymer binder can comprise a block copolymer. The block copolymer can provide hydrophobic water on the surface of the positive electrode. A hydrophobic polymer film can bond to the hydrophobic water on the surface of the positive electrode.

[0036] negative electrode In some embodiments, the negative electrode comprises (1) lithium metal, which is an electrochemically active component; and (2) a substrate, which serves as a current lead / current collector and as a contact with an external circuit. Lithium metal may be chemically unstable in air, therefore the contact can be made of another material, for example, a material that is chemically stable in air and in the battery chemistry environment. The other material can be chemically and electrochemically inert to avoid competing with lithium. In some embodiments, the negative electrode may comprise copper, aluminum, graphite-coated copper, nickel, silicon, silver, carbon (e.g., rough-surfaced carbon, graphene), lithiophilic materials, aluminum, gold, copper alloys (Cu-Zn, Cu-Al, Cu-Sn), or any combination thereof. The negative electrode may comprise a layer of lithium metal deposited thereon. The lithium metal may be deposited on the negative electrode with a thickness of at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 μm. Lithium metal can be deposited on the negative electrode with a thickness of at least about 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400 or 500 μm. Lithium metal can be categorized into the following ranges: between 1 and 380 μm, between 1 and 370 μm, between 1 and 360 μm, between 1 and 350 μm, between 1 and 340 μm, between 1 and 330 μm, between 1 and 320 μm, between 1 and 310 μm, between 1 and 300 μm, between 1 and 250 μm, between 1 and 200 μm, between 1 and 150 μm, between 1 and 100 μm, between 1 and 90 μm, between 1 and 80 μm, between 1 and 70 μm, between 1 and 60 μm, between 1 and 50 μm, between 1 and 45 μm, between 1 and 40 μm, between 1 and 35 μm, between 1 and 30 μm, between 1 and 25 μm, between 1 and 20 μm, and between 1 and 15 μm. Thicknesses between μm, between 1 and 10 μm, or between 1 and 5 μm.

[0037] In some embodiments, the lithium metal electrode has a specific capacity greater than about 3500, 3600, 3700, 3750, or 3800 mAh per gram. In some embodiments, the lithium metal electrode has a specific capacity less than about 3600, 3700, 3750, or 3800 mAh per gram. The overall capacity of the lithium metal electrode (e.g., in mAh) can be substantially matched to the capacity of the positive electrode. In some embodiments, the lithium metal electrode has a specific capacity of about 0.4 g / cm³. 3 Approximately 0.534 g / cm 3 The density is between [specific values]. In some embodiments, the lithium metal electrode has a density of approximately 0.45 g / cm³. 3 Approximately 0.543 g / cm 3 The density is between [specific values]. In some embodiments, the lithium metal electrode has a density greater than 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, or 0.53 g / cm³. 3 The density. In some embodiments, the lithium metal electrode has a density of less than 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, or 0.543 g / cm³. 3 The density.

[0038] In some embodiments, the lithium metal electrode may contain less than 0.1 wt% or at% nitrogen, oxygen, or both. In some embodiments, the lithium metal electrode may contain less than 0.1 wt% or at% boron. In some embodiments, the lithium metal electrode may contain less than 0.1 wt% or at% magnesium, aluminum, or both. In some embodiments, the lithium metal electrode may contain less than 0.1 wt% or at% non-conductive impurities. In some embodiments, the lithium metal electrode may contain less than 0.1 wt% lithium alloy. In some embodiments, the lithium metal electrode may contain less than one non-lithium subsurface structure / mm. 3 In some implementations, the lithium metal electrode may contain less than one non-lithium crystal subsurface structure / mm. 3 Not bound by any particular theory, it is assumed that some impurities in lithium can form a different phase from lithium after cycling experiments (e.g., LiN3 or microcrystals of another compound or another element). Therefore, lithium metal samples can be analyzed to detect the presence of impurities in a 3D image of the sample, which can reveal structural impurities in the lithium metal.

[0039] Lithium metal samples can be imaged using monochromatic hard X-rays with energies selected in the range of 22–25 keV. The X-rays can be generated using a synchrotron, illuminating the entire sample. The X-ray shadows projected onto the sample can be converted to visible light using a scintillator. An optical microscope can magnify the images and convert them to a digital format. The sample can be rotated up to 180 degrees in fractions of a degree to generate approximately 1000 images of the sample. The shadowed images can be converted into cross-sectional slices, which are stacked together to form a 3D reconstruction of the sample. The 3D reconstruction can reveal structural impurities, such as microcrystals.

[0040] Lithium metal may contain less than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of nonmetallic elements. ppm may be expressed by mass or by count. ppm may correspond to the reference value of the instrument used to detect nonmetallic elements. Lithium metal may contain less than 5 parts per million (5 ppm) of nonmetallic elements. In some embodiments, lithium metal contains no more than 1 ppm of nonmetallic elements by mass. The nonmetallic element may be nitrogen, boron, oxygen, carbon, hydrogen, or fluorine. The nonmetallic element may exist as an atomic or molecular species (e.g., Li3N, OH, lithium boron compounds, carbonates, or O2). In some implementations, nonmetallic elements can form resistive materials on the lithium metal surface. For example, LiCO3 or LiOH can generate resistive losses in lithium metal electrodes. The presence of nonmetallic elements can be detected using, for example, inductively coupled plasma optical emission spectrometry (ICP-OES) or X-ray microtomography. The presence of nonmetallic elements can be detected using focused ion beam (FIB) accompanied by secondary ion mass spectrometry (SIMS). The presence of nonmetallic elements can be detected using electron energy loss spectroscopy (EELS) and / or transmission electron microscopy (TEM) by detecting and mapping lithium through a high ionization cross-section of the shallow Li K-edge, which is 10-100 times larger than that of other light elements (e.g., O and F).

[0041] Lithium metal may contain trace amounts of metal less than 1500 ppm. Specifically, lithium metal may contain trace amounts of metal less than 1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm. Lithium metal may contain trace amounts of metal in quantities greater than parts per billion (ppb): 0, 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, 1000, 2000, 3000, 4000, or 5000. ppb can be measured by mass or by count. ppb can correspond to the reference standard of instruments used for detecting trace elements. Trace metals may be aluminum, barium, calcium, chromium, iron, iridium, magnesium, tungsten, zinc, cobalt, or sodium. In some embodiments, trace elements may form alloys with lithium. Alloying can reduce the capacity of the lithium metal electrode. Lithium metal may contain less than 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of aluminum. Lithium metal may contain less than 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of barium. Lithium metal may contain less than 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of calcium. Lithium metal may contain less than 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of chromium. Lithium metal may contain less than 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of iron. Lithium metal may contain less than 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of iridium. Lithium metal may contain less than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 ppm of magnesium.Lithium metal may contain less than 23, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of tungsten. Lithium metal may contain less than 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of zinc. Lithium metal may contain less than 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of sodium. Lithium metal may contain less than 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of cobalt. The presence of trace metals can be detected using, for example, inductively coupled plasma optical emission spectrometry (ICP-OES).

[0042] Lithium metal electrodes can contain low-density structural impurities, such as subsurface structural impurities. Without being bound by any particular theory, elemental or molecular impurities in lithium metal can form a different phase from lithium after cycling. Lithium metal can be heated when current flows through it. Higher temperatures can allow impurities to conduct or diffuse within the lithium metal, which can lead to the formation of more stable impurity phases (e.g., microcrystals) within the lithium metal. These structural impurities (phases with different crystalline structures or grain boundaries relative to the lithium metal phase in the lithium metal) can continue to grow once they begin to form. Structural impurities can be detected using 3D techniques such as X-ray computed tomography. Structural impurities can be present on the surface of the lithium metal or may be present below the surface. Structural impurities can provide sites for dendrite nucleation or growth and can fragment the surrounding lithium metal. In some embodiments, the lithium metal can contain fewer than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 structural impurities per mm. 3 In some embodiments, the lithium metal may contain structural impurities in amounts of less than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 ppm by weight.

[0043] membrane In some embodiments, the membrane may be disposed between the positive and negative electrodes. In some embodiments, the membrane may selectively conduct lithium ions between the positive and negative electrodes. In some embodiments, the membrane may substantially prevent or inhibit the transfer of channel organic solvents, lithium salt anions, water, or contaminants between the negative and positive electrodes. The membrane may comprise a single layer or multiple layers. In some embodiments, the membrane may comprise glass fiber, polyester, polyethylene, polypropylene, polyvinylidene fluoride (“PVDF”), polytetrafluoroethylene (“PTFE”), and combinations thereof. In some embodiments, the membrane may comprise a hydrophobic polymer. In some embodiments, the membrane may comprise lithium-ion conductive channels.

[0044] electrolytes In some embodiments, the electrolyte comprises an aqueous electrolyte. In some embodiments, the electrolyte comprises a non-aqueous electrolyte. In some embodiments, the electrolyte comprises a polymeric electrolyte. In some embodiments, the electrolyte comprises an organic electrolyte. In some embodiments, the electrolyte comprises a lithium salt. In some embodiments, the electrolyte comprises an ionic liquid. In some embodiments, the electrolyte comprises a eutectic solvent. In some embodiments, the electrolyte may be a cathodic electrolyte. In some embodiments, the electrolyte may be an anodic electrolyte. In some embodiments, the electrolyte may be both a cathodic and an anodic electrolyte.

[0045] In some embodiments, the electrolyte is anhydrous. In some embodiments, the electrolyte is non-flammable or fire-resistant. In some embodiments, the electrolyte is self-extinguishing. In some embodiments, the electrolyte contains additives, such as nitrogen, sulfur, phosphorus, or silicon compounds.

[0046] In some embodiments, the decomposition potential of the electrolyte is at least 2, 3, 4, 5, or 6 V. In some embodiments, the decomposition potential of the electrolyte is at most 2, 3, 4, 5, or 6 V. In some embodiments, the dielectric constant of the electrolyte is at least 2, 5, 10, 20, 30, 40, 50, 60, 70, or 80. In some embodiments, the dielectric constant of the electrolyte is at most 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90. The electrolyte can have various viscosities. Polymerized or polymer solution electrolytes can have high viscosity because above a critical molecular weight (e.g., entanglement molecular weight), viscosity can increase exponentially with the molecular weight of the polymer. In some embodiments, the viscosity of the electrolyte is 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 viscosity of the electrolyte is 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 Pa·s. In some embodiments, the viscosity of the electrolyte is 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 viscosity of the electrolyte is at most 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 viscosity of the electrolyte is at most 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.

[0047] A variety of 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-dioxacyclopentan-2-one, 4-methyl-1,3-dioxacyclopentan-2-one, oxacyclopentan-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, its fluorocarbonate derivative, or a combination thereof.

[0048] In some embodiments, the chain carbonate compound may be diethyl carbonate (“DEC”), dimethyl carbonate (“DMC”), dipropyl carbonate (“DPC”), methyl propyl carbonate (“MPC”), ethyl propyl carbonate (“EPC”), methyl ethyl carbonate (“MEC”), and combinations thereof. In some embodiments, the cyclic carbonate compound may be ethylene carbonate (“EC”), propylene carbonate (“PC”), butenyl carbonate (“BC”), fluoroethylene carbonate (“FEC”), ethylene ethylene carbonate (“VEC”), and combinations thereof. In one embodiment, 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, taking into account the dielectric constant and viscosity of the electrolyte, the carbonate compound may include a combination of cyclic and chain carbonates. In some embodiments, the carbonate compound may be a mixture of such chain carbonates and / or cyclic carbonates as described above with the fluorocarbonate compound. In some embodiments, the fluorocarbonate compound may increase the solubility of the lithium salt to improve the ionic conductivity of the electrolyte and may promote the formation of a thin film on the negative electrode. In some embodiments, the ester compounds are methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate (“MP”), ethyl propionate, γ-butyrolactone, decanolactone, valproic acid lactone, mevalonolactone, caprolactone, and methyl formate. In some embodiments, the ether compounds are dibutyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 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 ethanol or isopropanol. In some embodiments, the aprotic solvent may be a nitrile (such as R-CN, where R is C2-C). 20The linear, branched, or cyclic hydrocarbon moiety may include double bonds, aromatic rings, or ether bonds, amides (such as formamide and dimethylformamide), dioxacyclopentanes (such as 1,2-dioxacyclopentane and 1,3-dioxacyclopentane), methyl sulfoxides, sulfolane (such as sulfolane and methyl sulfolane), 1,3-dimethyl-2-imidazolium ketones, N-methyl-2-pyrrolidones, nitromethanes, trimethyl phosphates, triethyl phosphates, trioctyl phosphates, and triphosphates. In some embodiments, the electrolyte may include an aromatic organic solvent in a carbonate solvent. In some embodiments, the aromatic organic solvent may be 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, 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.

[0049] A variety of polymeric 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. These polymeric electrolytes may inherently conduct lithium ions, or be doped with one or more lithium salts to make the polymer lithium conductive.

[0050] A variety of ionic liquids can be used, such as any of the ionic liquids listed in the National Institute of Standards and Technology's Ionic Liquid Database (ILThermo).

[0051] A variety of lithium salts can be used. Lithium salts may include lithium 12-hydroxystearate, lithium acetate, lithium amino, lithium aspartate, lithium azide, lithium bis(trifluoromethanesulfonyl)imide, lithium borohydride, lithium bromide, lithium carbonate, lithium chlorate, lithium chloride, lithium citrate, lithium cyanide, lithium diphenylphosphide, lithium hexafluorogermanate, lithium hexafluorophosphate, lithium hypochlorite, lithium hypofluorite, lithium metaborate, lithium methoxy, 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 tetra(pentafluorophenyl)borate, lithium trifluoromethanesulfonate, lithium tungstate, or any combination thereof. In some embodiments, the electrolyte may include a lithium salt comprising an organic anion selected from: trifluoromethanesulfonylimide (TFSI), N-butyl-N-methylpyrrolidone-bis(trifluoromethanesulfonyl)imide (PyruTFSI), trifluoromethanesulfonylimide, bis(trifluoromethanesulfonyl)imide (LiTFSI), and 1-ethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (EMI-TFSI). In some embodiments, the cathode electrolyte 290 comprises an ionic liquid-formed salt dissolved in 1,3-dioxane (DOL), 1,2-dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME). In some embodiments, the electrolyte may include Li₂SO₄, Li₂CO₃, LiPF₆, LiBF₄, LiClO₄, LiTFSI, and combinations thereof. In some embodiments, the electrolyte may include LiPF6, LiBF4, LiSbF6, LiAsF6, LiSbF6, LiCF3SO3, Li(CF3SO2)3C, Li(CF3SO2)2N, LiC4F9SO3, LiClO4, LiAlO4, LiAlCl4, LiAlF4, LiBPh4, LiBiOCl, CH3SO3Li, C4F3SO3Li, (CF3SO2)2NLi, LiN(C x F 2x+1 SO2)(C x F 2y+1The lithium salts are: CF3CO2Li, LiCl, LiBr, LiI, LIBOB (lithium dioxolane-borate), lower aliphatic carboxylic acids, lithium triphenylborate, lithium imine, and any combination thereof. In some embodiments, the concentration of the lithium salt can range from 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 implementations, the concentration of the lithium salt is at most 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.

[0052] positive electrode In some embodiments, the positive electrode comprises a current collector. In some embodiments, the positive electrode comprises an active material. In some embodiments, the positive electrode comprises an active material disposed on the current collector. In some embodiments, 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. In some embodiments, the current collector may have a thickness of at most 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. In some embodiments, the current collector comprises copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, or silver, and aluminum-cadmium alloys. In some embodiments, the current collector contains fine irregularities on its surface to enhance the adhesion strength between the positive electrode current collector and the positive electrode active material. In some embodiments, the current collector can comprise various forms, including thin layers, sheets, foils, meshes, porous structures, foams, and nonwoven fabrics. In some embodiments, the current collector comprises carbon, carbon paper, carbon cloth, or metal or precious metal meshes or foils.

[0053] In some embodiments, the positive electrode comprises a surface coating. In some embodiments, the surface coating comprises an oxide, hydroxide, hydroxyoxide, oxycarbonate, or hydroxycarbonate. In some embodiments, the surface coating is amorphous or crystalline. In some embodiments, the surface coating comprises 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), or any combination thereof. In some embodiments, the surface coating is formed using a spraying method, a dip-coating method, or any other suitable method.

[0054] In some embodiments, the positive electrode comprises an adhesive. The adhesive binds the active material to the current collector. In some embodiments, the adhesive comprises polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber (“SBR”), acrylated SBR, epoxy resin, and nylon. In some embodiments, the adhesive is conductive. In some embodiments, the adhesive comprises carbon black or vapor-milled carbon fibers. In some embodiments, the adhesive comprises polyvinylidene fluoride (PVDF), sodium alginate, and sodium carboxymethyl cellulose. In some embodiments, the adhesive comprises PVDF, polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and polyimide. In some embodiments, the adhesive comprises graphene or carbon nanotubes.

[0055] In some embodiments, the positive electrode comprises an electron-intercalated material. In some embodiments, the positive electrode comprises a multi-electron-intercalated material. In some embodiments, the positive electrode comprises a transition metal that undergoes at least two oxidation state changes between charge and discharge states. In some embodiments, the positive electrode comprises titanium disulfide. In some embodiments, the positive electrode comprises a metal oxide. In some embodiments, the positive electrode comprises Li. x MO2, where M is a metal. In some embodiments, the positive electrode comprises vanadium. In some embodiments, the positive electrode comprises vanadium, cobalt, nickel, cobalt-aluminum alloy, manganese, niobium, molybdenum, technetium, tungsten, rhenium, rhodium, ruthenium, iridium, palladium, or platinum. In some embodiments, the positive electrode comprises a polyatomic anion. In some embodiments, the polyatomic anion includes PO4.

[0056] In some embodiments, the positive electrode comprises a vanadium oxide group. In some embodiments, the positive electrode comprises a phosphate. In some embodiments, the positive electrode comprises V₂O₅. In some embodiments, the positive electrode comprises vanadium oxyphosphate (VOPO₄). In some embodiments, VOPO₄ may comprise α(I)-VOPO₄, α(II)-VOPO₄, β-VOPO₄, ε-VOPO₄, δ-VOPO₄, ω-VOPO₄, or γ-VOPO₄.

[0057] In some embodiments, the positive electrode comprises a sheet, strip, particle, or other form. In some embodiments, the positive electrode comprises a microstructure. In some embodiments, the positive electrode comprises a nanostructure. The microstructure or nanostructure may include substantially spherical, cylindrical, or lamellar morphologies, or any combination thereof.

[0058] In some embodiments, the vanadium oxyphosphate positive electrode comprises two redox pairs of vanadium cations (V0, V ... 5+ / V 4+ and V 4 + / V 3+ In some implementations, the two redox pairs can allow each vanadium ion to store more than one lithium ion in the unit structure.

[0059] In some embodiments, the positive electrode comprises additives. In some embodiments, the positive electrode comprises 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, and layered Ni. 0.5 Mn 0.5 O2 and V6O 15 Nanorods; layered sulfides, such as TiS2; perovskite transition metal fluorides, or mixtures thereof.

[0060] In some embodiments, the positive electrode comprises ε-VOPO4. The ε-polymorph of vanadium oxyphosphate, ε-VOPO4, can be manufactured from H2VOPO4 synthesized hydrothermally or solvothermally. In some embodiments, VOPO4 can be synthesized using carbothermal reduction, ball milling, microwave-assisted solvothermal synthesis, stripping from a sheet, or any combination thereof. In some embodiments, VOPO4 can be annealed.

[0061] In some embodiments, the positive electrode includes a coulombic 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% for at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 90, 90, 1000 cycles. In some implementations, the positive electrode includes a coulombic 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, 99.9, or 100% for up to 10, 20, 30, 40, 50, 60, 70, 80, 90, 90, 90, 1000 cycles. In some implementations, the positive electrode containing ε-VOPO4 has a coulombic 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% for at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 90, 90, 1000 cycles. In some embodiments, the positive electrode comprising ε-VOPO4 includes at most 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 cycles with at most 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, 99.9, or 100% coulombic efficiency. In some embodiments, the cycles may include charge / discharge cycles between 1.6 and 4.5 volts, between 1.6 and 3 volts, and between 3 and 4.5 volts. The voltage may be referenced to lithium metal. In some embodiments, the cycle may include charge / discharge cycle rates of at least C / 50, C / 20, C / 10, C / 5, C / 4, C / 3, C / 2, C / 1, 2C, 3C, 4C, or 5C. In some embodiments, the cycle may include charge / discharge cycle rates of up to C / 50, C / 20, C / 10, C / 5, C / 4, C / 3, C / 2, C / 1, 2C, 3C, 4C, or 5C.

[0062] In some embodiments, the positive electrode has a capacity of at least 275, 280, 290, 300, or 305 mAh / g.

[0063] In some embodiments, the positive electrode comprises ε-VOPO4 and a conductive filler. In some embodiments, the conductive filler comprises graphene. In some embodiments, the positive electrode comprises ε-VOPO4 and at least 2.5% by weight, at least 3.0% by weight, at least 3.5% by weight, at least 4.0% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, or at least 10% by weight of conductive filler. The positive electrode may comprise, for example, at least 75% by weight ε-VOPO4, at least 5% by weight graphene nanoplatelets, and at least 5% by weight polyvinylidene fluoride (PVDF) binder. The intercalated electrode composition may comprise 85% by weight ε-VOPO4, at least 5% by weight graphene nanoplatelets, and 10% by weight binder. The intercalated electrode composition may contain 75% ε-VOPO4 by weight, 15% graphene nanosheets by weight, and 10% polyvinylidene fluoride (PVDF) binder by weight.

[0064] polymer In some embodiments, the lithium-conductive polymer comprises a copolymer. In some embodiments, the polymer may comprise a block copolymer or a random copolymer. In some embodiments, a portion of the block copolymer is in contact with lithium metal, wherein this portion is substantially non-reactive with the lithium metal. For example, the block copolymer may be annealed to induce microphase separation, providing an exposed hydrophobic surface that is substantially non-reactive with the lithium metal. Simultaneously, the block copolymer may also comprise a permeating hydrophilic water layer that provides a pathway for lithium ions to cross from one side of the block copolymer to the other. In some embodiments, the block copolymer includes diblock copolymers, triblock copolymers, triblock ternary copolymers, and multiblock copolymers and graft copolymers. In some embodiments, the block copolymer may comprise PDMS-PEG (e.g., poly(dimethylsiloxane methacrylate)-b-poly(poly(ethylene glycol) methacrylate)). In some embodiments, the block copolymer may include POEM-b-PLMA (poly(ethylene methacrylate)-b-poly(lauryl methacrylate)), POEM ((polyoxyethylene methyl methacrylate))-P (PDMSMA (polydimethylsiloxane methacrylate)), 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), polyurethane (PU), poly(butadiene) (PB), poly(polyvinyl dimethacrylate) (PPVDFMA), poly(tetrafluoroethylene methacrylate) (PPTFEMA), poly(perfluoropolyether) (PFPE), poly(perfluoropolymethacrylate) (PFPEMA), poly(perfluoropolyacrylate) (PFPEA), poly(poly(ethylene glycol) methacrylate) (PPEGMA), poly(poly(ethylene glycol) acrylate) (PPEGA), poly(perfluoropolymethacrylate) (PFPEMA), poly(perfluoropolyacrylate) (PFPEA), or any combination thereof.

[0065] Hydrophobic polymers may include, for example, cyclic olefin copolymers, fluorinated ethylene propylene, ethylene-methyl acrylate copolymers, polychlorotrifluoroethylene, perfluoroalkoxy polymers, polymethylpentene, polypropylene, polyphenylene sulfide, polystyrene, polytetrafluoroethylene, polyvinyl chloride, polyethylene, ethylene vinyl acetate, or any combination thereof.

[0066] While preferred embodiments of this disclosure have been shown and described herein, it will be apparent to those skilled in the art that these embodiments are provided by way of example only. Various modifications, alterations, and substitutions will occur to those skilled in the art without departing from this disclosure. It should be understood that various alternatives to the embodiments of this disclosure may be employed in carrying out this disclosure. The appended claims are intended to define the scope of this disclosure, and the methods and structures within the scope of these claims, and their equivalents, should be covered within the scope of this disclosure.

[0067] Example The following examples further illustrate some embodiments of this disclosure, but are not intended to limit the scope of this disclosure; by their illustrative nature it will be understood that other procedures, methods or techniques known to those skilled in the art may be used alternatively.

[0068] Example 1: Battery Construction This example describes how to construct an electrochemical cell with an ε-VOPO4 positive electrode.

[0069] The monoclinic H₂VOPO₄ precursor was calcined. VCl₃ and P₂O₅ were dissolved in 190% proof ethanol. The solution was placed in a reactor and heated to 180°C. o C. The reaction was set to continue for several days. The product was collected by centrifugation and heated to 550°C for several hours under flowing oxygen. o C is used to generate ε-VOPO4.

[0070] ε-VOPO4 was chemically lithiumized at ambient temperature under a helium atmosphere. The ε-VOPO4 powder was dispersed in hexane and stirred. An excess of N-butyllithium was added to the solution. After several days, the solid was washed with hexane and collected.

[0071] Solid ε-VOPO4 was mixed with graphene nanosheets, polyvinylidene fluoride, and 1-methyl-2-pyrrolidone to form a slurry. The slurry was laminated onto an aluminum foil current collector. The laminate was vacuum dried overnight.

[0072] The dried laminate (positive electrode) and pure lithium electrode (approximately 20 micrometers thick and less than 0.1 wt% non-metallic elements) were assembled in a helium-purged glove box. Lithium hexafluorophosphate (LiPF6) in ethylene carbonate / dimethyl carbonate was used as the electrolyte. Celgard 2400 was used as the separator. The assembly constituted an electrochemical cell.

[0073] Example 2: ɛ-VOPO4 This embodiment provides an experiment conducted using an electrochemical cell with an ε-VOPO4 positive electrode. Table 1 below summarizes the parameters used in the experiment.

[0074] Table 1. Experimental parameters of electrochemical cells.

[0075]

[0076] VOPO4 samples were obtained and experiments were conducted to confirm their morphology and composition. Figure 1A The image shows a scanning electron microscope (SEM) image of ε-VOPO4 before cycling. Figure 1B Energy-dispersive X-ray spectroscopy (EDS) images of ε-VOPO4 before cycling are shown. SEM and EDS experiments show that the morphology and composition are consistent with those expected for ε-VOPO4.

[0077] An electrochemical cell (cell A) was constructed using 40 μm lithium metal as the negative electrode, ε-VOPO4 as the positive electrode, and 1 M LiPF6 in an EC:DMC (1:1) mixture as the electrolyte. EC refers to ethylene carbonate and DMC refers to dimethyl carbonate. The positive electrode was initially wetted with the electrolyte leaving the circulator for over 24 hours. The electrochemical cell was formed by cycling once at a C-rate of symmetrical C / 20:C / 20 from 1.6 to 4.5 volts (V). The temperature was approximately 23 degrees Celsius. o C). Then, the electrochemical cell was cycled for about 40 days at a C rate of symmetrical C / 5:C / 5 between 1.6 and 4.5 V.

[0078] Figure 2A The cycle life and capacity of battery A are shown. A significant increase in capacity was observed at approximately 35 cycles, which is likely due to the increased temperature in the laboratory environment. Figure 2B The specific capacity and voltage of battery A are shown. Note some capacity loss, which is likely due to polarization during discharge. The maximum specific capacity is approximately 332.79 mAh / g, and the maximum areal capacity is approximately 1.01 mAh / cm². 2 No significant capacity decay was subsequently observed over up to 130 cycles.

[0079] Three additional electrochemical cells (cell B-cell D) were constructed. Each cell contained 40 μm lithium metal as the negative electrode, ε-VOPO4 as the positive electrode, and 1 M LiPF6 in EC:DMC (1:1) as the electrolyte. Each of cells B-cell D was formed by discharging to the target voltage and cycling twice at C / 20:C / 20 within the cycling voltage range (see Table 1). Each of cells B-cell D was then cycled at a series of different C rates (see Table 1).

[0080] Figures 3A-3D show the experimental results for battery B.

[0081] Figure 4A- Figure 4EThe experimental results for battery C are shown. Battery C exhibits a specific capacity of approximately 125 mAh / g. Even after 2C and 3C cycles, the battery is able to recover its initial C / 5 capacity. After approximately 110 C / 2:C / 2 cycles, the battery was subjected to (3) C / 5:5C cycles (see...). Figure 4E (arrow symbol). After a 5C discharge, the battery can recover and continue cycling at full capacity.

[0082] Figures 5A-5D show the experimental results for battery D.

[0083] Even at high discharge rates (e.g., 2C and 3C), the battery maintains its capacity without significant capacity decay. Overall, ε-VOPO4 exhibits excellent rate capacity under asymmetric charge / discharge cycles up to C / 5:3C.

[0084] Example 3: X-ray microtomography This embodiment describes an X-ray microtomography experiment for detecting the presence of impurities in lithium metal.

[0085] The electrochemical cell was disassembled after cycling experiments to remove the lithium metal negative electrode. Without being bound by any particular theory, it was assumed that some impurities in lithium could form a different phase from lithium after cycling (e.g., LiN3 or microcrystals of another compound or element). Therefore, the presence of impurities could be detected in a 3D image of the lithium metal, revealing structural impurities within the lithium metal.

[0086] Lithium metal samples are imaged using monochromatic hard X-rays with energies selected in the range of 22–25 keV. The X-rays are generated using a synchrotron and can illuminate the entire sample. The X-ray shadows projected onto the sample are converted to visible light using a scintillator. The images are magnified using an optical microscope and converted to a digital format. The sample is rotated up to 180 degrees in fractions of a degree to generate approximately 1000 images of the sample. The shadowed images are converted into cross-sectional slices, which are stacked together to form a 3D reconstruction of the sample. This 3D reconstruction reveals structural impurities, such as microcrystals.

Claims

1. A rechargeable energy system, comprising: Positive electrode, comprising redox materials and having a specific capacity of at least 300 mAh / g; as well as The negative electrode comprises a lithium metal layer having a purity level greater than about 90%.

2. A rechargeable energy system, comprising: The positive electrode comprises a reducing agent having a specific capacity of at least 300 mAh / g; as well as The negative electrode comprises a lithium metal layer having a thickness ranging from about 1 μm to about 20 μm.

3. A rechargeable energy system, comprising: The positive electrode contains redox raw materials; as well as The negative electrode comprises a lithium metal layer having an impurity level of less than about 100 ppm by mass; The positive electrode is configured to maintain a specific capacity of at least 100 charge / discharge cycles between 1.6 and 4.5 volts at a charge / discharge rate of C / 10 or higher.

4. The rechargeable system of claim 3, wherein the positive electrode is configured to maintain the specific capacity for at least 100 charge / discharge cycles at a charge / discharge rate of C / 5 or higher.

5. The rechargeable system according to any one of claims 1-4, wherein the reducing agent is configured to intercalate lithium.

6. The rechargeable system according to any one of claims 1-5, wherein the redox material comprises a multi-electron intercalation material.

7. The rechargeable system according to any one of claims 1-6, wherein the positive electrode comprises at least 70% by weight of the redox material.

8. The rechargeable system according to any one of claims 1-7, wherein the positive electrode comprises a polymer binder.

9. The rechargeable system of claim 8, wherein the polymer adhesive comprises a block copolymer.

10. The rechargeable system of claim 9, wherein the block copolymer provides a hydrophobic area on the surface of the positive electrode.

11. The rechargeable system of claim 10, further comprising a hydrophobic polymer film bonded to the hydrophobic water area on the surface of the positive electrode.

12. The rechargeable system according to any one of claims 1-11, wherein the reducing agent comprises a transition metal reducing agent.

13. The rechargeable system of claim 12, wherein the transition metal redox material comprises at least one of the following: vanadium, cobalt, nickel, cobalt-aluminum alloy, manganese, niobium, molybdenum, technetium, tungsten, rhenium, rhodium, ruthenium, iridium, palladium, or platinum.

14. The rechargeable system according to any one of claims 1-13, wherein the redox material comprises polyatomic anions.

15. The rechargeable system of claim 14, wherein the polyatomic anion comprises PO4.

16. The rechargeable system according to any one of claims 1-15, wherein the reducing agent comprises VOPO4.

17. The rechargeable system of claim 16, wherein the VOPO4 comprises α(I)-VOPO4, α(II)-VOPO4, β-VOPO4, ε-VOPO4, δ-VOPO4, ω-VOPO4 or γ-VOPO4.

18. The rechargeable system according to any one of claims 1-15, wherein the reducing agent comprises V2O5.

19. The rechargeable system according to any one of claims 1-18, wherein the lithium metal layer comprises less than 0.1 wt% or at% nitrogen, oxygen, or both.

20. The rechargeable system according to any one of claims 1-19, wherein the lithium metal layer contains less than 0.1 wt% or at% boron.

21. The rechargeable system according to any one of claims 1-20, wherein the lithium metal layer comprises less than 0.1 wt% or at% magnesium, aluminum, or both.

22. The rechargeable system according to any one of claims 1-21, wherein the lithium metal layer contains less than 0.1 wt% or at% of non-conductive impurities.

23. The rechargeable system according to any one of claims 1-22, wherein the lithium metal layer comprises less than 0.1 wt% lithium alloy.

24. The rechargeable system according to any one of claims 1-23, wherein the lithium metal layer comprises per mm 3 Less than one non-lithium undersurface structure.

25. The rechargeable system according to any one of claims 1-24, wherein the lithium metal layer comprises per mm 3 Less than one non-lithium crystal surface structure.

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