System and method for a rechargeable energy source system having a redox-activated cathode

Abstract

In some embodiments, the present disclosure provides a rechargeable energy source system. The system may comprise a positive electrode comprising a redox material having a specific capacity of at least 300 mAh / g. The system may comprise a negative electrode comprising a layer of lithium metal having a purity level greater than about 90% and a thickness ranging from about 1 μm to about 20 μm. The positive electrode may be configured to maintain its specific capacity at a charge / discharge rate of C / 10 or greater for at least 100 charge / discharge cycles at 1.6 to 4.5 volts.

Description

[Technical Field]

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

[0002] The large-scale implementation of renewable energy, the increasing proliferation of portable electronic devices, and next-generation electric vehicles are creating a greater need for advanced energy storage systems for transportation, commercial, industrial, residential, and consumer applications. [Overview of the project] [Means for solving the problem]

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

[0004] In some embodiments, the Disclosure provides a rechargeable energy source system comprising: a positive electrode comprising a redox material having a specific capacity of at least 300 mAh / g; and a negative electrode comprising a layer of lithium metal, wherein the lithium metal layer has a thickness in the range of about 1 μm to about 20 μm.

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

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

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

[0008] In some embodiments, the redox material includes a multi-electron intercalated material.

[0009] In some embodiments, the positive electrode comprises at least 70% by mass of redox material.

[0010] In some embodiments, the positive electrode includes a polymer binder.

[0011] In some embodiments, the polymer binder includes a block copolymer.

[0012] In some embodiments, the block copolymer provides hydrophobic domains on the surface of the cathode.

[0013] In some embodiments, the system further comprises a hydrophobic polymer film bonded to hydrophobic domains on the surface of the positive electrode.

[0014] In some embodiments, the redox material includes a transition metal redox material.

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

[0016] In some embodiments, the redox material includes polyatomic anions.

[0017] In some embodiments, the polyatomic anion contains PO4.

[0018] In some embodiments, the redox material contains VOPO4.

[0019] In some embodiments, VOPO4 contains alpha(I)-VOPO4, alpha(II)-VOPO4, beta-VOPO4, epsilon-VOPO4, delta-VOPO4, omega-VOPO4, or gamma-VOPO4.

[0020] In some embodiments, the redox material contains V2O5.

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

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

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

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

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

[0026] In some embodiments, the layer of lithium metal contains less than 1 per mm3 of non-lithium subsurface structures.

[0027] In some embodiments, the layer of lithium metal contains less than 1 per mm

[0026] , ,<0000

此处原文似乎有误,推测为0000115

[0027] , of non-lithium crystalline subsurface structures.

[0028] Built-in by 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.

[0029] 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]

[0030] [Figure 1A] This figure shows a scanning electron microscope (SEM) image of ε-VOPO4 before cycling. [Figure 1B] This figure shows an energy-dispersive X-ray spectroscopy (EDS) image of ε-VOPO4 before cycling.

[0031] [Figure 2A] This figure shows the cycle versus capacity for cell A. [Figure 2B] This figure shows the specific capacitance versus voltage for cell A. [Figure 3A] This figure shows the experimental results for cell B.

[0032] [Figure 3B] This figure shows the experimental results for cell B. [Figure 3C] This figure shows the experimental results for cell B. [Figure 3D] This figure shows the experimental results for cell B.

[0033] [Figure 4A]This figure shows the experimental results for cell C. [Figure 4B] This figure shows the experimental results for cell C. [Figure 4C] This figure shows the experimental results for cell C. [Figure 4D] This figure shows the experimental results for cell C. [Figure 4E] This figure shows the experimental results for cell C.

[0034] [Figure 5A] This figure shows the experimental results for cell D. [Figure 5B] This figure shows the experimental results for cell D. [Figure 5C] This figure shows the experimental results for cell D. [Figure 5D] This figure shows the experimental results for cell D. [Modes for carrying out the invention]

[0035] In some embodiments, this application provides a rechargeable energy source system. The rechargeable energy source system may include a redox material. The redox material may have a specific capacity of at least 300 mAh / g. The rechargeable energy source system may include a negative electrode comprising a layer of lithium metal. The lithium metal layer may have a purity level greater than about 90% by weight. The lithium metal layer may have a thickness in the range of about 1 μm to about 20 μm. The lithium metal layer may have an impurity level of less than about 100 ppm by mass. The positive electrode may be configured to maintain a specific capacity at a charge / discharge rate of C / 10 or higher for at least 100 charge / discharge cycles at 1.6 to 4.5 volts. The positive electrode may be configured to maintain a specific capacity at a charge / discharge rate of C / 5 or higher for at least 100 charge / discharge cycles.

[0036] The redox material can be configured to intercalate lithium. The redox material may include a multi-electron intercalating material. The cathode may include at least 70% by mass of the redox material. The cathode may include a polymer binder. The polymer binder may include a block copolymer. The block copolymer can provide hydrophobic domains on the surface of the cathode. The hydrophobic polymer film can bond to the hydrophobic domains on the surface of the cathode.

[0037] negative electrode In some embodiments, the negative electrode comprises (1) lithium metal, which is an electrochemically active component, and (2) a substrate that functions as a current lead / collector and contact to an external circuit. Since lithium metal may be chemically unstable in air, contact can be made via another material, e.g., a material that is chemically stable in air and the cell chemical environment. The other material may be chemically and electrochemically inert so as not to compete with lithium. In some embodiments, the negative electrode may include copper, aluminum, graphite-clad copper, nickel, silicon, silver, carbon (e.g., rough-faced carbon, graphene), lithophilic materials, aluminum, gold, copper alloys (Cu-Zn, Cu-Al, Cu-Sn), or any combination thereof. The negative electrode may include a layer of lithium metal deposited thereon. The lithium metal can 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 approximately 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, or 500 μm. Lithium metal can be deposited on the negative electrode with a maximum thickness of approximately 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, or 500 μm. Lithium metals can include thicknesses of 1-380 μm, 1-370 μm, 1-360 μm, 1-350 μm, 1-340 μm, 1-330 μm, 1-320 μm, 1-310 μm, 1-300 μm, 1-250 μm, 1-200 μm, 1-150 μm, 1-100 μm, 1-90 μm, 1-80 μm, 1-70 μm, 1-60 μm, 1-50 μm, 1-45 μm, 1-40 μm, 1-35 μm, 1-30 μm, 1-25 μm, 1-20 μm, 1-15 μm, 1-10 μm, or 1-5 μm.

[0038] In some embodiments, the lithium metal electrode has a specific capacity exceeding 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 total capacity of the lithium metal electrode (e.g., on a mAh basis) can be made to substantially match the capacity of the positive electrode. In some embodiments, the lithium metal electrode has a density of about 0.4 g / cm 3 ~ about 0.534 g / cm 3 . In some embodiments, the lithium metal electrode has a density of about 0.45 g / cm 3 ~ about 0.543 g / cm 3 . In some embodiments, the lithium metal electrode has a density exceeding 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, or 0.53 g / cm 3 . In some embodiments, the lithium metal electrode has a density less than 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, or 0.543 g / cm 3 .

[0039] In some embodiments, the lithium metal electrode can contain less than 0.1 wt% or less than 0.1 at% of nitrogen, oxygen, or both. In some embodiments, the lithium metal electrode can contain less than 0.1 wt% or less than 0.1 at% of boron. In some embodiments, the lithium metal electrode can contain less than 0.1 wt% or less than 0.1 at% of magnesium, aluminum, or both. In some embodiments, the lithium metal electrode can contain less than 0.1 wt% or less than 0.1 at% of non-conductive impurities. In some embodiments, the lithium metal electrode can contain less than 0.1 wt% of a lithium alloy. In some embodiments, the lithium metal electrode can have a sub-surface structure of less than 1 per mm 3 of non-lithium. In some embodiments, the lithium metal electrode can have a sub-surface structure of less than 1 per mm 3It may have a non-lithium crystalline subsurface structure of less than 100. Although not bound by any particular theory, it is hypothesized that some impurities in lithium may form a different phase from lithium (e.g., LiN3 or crystallites of another compound or another element) after cycling experiments. Therefore, by analyzing a sample of lithium metal, it is possible to detect the presence of impurities in a 3D image of the sample, which can indicate structural impurities in the lithium metal.

[0040] Lithium metal samples can be imaged using monochromatic hard X-rays with selected energies in the 22–25 keV range. The X-rays can be generated using a synchrotron capable of irradiating the entire sample. The X-ray shadow projected by the sample can be converted to visible light using a scintillator. An optical microscope can then magnify the images and convert them to digital format. The sample can be rotated in increments of less than 1 degree up to 180 degrees, generating approximately 1000 sample images. The shadow images can be converted into cross-sectional slides that are stacked together to render a 3D reconstruction of the sample. The 3D reconstruction can reveal structural impurities, such as crystallites.

[0041] Lithium metal may contain nonmetallic elements in amounts 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. ppm may be by mass or count. ppm may correspond to the standard used by the instrument to detect nonmetallic elements. Lithium metal may contain nonmetallic elements in amounts less than 5 parts per million (ppm). In some embodiments, lithium metal contains nonmetallic elements in amounts less than 1 mass ppm. Nonmetallic elements may be nitrogen, boron, oxygen, carbon, hydrogen, or fluorine. Nonmetallic elements can exist as atomic or molecular species (e.g., as Li3N, OH, lithium boron compounds, carbonates, or O2). In some embodiments, nonmetallic elements can form a resistive material on the surface of lithium metal. For example, LiCO3 or LiOH may cause resistive losses in lithium metal electrodes. The presence of nonmetallic elements can be detected, for example, using inductively coupled plasma emission spectroscopy (ICP-OES) or X-ray microtomography. The presence of nonmetallic elements can be detected using focused ion beam (FIB) with secondary ion mass spectrometry (SIMS). The presence of nonmetallic elements can be detected by detecting and mapping lithium through a shallow Li K-edge high ionization cross-section that is 10 to 100 times larger than the ionization cross-sections of other light elements, such as O and F, using electron energy loss spectroscopy (EELS) and / or transmission electron microscopy (TEM).

[0042] Lithium metal may contain trace metals in amounts less than 1500 ppm. Lithium metal may contain trace metals in amounts 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 metals may contain trace metals in amounts exceeding 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 parts per billion (ppb) units. ppb can be mass or count. ppb can correspond to a standard used by the instrument to detect trace elements. Trace metals may include aluminum, barium, calcium, chromium, iron, iridium, magnesium, tungsten, zinc, cobalt, or sodium. In some embodiments, trace elements may form alloys with lithium. Alloys 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 calcium in amounts of 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 less than 0.1 ppm. Lithium metal may contain chromium in amounts of 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or less than 0.1 ppm. Lithium metal may contain iron in amounts of 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or less than 0.1 ppm.Lithium metal may contain iridium in amounts of 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 less than 0.1 ppm. Lithium metal may contain magnesium in amounts of 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 5, 040, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or less than 1 ppm. Lithium metal may contain tungsten in amounts of 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 less than 0.1 ppm. Lithium metal may contain zinc in amounts of 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or less than 0.1 ppm. Lithium metal may contain sodium in amounts of 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 less than 0.1 ppm. Lithium metal may contain cobalt in amounts of 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 less than 0.1 ppm. The presence of trace metals can be detected, for example, using inductively coupled plasma atomic emission spectroscopy (ICP-OES).

[0043] Lithium metal electrodes may contain low-density structural impurities, such as subsurface structural impurities. While not bound by any particular theory, elemental or molecular impurities in lithium metal may form phases different from lithium during cycling. When current passes through lithium metal, the lithium metal may heat up. Higher temperatures allow impurities to conduct or diffuse into the lithium metal, potentially leading to the formation of more stable phases (e.g., crystallites) of the impurities in the lithium metal. Once such structural impurities (phases with different crystal structures, or phases with grain boundaries to the lithium metal phase in the lithium metal) begin to form, they may continue to grow. Structural impurities can be detected by 3D techniques, such as X-ray tomography. Structural impurities may be present on or below the surface of the lithium metal. Structural impurities may provide sites for dendrite nucleation or growth, potentially causing cracks in the surrounding lithium metal. In some embodiments, the lithium metal is present in quantities of 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 pieces / mm 3 It may contain structural impurities of less than 1 ppm by weight. In some embodiments, the lithium metal may contain structural impurities of less than 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 5, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 ppm by weight.

[0044] film In some embodiments, the membrane may be positioned 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 movement of permeable organic solvents, lithium salt anions, water, or contaminants between the negative and positive electrodes. The membrane may include a single layer or multiple layers. In some embodiments, the membrane may include glass fiber, polyester, polyethylene, polypropylene, polyvinylidene fluoride ("PVDF"), polytetrafluoroethylene ("PTFE"), and combinations thereof. In some embodiments, the membrane may include a hydrophobic polymer. In some embodiments, the membrane may comprise lithium ion conductive channels.

[0045] 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. In some embodiments, the electrolyte may be a cathode solution. In some embodiments, the electrolyte may be an anode solution. In some embodiments, the electrolyte may be both a cathode solution and an anode solution.

[0046] 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.

[0047] In some embodiments, the electrolyte has a decomposition potential of at least 2, 3, 4, 5, or 6 V. In some embodiments, the electrolyte has a decomposition potential of up to 2, 3, 4, 5, or 6 V. In some embodiments, the electrolyte has a dielectric constant of at least 2, 5, 10, 20, 30, 40, 50, 60, 70, or 80. In some embodiments, the electrolyte has a dielectric constant of up to 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90. The electrolyte can contain a variety of viscosities. Polymer or polymer solution electrolytes can contain high viscosities because their viscosity can scale exponentially with the molecular weight of the polymer above its 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.

[0048] 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.

[0049] 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 to improve the ionic conductivity of the electrolyte and promote 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 compound is 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 is a nitrile (e.g., R-CN, where R is a C2-C bond that may include a double bond, an aromatic ring, or an ether bond). 20The electrolyte may be a linear, branched, or cyclic hydrocarbon (the linear, branched, or cyclic hydrocarbon portion of ), an amide (e.g., formamide and dimethylformamide), a dioxolane (e.g., 1,2-dioxolane and 1,3-dioxolane), a methyl sulfoxide, a sulfolane (e.g., sulfolane and methylsulfolane), 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidinone, nitromethane, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate triesters. In some embodiments, the electrolyte may contain an aromatic hydrocarbon organic solvent in the 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.

[0050] Various polymer electrolytes can be used. These 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.

[0051] Any of the various ionic liquids listed in the Ionic Liquid Database (ILThermo) of the U.S. Institute of Standards and Technology can be used.

[0052] 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 diphenyl phosphate, 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 trifluoromethanesulfonate, 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, LiClO4, LiTFSI, and combinations thereof.In some embodiments, the electrolyte is 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+1 The following can be included: SO2) (wherein x and y are natural numbers), CF3CO2Li, LiCl, LiBr, LiI, LIBOB (lithium bisoxalatoborate), lithium lower aliphatic carboxylates, lithium terphenyl borate, 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.

[0053] positive electrode In some embodiments, the positive electrode includes a current collector. In some embodiments, the positive electrode includes active material. In some embodiments, the positive electrode includes 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 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, 900, or 1000 μm. In some embodiments, the current collector includes 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 has fine irregularities on its surface to increase the adhesion strength of the positive electrode current collector to the positive electrode active material. In some embodiments, the current collector can take various forms, including films, sheets, foils, nets, porous structures, foams, and nonwoven fabrics. In some embodiments, the current collector includes carbon, carbon paper, carbon cloth, or metal or precious metal mesh or foil.

[0054] In some embodiments, the positive electrode includes a surface coating. In some embodiments, the surface coating includes an oxide, hydroxide, oxyhydroxide, oxycarbonate, or hydroxycarbonate. In some embodiments, the surface coating is amorphous or crystalline. In some embodiments, the surface coating includes 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 spray coating method, a dipping method, or any other preferred method.

[0055] In some embodiments, the positive electrode includes a binder. The binder can bond the active material to the current collector. In some embodiments, the binder includes polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber ("SBR"), acrylic SBR, epoxy resin, and nylon. In some embodiments, the binder is conductive. In some embodiments, the binder includes carbon black or steam-pulverized carbon fibers. In some embodiments, the binder includes polyvinylidene fluoride (PVDF), sodium alginate, and sodium carboxymethylcellulose. In some embodiments, the binder includes PVDF, polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and polyimide. In some embodiments, the binder includes graphene or carbon nanotubes.

[0056] In some embodiments, the positive electrode includes an electron intercalating material. In some embodiments, the positive electrode includes a multi-electron intercalating material. In some embodiments, the positive electrode includes a transition metal that undergoes at least two oxidation state changes between a charged state and a discharged state. In some embodiments, the positive electrode includes titanium disulfide. In some embodiments, the positive electrode includes a metal oxide. In some embodiments, the positive electrode is Li x It contains MO2, where M is a metal. In some embodiments, the positive electrode contains vanadium. In some embodiments, the positive electrode contains vanadium, cobalt, nickel, cobalt-aluminum alloy, manganese, niobium, molybdenum, technetium, tungsten, rhenium, rhodium, ruthenium, iridium, palladium, or platinum. In some embodiments, the positive electrode contains a polyatomic anion. In some embodiments, the polyatomic anion contains PO4.

[0057] In some embodiments, the positive electrode contains vanadyl. In some embodiments, the positive electrode contains a phosphate. In some embodiments, the positive electrode contains V2O5. In some embodiments, the positive electrode contains vanadyl phosphate (VOPO4). In some embodiments, VOPO4 may include alpha(I)-VOPO4, alpha(II)-VOPO4, beta-VOPO4, epsilon-VOPO4, delta-VOPO4, omega-VOPO4, or gamma-VOPO4.

[0058] In some embodiments, the positive electrode includes a sheet, ribbon, particles, or other form. In some embodiments, the positive electrode includes a microstructure. In some embodiments, the positive electrode includes a nanostructure. The microstructure or nanostructure may include a substantially spherical, cylindrical, or layered form, or any combination thereof.

[0059] In some embodiments, the vanadyl phosphate cathode is a vanadium cation (V 5+ / V 4+ and V 4+ / V 3+It includes two redox pairs. In some embodiments, the two redox pairs can allow two or more lithium ions per vanadium ion to be stored in the unit structure.

[0060] In some embodiments, the positive electrode includes additives. In some embodiments, the positive electrode is made of phosphate-based materials such as FePO4, VPO4F, V2(PO4)2F3, FePO4F, and V2(PO4)3; CoO2, V2O5, orthorhombic MnO2, layered iron oxide FeO2, chromium oxide CrO2, layered Ni 0.5 Mn 0.5 O2 and V6O 15 This includes oxides such as nanorods; layered sulfides such as TiS2; perovskite transition metal fluorides; or mixtures thereof.

[0061] In some embodiments, the cathode contains ε-VOPO4. The epsilon polymorph of vanadyl phosphate, ε-VOPO4, can be prepared from hydrothermal or solvothermal synthesis of H2VOPO4. In some embodiments, VOPO4 can be synthesized using carbonothermal reduction, ball mill grinding, microwave-assisted solvothermal synthesis, exfoliation from a sheet, or any combination thereof. In some embodiments, VOPO4 can be annealed.

[0062] 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 at least 10, 20, 30, 40, 50, 60, 700, 800, 900, or 1000 cycles. In some embodiments, the positive electrode includes 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, 99.9, or 100% over up to 10, 20, 30, 40, 50, 60, 700, 800, 900, or 1000 cycles. In some embodiments, the positive electrode containing ε-VOPO4 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 at least 10, 20, 30, 40, 50, 60, 700, 800, 900, or 1000 cycles. In some embodiments, the positive electrode containing ε-VOPO4 includes 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, 99.9, or 100% over up to 10, 20, 30, 40, 50, 60, 700, 800, 900, or 1000 cycles. In some embodiments, the cycles can include charge / discharge cycles of 1.6–4.5 volts, 1.6–3 volts, or 3–4.5 volts. The voltage can be referenced to lithium metal. In some embodiments, the cycle may include charge / discharge cycle rates of at least C / 50, C / 20, C / 10C / 5, C / 4, C / 3, C / 2, C / 1, 2C, 3C, 4C, or 5C.In some embodiments, the cycles may include charge / discharge cycle rates of up to C / 50, C / 20, C / 10C / 5, C / 4, C / 3, C / 2, C / 1, 2C, 3C, 4C, or 5C.

[0063] 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 up to 275, 280, 290, 300, or 305 mAh / g.

[0064] 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 wt% conductive filler, at least 3.0 wt% conductive filler, at least 3.5 wt% conductive filler, at least 4.0 wt% conductive filler, at least 5 wt% conductive filler, at least 6 wt% conductive filler, at least 7 wt% conductive filler, at least 8 wt% conductive filler, at least 9 wt% conductive filler, or at least 10 wt% conductive filler. The positive electrode may, for example, include at least 75 wt% ε-VOPO4, at least 5 wt% graphene nanoplatelets, and at least 5 wt% polyvinylidene fluoride (PVDF) binder. The intercalation electrode composition may include 85 wt% ε-VOPO4, at least 5 wt% graphene nanoplatelets, and 10 wt% binder. The intercalation electrode composition may comprise 75% by weight of ε-VOPO4, 15% by weight of graphene nanoplatelets, and 10% by weight of polyvinylidene fluoride (PVDF) binder.

[0065] polymer In some embodiments, the lithium-conducting polymer includes copolymers. In some embodiments, the polymer may include block copolymers or random copolymers. 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 annealed, for example, to undergo microphase separation, providing an exposed hydrophobic surface that is substantially inactive with the lithium metal. On the other hand, 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, triblockter copolymers and multiblock copolymers, as well as grafted copolymers. In some embodiments, the block copolymer may include PDMS-PEG (e.g., poly(polydimethylsiloxane)-b-poly(poly(ethylene glycol) methacrylate)). In some embodiments, the block copolymer may include POEM-b-PLMA(poly(oxyethylene 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), 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.

[0066] 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.

[0067] 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. Numerous variations, modifications, and substitutions will be conceivable to those skilled in the art without departing from the Disclosure. It should be understood that various alternative forms to the embodiments of the Disclosure may be used when implementing 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.

[0068] [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; by their exemplary nature, it will be understood that other procedures, methodologies, or techniques known to those skilled in the art may be used instead.

[0069] Example 1: Cell Construction This example describes a method for constructing an electrochemical cell using an ε-VOPO4 cathode.

[0070] A monoclinic H2VOPO4 precursor is calcined. VCl3 and P2O5 are dissolved in 190 proof ethanol. The solution is placed in a reactor and heated to 180°C. The reaction is allowed to proceed for several days. The product is collected by centrifugation and heated to 550°C for several hours under liquid oxygen to produce ε-VOPO4.

[0071] ε-VOPO4 is chemically lithiuminated in a helium atmosphere at ambient temperature. The ε-VOPO4 powder is dispersed in hexane and stirred. An excess amount of N-butyllithium is added to the solution. After several days, the discharged solid is washed with hexane and collected.

[0072] Solid ε-VOPO4 is mixed with graphene nanoplatelets, polyvinylidene fluoride, and 1-methyl-2-pyrrolidinone to create a slurry. The slurry is laminated onto an aluminum foil current collector. The laminate is vacuum-dried overnight.

[0073] A dry laminate (positive electrode) is assembled in a helium-purged glove box with a pure lithium electrode approximately 20 microns thick and containing less than 0.1% by weight of nonmetallic elements. Lithium hexafluoride phosphate (LiPF6) in ethylene carbonate / dimethyl carbonate is the electrolyte. Celgard 2400 is the separator. The assembly constitutes an electrochemical cell.

[0074] Example 2: ε-VOPO4 This example provides an experiment conducted using an electrochemical cell with an ε-VOPO4 cathode. Table 1 below summarizes the parameters used in the experiment. [Table 1]

[0075] Samples of VOPO4 were obtained, and experiments were conducted to confirm their morphology and composition. Figure 1A shows a scanning electron microscope (SEM) image of ε-VOPO4 before cycling. Figure 1B shows an energy-dispersive X-ray spectroscopy (EDS) image of ε-VOPO4 before cycling. The SEM and EDS experiments show morphology and composition consistent with what is expected for ε-VOPO4.

[0076] 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 EC:DMC (1:1) as the electrolyte. EC refers to ethylene carbonate, and DMC refers to dimethyl carbonate. First, the positive electrode was moistened with the electrolyte for more than 24 hours while removed from the cycler. The electrochemical cell was formed by cycling once at 1.6–4.5 volts (V) with a symmetric C / 20:C / 20 carbon rate. The temperature was approximately 23 degrees Celsius (°C). The electrochemical cell was then cycled at 1.6–4.5 V for approximately 40 days with a symmetric C / 5:C / 5 carbon rate.

[0077] Figure 2A shows the cycle-versus-capacitance ratio for cell A. A significant increase in capacity was observed at approximately 35 cycles, which may be due to the rise in laboratory ambient temperature. Figure 2B shows the specific capacity-versus-voltage ratio for cell A. Some capacity loss was observed, which may be due to polarization during discharge. The maximum specific capacity was approximately 332.79 mAh / g, and the maximum area capacity was approximately 1.01 mAh / cm². 2 Subsequently, no significant volume decrease was observed up to 130 cycles.

[0078] Three further electrochemical cells were constructed (cells B–D). The cells 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–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–D was then cycled at a series of different C rates (see Table 1).

[0079] Figures 3A to 3D show the experimental results for cell B.

[0080] Figures 4A to 4E show the experimental results for cell C. Cell C demonstrated a specific capacity of approximately 125 mAh / g. The cell was able to recover its initial C / 5 capacity even after 2C and 3C cycling. After approximately 110 cycles of C / 2:C / 2, the cell was subjected to (3) cycles of C / 5:5C cycling (see arrow indicator in Figure 4E). After 5C discharge, the cell recovered and could continue cycling at its maximum capacity.

[0081] Figures 5A to 5D show the experimental results for cell D.

[0082] The cells were able to maintain their capacity without significant capacity degradation, even at high discharge rates such as 2C and 3C. Overall, ε-VOPO4 demonstrated excellent rate capability in asymmetrical charge / discharge cycles up to C / 5:3C.

[0083] Example 3: X-ray microtomography This example describes an X-ray microtomography experiment for detecting the presence of impurities in lithium metal.

[0084] After the cycling experiment, the electrochemical cell is disassembled to extract the lithium metal anode. While not bound by any specific theory, it is hypothesized that some impurities in lithium may form a different phase from lithium (e.g., LiN3 or crystallites of another compound or element) after the cycling experiment. Therefore, by analyzing a sample of lithium metal, it is possible to detect the presence of impurities in a 3D image of the sample, which can indicate structural impurities in the lithium metal.

[0085] Lithium metal samples are imaged using monochromatic hard X-rays with selected energies in the 22–25 keV range. The X-rays can be generated using a synchrotron capable of irradiating the entire sample. The X-ray shadow projected by the sample is converted to visible light using a scintillator. An optical microscope magnifies the image and converts it to digital format. The sample is rotated in increments of less than 1 degree up to 180 degrees to generate approximately 1000 sample images. The shadow images are converted into cross-sectional slides that are stacked together to render a 3D reconstruction of the sample. The 3D reconstruction can reveal structural impurities, such as crystallites.

Claims

1. A rechargeable energy source system, A positive electrode comprising a redox material and having a specific capacity of at least 300 mAh / g, A negative electrode comprising a layer of lithium metal, wherein the lithium metal layer has a purity level of over approximately 90%, A rechargeable energy source system equipped with [a specific feature / feature].

2. A rechargeable energy source system, A cathode comprising a redox material having a specific capacity of at least 300 mAh / g, A negative electrode comprising a layer of lithium metal, wherein the lithium metal layer has a thickness in the range of approximately 1 μm to approximately 20 μm, A rechargeable energy source system equipped with [a specific feature / feature].

3. A rechargeable energy source system, A positive electrode containing redox material, A negative electrode comprising a layer of lithium metal, wherein the lithium metal layer has an impurity level of less than approximately 100 ppm by mass, A rechargeable energy source system comprising, wherein the positive electrode is configured to maintain a specific capacity at a charge / discharge rate of C / 10 or higher for at least 100 charge / discharge cycles at 1.6 to 4.5 volts.

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

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

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

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

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

9. The rechargeable system according to claim 8, wherein the polymer binder comprises a block copolymer.

10. The rechargeable system according to claim 9, wherein the block copolymer provides hydrophobic domains on the surface of the positive electrode.

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

12. The rechargeable system according to any one of claims 1 to 11, wherein the redox material includes a transition metal redox material.

13. The rechargeable system according to claim 12, wherein the transition metal redox material comprises at least one of 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 to 13, wherein the redox material comprises polyatomic anions.

15. The aforementioned polyatomic anion, PO ４ The rechargeable system according to claim 14, including the following:

16. The aforementioned redox material is VOPO ４ A rechargeable system according to any one of claims 1 to 15, including the following:

17. The above VOPO ４ is alpha (I)-VOPO ４ alpha (II)-VOPO ４ beta-VOPO ４ epsilon-VOPO ４ delta-VOPO ４ omega-VOPO ４ or gamma-VOPO ４ The rechargeable system according to claim 16, comprising.

18. The aforementioned redox material is V ２ O ５ A rechargeable system according to any one of claims 1 to 15, including the following:

19. The rechargeable system according to any one of claims 1 to 18, wherein the lithium metal layer contains less than 0.1% by weight or less than 0.1 atomic percent of nitrogen, oxygen, or both.

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

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

22. The rechargeable system according to any one of claims 1 to 21, wherein the lithium metal layer contains less than 0.1% by weight or less than 0.1% atomically charged nonconductive impurities.

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

24. The lithium metal layer is 1 mm ３ A rechargeable system according to any one of claims 1 to 23, comprising a non-lithium subsurface structure of less than 1 per unit.

25. The lithium metal layer is 1 mm ３ A rechargeable system according to any one of claims 1 to 24, comprising a non-lithium crystalline bottom surface structure of less than 1 per unit.

Images