Rechargeable battery having mixed positive electrode comprising converting active material and embedded active material

Abstract

The invention discloses a rechargeable battery. The rechargeable battery includes a negative electrode, a positive electrode comprising a lithium ion intercalation host, and an electrolyte comprising a solvent and a halogen-containing compound acting as an active positive electrode conversion material, wherein the electrolyte is in contact with the negative electrode and the positive electrode.

Description

Background Art

[0001] The present invention relates generally to the field of energy storage devices, and more particularly to energy storage devices having one or more positive electrodes formed from a plurality of active materials, including at least one active material that utilizes a chemical conversion mechanism for energy storage, and at least one other active material that utilizes an ion intercalation mechanism for energy storage.

[0002] A secondary energy storage device, or rechargeable battery for short, is an energy storage device that can be recharged to its initial pre-discharge state after use by passing an electric current through a circuit in the opposite direction to the current during discharge. Energy storage devices such as lithium-ion batteries can have high energy density and provide a compact rechargeable energy source suitable for use in portable electronic devices, electric vehicles, and renewable energy storage. Rechargeable batteries using metallic lithium as the negative electrode active material allow for higher energy density than prior art lithium-ion batteries that use graphite for this purpose.

[0003] Rechargeable batteries are in high demand across a wide range of applications, from small batteries for industrial equipment and medical devices to large batteries for electric vehicles (EVs) and grid energy storage systems. Each application requires a specific set of electrochemical performance characteristics, and in many of today's key and growing application categories such as EVs, battery performance is still seen as the main limiting factor in meeting high performance standards to meet customer needs.

[0004] Currently, the two types of rechargeable batteries commonly discussed in both industry and academia are those that operate by electrochemical insertion / deintercalation of active ions, and those that operate by conversion of active electrode materials / electrolyte materials. The most widely used rechargeable battery (besides lead-acid batteries used in internal combustion engine vehicles) is the lithium-ion battery (LIB). Generally speaking, most commercial LIBs today use lithium insertion materials based on metal oxides or metal phosphates as the positive electrode, carbon-graphite-based insertion materials as the negative electrode, and move lithium ions back and forth between them through a liquid electrolyte as the battery is charged and discharged.

[0005] Despite the rapid development and success of LIBs, there are still some shortcomings that need to be overcome to meet the rapidly growing market demand for high-performance batteries. The relatively low energy density and relatively high cost of cathode materials such as cobalt and nickel have been one of the biggest issues hindering the wider application of lithium-ion batteries. However, as lithium-ion batteries approach and in some cases even exceed the 300 watt-hour per kilogram (Wh / kg) specific energy mark, it is generally believed that we are reaching the limits of the specific energy and energy density of lithium-ion batteries that science and engineering can push. Summary of the invention

[0006] As recognized by the present invention, there is a need for lithium-ion batteries with higher energy density cathodes formed from cheaper cathode materials. Embodiments of the present invention provide methods for increasing the energy density and / or reducing the cost of a rechargeable lithium-ion battery cathode by mixing a conventional lithium-ion intercalation cathode material with a halogen conversion cathode material or a metal halide conversion cathode material to form an improved cathode and the resulting hybrid energy storage device.

[0007] According to at least one embodiment of the present invention, the shortcomings of current lithium ion batteries are made up and additional advantages are provided by a dissolved phase hybrid cathode lithium-ion battery (also referred to herein as the first rechargeable battery). The dissolved phase hybrid cathode lithium ion battery comprises a negative electrode, a positive electrode comprising a lithium ion embedding host, and an electrolyte comprising a solvent and a first halogen-containing compound serving as an active positive electrode conversion material, wherein the electrolyte contacts the negative electrode and the positive electrode.

[0008] In embodiments, the cathode further comprises a second halogen-containing compound that acts as an active cathode conversion material.

[0009] In an embodiment, the first halogen-containing compound contained in the electrolyte and serving as the active cathode conversion material and the second halogen-containing compound contained in the cathode and serving as the active cathode conversion material are the same.

[0010] In an embodiment, the first halogen-containing compound contained in the electrolyte and serving as the active cathode conversion material and the second halogen-containing compound contained in the cathode and serving as the active cathode conversion material are different.

[0011] In an embodiment, the halogen-containing compound contained in the electrolyte that acts as the active positive conversion material is a metal halide.

[0012] In an embodiment, the metal halide dissociates in a solvent into a corresponding halide ion and a corresponding metal ion, and wherein the halide ion comprises I - Br - , Cl - or F - At least one of the metal ions, and the metal ions include Li + 、Al 3+ Mg 2 + Or Na + At least one of .

[0013] In embodiments, the lithium ion intercalation host is selected from the group consisting of lithium cobalt oxide, nickel cobalt aluminum, lithium ion manganese oxide, lithium nickel manganese cobalt oxide, nickel cobalt manganese oxide, lithium iron phosphate, and mixtures and combinations thereof.

[0014] In an embodiment, the solvent of the electrolyte is selected from the group consisting of carbonate compounds, heterocyclic compounds, ethers, esters, cyclic ethers, cyclic esters, nitriles, ethereal nitrile, mixtures thereof, and combinations thereof.

[0015] In embodiments, the dissolved phase hybrid cathode lithium ion battery further comprises one or more than one oxidizing gas selected from the group consisting of air, oxygen, nitric oxide, nitrogen dioxide, mixtures thereof, and combinations thereof.

[0016] According to at least one embodiment of the present invention, the shortcomings of current lithium ion batteries are compensated and additional advantages are provided by a solid phase hybrid positive electrode lithium ion battery (also referred to herein as a second rechargeable battery). A solid phase hybrid positive electrode lithium ion battery is disclosed. The solid phase hybrid positive electrode lithium ion battery includes a negative electrode, a positive electrode containing a halogen compound that contains a lithium ion embedding host and acts as an active positive electrode conversion material, and an electrolyte containing a solvent and a lithium-containing compound, wherein the electrolyte is in contact with the negative electrode and the positive electrode.

[0017] In an embodiment, the halogen-containing compound contained in the positive electrode of the solid phase hybrid positive electrode lithium ion battery, which acts as an active positive electrode conversion material, is a halogen or a metal halide.

[0018] The metal halide comprises a corresponding halide ion and a corresponding metal ion, and wherein the halide ion comprises I - Br - , Cl - or F - At least one of the metal ions, and the metal ions include Li + 、Al 3+ Mg 2+ Or Na + At least one of .

[0019] In an embodiment, the lithium-containing compound contained in the electrolyte is a lithium salt.

[0020] In embodiments, the lithium ion intercalation host is selected from the group consisting of lithium cobalt oxide, nickel cobalt aluminum, lithium ion manganese oxide, lithium nickel manganese cobalt oxide, nickel cobalt manganese oxide, lithium iron phosphate, and mixtures and combinations thereof.

[0021] In an embodiment, the solvent of the electrolyte is selected from the group consisting of carbonate compounds, heterocyclic compounds, ethers, esters, cyclic ethers, cyclic esters, nitriles, ether nitriles, mixtures thereof, and combinations thereof.

[0022] In an embodiment, the solid phase hybrid cathode lithium ion battery further comprises one or more than one oxidizing gas selected from the group consisting of air, oxygen, nitric oxide, nitrogen dioxide, mixtures thereof, and combinations thereof.

[0023] According to at least one embodiment of the present invention, by forming a method for dissolving a phase mixed positive lithium ion battery (i.e., a first rechargeable battery), the shortcomings of current lithium ion batteries are compensated and additional advantages are provided. The method includes applying a slurry containing a lithium-containing intercalation material to a positive current collector. The method also includes dissolving a positive conversion material containing at least one of a metal halide or a halogen in a solvent to form a solution. The method also includes stacking a negative electrode, a separator, and a positive current collector to form a dissolved phase mixed positive lithium ion battery. The dissolved phase mixed positive lithium ion battery includes a negative electrode, an electrolyte containing a solution, a separator, and a positive current collector coated with a slurry, wherein at least one of the metal halide or halogen of the electrolyte acts as an active positive conversion material.

[0024] In embodiments, the method includes adding a second halogen or a second metal halide to the cathode, wherein the second halogen or second metal halide also serves as an active cathode conversion material.

[0025] In an embodiment, the second halogen or second metal halide added to the positive electrode is the same as the halogen or metal halide contained in the electrolyte.

[0026] In embodiments, the second halogen or second metal halide added to the positive electrode is different from the halogen or metal halide contained in the electrolyte.

[0027] In embodiments, the method includes replacing a portion of the lithium ion intercalation material with a second metal halide or a second halogen, wherein the second metal halide or the second halogen also serves as an active positive electrode conversion material.

[0028] In an embodiment, the second metal halide or second halogen that replaces a portion of the lithium ion intercalation material is the same as the halogen or metal halide contained in the electrolyte.

[0029] In embodiments, the second metal halide or second halogen that replaces a portion of the lithium ion intercalation material is different from the halogen or metal halide contained in the electrolyte.

[0030] According to at least one embodiment of the present invention, the shortcomings of current lithium-ion batteries are compensated and additional advantages are provided by a solid phase hybrid positive lithium-ion battery. The method includes coating a slurry containing at least one of a halogen or a metal halide and a lithium ion embedding material onto a positive current collector. The method also includes dissolving a lithium salt in a solvent to form an electrolyte. The method also includes stacking a negative electrode, a separator, and a positive current collector to form a solid phase hybrid positive lithium-ion battery. The solid phase hybrid positive lithium-ion battery comprises a negative electrode, an electrolyte, a separator, and a positive current collector coated with a slurry, wherein at least one of the halogen or metal halide of the slurry acts as an active positive conversion material. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings included in this disclosure are incorporated into this specification and form a part of this specification. They illustrate embodiments of the present invention and are used together with this specification to explain the principles of the present invention. The accompanying drawings are only illustrations of certain embodiments and do not limit the present invention.

[0032] Figure 1 is a conceptual diagram illustrating an exemplary solid phase hybrid battery, generally designated 100 , in accordance with at least one embodiment of the present invention.

[0033] Figure 2 FIG. 1 is a diagram showing a closed battery system according to at least one embodiment of the present invention. Figure 1 0045] A conceptual diagram of an example solid phase hybrid battery 100 is shown in FIG. 1 , wherein the closed battery system is generally designated 200.

[0034] Figure 3 is a conceptual diagram illustrating an example dissolved phase hybrid battery, generally designated 300, in accordance with at least one embodiment of the present invention.

[0035] Figure 4 FIG. 1 is a diagram showing a closed battery system according to at least one embodiment of the present invention. Figure 3 0047 is a conceptual diagram of an exemplary dissolved phase hybrid battery 300 in which the closed battery system is generally designated 400.

[0036] Figure 5 is a graph of the areal capacity of a battery with a dissolved LiI positive electrode.

[0037] Figure 6 It is a graph of the area capacity of a battery having a LiFePO4 positive electrode.

[0038] Figure 7 is a graph of the area capacity of the first battery having a hybrid dissolved LiI positive electrode / solid phase LiFePO4 positive electrode.

[0039] Figure 8 is a graph of the area capacity of a second battery having a mixed dissolved LiI positive electrode / solid phase LiFePO4 positive electrode.

[0040] Fig. 9 is a graph of the cycling performance of the first battery formed by a mixed dissolved phase LiI positive electrode / solid phase LiFePO4 positive electrode.

[0041] Fig.10 is a graph of the cycling performance of a second battery formed of a mixed dissolved phase LiI positive electrode / solid phase LiFePO4 positive electrode.

[0042] Fig.11It is a graph of the cycle performance of the third battery formed by the mixed dissolved phase LiI positive electrode / solid phase LiFePO4 positive electrode. DETAILED DESCRIPTION

[0043] The present invention relates generally to the field of energy storage devices, and more particularly to energy storage devices having one or more positive electrodes formed from a plurality of active materials, including at least one active material that utilizes a chemical conversion mechanism for energy storage, and at least one other active material that utilizes an ion intercalation mechanism for energy storage.

[0044] Embodiments of the present invention provide a method for increasing the energy density of a rechargeable lithium ion battery positive electrode and / or reducing the cost of a rechargeable lithium battery positive electrode by mixing a conventional lithium ion embedding positive electrode material with a halogen positive electrode conversion material or a metal halide positive electrode conversion material to form an improved positive electrode, and the resulting energy storage device. According to an embodiment of the present invention, an energy storage device with a hybrid positive electrode is provided, wherein the energy density of a conventional metal ion embedding positive electrode (e.g., lithium nickel manganese cobalt oxide (Li-NMC), lithium cobalt oxide (LCO), lithium iron phosphate (LFP)) is increased by adding a halogen conversion material or a metal halide conversion material (e.g., iodine (I2) or lithium iodide (LiI)).

[0045] The motivation behind creating a hybrid positive electrode material formed from a lithium-ion intercalation material and a halogen conversion material or a metal halide conversion material is two-fold. First, embodiments of the present invention recognize that the cost of a positive electrode formed in part from cobalt and / or nickel continues to increase, and that the market for these metals is generally very volatile. In addition, there are supply chain issues for cobalt and nickel due to the increase in environmental stability measures implemented for mining these metals. Embodiments of the present invention provide a hybrid energy storage device with reduced cost and improved environmental impact by generating a hybrid positive electrode formed from a halogen conversion material or a metal halide conversion material and an intercalation positive electrode based on NMC or LCO. It should be understood that by replacing a portion of the cobalt and / or nickel used to form the positive electrode with a lower cost and more environmentally sustainable halogen conversion material or a metal halide conversion material, a hybrid energy storage device having an energy density similar to and / or exceeding the energy density of current lithium-ion batteries having a positive electrode formed entirely from NMC or LCO can be achieved.

[0046] Second, the embodiments of the present invention recognize that although the lithium-ion battery having a positive electrode formed entirely of iron phosphate is already very cost-effective, its energy density (theoretical specific capacity of about 170 mAh / g) is less than the energy density of the lithium-ion battery having a positive electrode formed entirely of NMC or LCO. This lower energy density greatly limits the scope of application of lithium-ion batteries with a positive electrode formed of iron phosphate. The embodiments of the present invention provide an increased energy density of a lithium-ion battery having a positive electrode formed of iron phosphate by generating a hybrid positive electrode formed of a halogen conversion material or a metal halide conversion material and LFP, while maintaining a relatively low manufacturing cost. It should be understood that by replacing part of the iron phosphate used to form the positive electrode with a halogen conversion material or a metal halide conversion material, a cheaper and more environmentally sustainable hybrid energy storage device with increased energy density is achieved.

[0047] According to one embodiment of the present invention, a solid phase hybrid positive lithium ion battery is formed by an embedding material and a halogen or metal halide-based conversion material, wherein both the embedding material and the halogen or metal halide-based conversion material are prepared into a slurry and the slurry is coated on a current collector. According to another embodiment of the present invention, a "dissolved phase" or "liquid phase" hybrid positive lithium ion battery formed by an embedding material and a halogen or metal halide-based positive conversion material, wherein only the embedding material is prepared into a slurry and coated on a current collector, and the halogen or metal halide-based positive conversion material is dissolved in an electrolyte having one or more other ionic salts. In this case, the halogen or metal halide-based positive conversion material plays a dual role as an electrolyte (promoting lithium ion transport) and an active positive conversion material.

[0048] The description of various embodiments of the present invention is presented for the purpose of illustration, but is not intended to be exhaustive or limited to the disclosed embodiments. Various modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, practical application or technical improvement of technologies found in the marketplace, or to enable other persons of ordinary skill in the art to understand the embodiments disclosed herein.

[0049] The present invention will now be described in detail with reference to the accompanying drawings. Figure 1 is a conceptual diagram illustrating an example solid phase hybrid positive electrode battery (hereinafter referred to as battery 100 and generally designated as battery 100 ) according to at least one embodiment of the present invention. Figure 1The description of only one embodiment is provided and does not imply any limitation on the conditions under which the different embodiments can be implemented. A person skilled in the art may make various modifications to the conditions without departing from the scope of the invention as described in the claims.

[0050] The battery 100 includes a negative electrode current collector 110, a negative electrode 112, an electrolyte 114, a separator 116, a positive electrode 118, and a positive electrode current collector 120. The battery 100 operates through a reduction-oxidation (redox) reaction. For example, the battery 100 utilizes different oxidation states and different redox reactions of one or more components or elements to charge and discharge the battery 100.

[0051] The negative electrode current collector 110 may include a material with suitable conductivity, which collects electrons generated by the redox reaction during the discharge of the battery 100 and provides a conductive path to the external circuit to which the battery 100 is connected. Similarly, during the recharging of the battery 100, the negative electrode current collector 110 provides a conductive path between the external voltage source and the negative electrode 112, thereby providing voltage for another redox reaction, thereby charging the battery 100. The negative electrode current collector 110 may be formed of any material that is stable or passivated at the corresponding electrochemical potential of the negative electrode 112. In an embodiment, the negative electrode current collector 110 may include woven or non-woven metal fibers, metal foams, metal foils, or woven or non-woven carbon fibers. In an embodiment, the negative electrode current collector 110 may additionally or alternatively include a stainless steel mesh, a copper (Cu) mesh, a nickel (Ni) foam, and / or carbon paper. For example, the negative electrode current collector 110 may include a stainless steel mesh on which carbon nanoparticles are deposited. In another embodiment, the negative electrode current collector 110 may be a conductive porous material.

[0052] The negative electrode 112 absorbs metal ions from the electrolyte 114 during charging and releases metal ions into the electrolyte 114 during discharging. The negative electrode 112 can be any negative electrode. For example, the negative electrode 112 can be formed from, but not limited to, lithium, magnesium, sodium, or any possible combination thereof. In some embodiments, the negative electrode 112 is essentially composed of elemental lithium, elemental magnesium, or elemental sodium, or a lithium alloy, magnesium alloy, or sodium alloy formed with one or more than one other element. In an embodiment, the negative electrode 112 is lithium metal.

[0053] The electrolyte 114 includes at least one solvent and at least one lithium-containing compound. In some embodiments, at least one solvent of the electrolyte 114 may be selected from, but not limited to, carbonate compounds, heterocyclic compounds, ethers, esters, cyclic ethers, cyclic esters, nitriles, and mixtures thereof and combinations thereof. In some embodiments, at least one solvent of the electrolyte 114 may also be selected from, for example, non-aqueous organic solvents, such as ethers, ethylene glycol dimethyl ether, carbonates, nitriles, amides, amines, organic sulfur solvents, organic phosphorus solvents, organic silicon solvents, fluorinated solvents, adiponitrile (ADN), propylene carbonate (PC), dioxolanes, dimethoxyethane (DME), and mixtures thereof and combinations thereof. In an embodiment, the electrolyte 114 includes equal parts of solvents containing 1,3-dioxolanes and 1,2-dimethoxyethane. In an embodiment, the lithium-containing compound is a lithium salt, such as lithium bis(trifluoromethanesulfonyl)imide or LiTFSI. In an embodiment, the electrolyte 114 also includes at least one salt. For example, the salt may be provided by a lithium-containing compound of the electrolyte 114 , such as LiTFSI.

[0054] In some embodiments, the electrolyte 114 also includes one or more oxidizing gases. In embodiments, the electrolyte 114 may be in the presence of an oxidizing gas, and the phrase "comprising an oxidizing gas" is intended to include such a configuration. In embodiments, one or more oxidizing gases may be dissolved in a solvent comprising at least one salt and at least one lithium-containing compound of the electrolyte 114. In embodiments, the oxidizing gas may include, but is not limited to, at least one of air, oxygen, nitric oxide, nitrogen dioxide, or a mixture thereof and a combination thereof. The oxidizing gas helps to cause the redox reaction of the battery 100 as described above, and helps to achieve a highly reversible redox reaction, which can contribute to the enhanced electrochemical performance of the battery 100. It should be noted that although the oxidizing gas can help to cause such a redox reaction, the oxidizing gas will not be consumed or generated during the use of the battery 100 (i.e., the oxidizing gas does not participate in the redox reaction of the battery 100).

[0055] The separator 116 provides an electronic insulation barrier between the negative electrode 112 and the positive electrode 118, thereby forcing the electrons to pass through the external circuit to which the battery 100 is connected, which prevents the electrons from passing through the battery 100 (e.g., through the electrolyte 114 of the battery 100), while the metal ions can still flow through the battery 100 during charging and discharging. In various embodiments, the separator 116 can be coated with the electrolyte 114, soaked with the electrolyte 114, placed in the electrolyte 114, or surrounded / immersed in the electrolyte 114. In an embodiment, the separator 116 includes a non-conductive material to prevent the electrons from moving through the battery 100, which allows the electrons to move through the external circuit instead. For example, the separator 116 can include glass, non-woven fibers, polymer films, or rubber.

[0056] The positive electrode 118 includes an active positive conversion material (also interchangeably referred to herein as a "positive conversion material" or simply a "conversion material") and a lithium ion insertion host (also interchangeably referred to herein as a "positive insertion material" or simply a "insertion material"). In some embodiments, the active positive conversion material is a halogen molecule. For example, the halogen molecule can be selected from, but not limited to, F2, Cl2, Br2, and I2. In some embodiments, the active positive conversion material is a metal halide (e.g., MX, where M is a metal element and X is a halogen element). In an embodiment, the metal halide can be dissolved in a solvent and dissociated into a corresponding metal ion and a corresponding halide ion. In an embodiment, the metal ion can be selected from, but not limited to, Li + 、Al 3+ Mg 2+ Or Na + At least one of (for example, M may be Li, Al, Mg or Na), and the halide ions may include but are not limited to I - Br - , Cl - or F - In some embodiments, the active cathode conversion material is an organic halide compound (e.g., AX, where A is a positively charged organic species and X is a negatively charged halogen element). In embodiments, the organic halide compound can be dissolved in a solvent and dissociated into a corresponding organic cation and a corresponding halide anion. In embodiments, the organic cation can be selected from, but not limited to, ammonium, alkylammonium, imidazole, or pyrrolidine At least one of the following, and the halide anion may include but is not limited to I - Br - , Cl - or F - At least one of the ions (eg, X may be I, Br, Cl, or F).

[0057] In an embodiment, the lithium ion intercalation host is a metal oxide compound. For example, the lithium ion intercalation host can be selected from, but not limited to, lithium cobalt oxide (LCO) (e.g., LiCoO2), nickel cobalt aluminum (NCA) (e.g., LiNi x Co y Al z O2、LiNi 0.8 Co 0.15 Al 0.05O2), lithium manganese oxide (LMO) (e.g. LiMn2O4), lithium nickel manganese cobalt oxide (NMC) (e.g. LiNiMnCoO2), nickel cobalt manganese oxide (NCM) (e.g. LiNi x Co y Mn z O2、LiNi 0.33 Co 0.33 Mn 0.33 O2), lithium iron phosphate (LFP, such as LiFePO4), and mixtures and combinations thereof.

[0058] The positive electrode 118 is in electrochemical contact and / or physical contact with the positive current collector 120. In some embodiments, the positive electrode 118 of the battery 100 is in a viscous state or a slurry state. In other embodiments, the positive electrode 118 of the battery 100 is in a solid phase. In the embodiment in which the positive electrode 118 remains in a solid phase, the density of the positive electrode 118 needs to be, but not necessarily, greater than the density of the positive current collector 120. In the embodiment, the positive electrode 118 is initially formed in a viscous state or a slurry state, is coated on at least the bottom surface of the positive current collector 120, and solidifies to form a final solid positive electrode.

[0059] The positive electrode current collector 120 may include a material with suitable conductivity, which collects electrons generated by the redox reaction during the discharge of the battery 100 and provides a conductive path to the external circuit to which the battery is connected. Similarly, during the recharging of the battery 100, the positive electrode current collector 120 provides a conductive path between the external voltage source and the positive electrode 118, thereby providing voltage for another redox reaction, thereby charging the battery 100. The positive electrode current collector 120 may be formed of any material that is stable or passivated at the corresponding electrochemical potential of the positive electrode 118. In an embodiment, the positive electrode current collector 120 may include woven or non-woven metal fibers, metal foams, metal foils, or woven or non-woven carbon fibers. In an embodiment, the positive electrode current collector 120 may additionally or alternatively include a stainless steel mesh, an aluminum (Al) mesh, a nickel (Ni) foam, and / or carbon paper. For example, the positive electrode current collector 120 may include a stainless steel mesh on which aluminum nanoparticles are deposited. In another embodiment, the positive electrode current collector 120 may be a conductive porous material.

[0060] In some embodiments, the battery 100 has a closed volume. For example, the negative electrode current collector 110, the negative electrode 112, the electrolyte 114, the separator 116, the positive electrode 118, and the positive electrode current collector 120 are in a closed battery or other enclosure. In this way, one or more than one oxidizing additives in the battery 100 remain confined inside the battery 100. In other embodiments, the battery 100 has a substantially closed volume. For example, the negative electrode current collector 110, the negative electrode 112, the electrolyte 114, the separator 116, the positive electrode 118, and the positive electrode current collector 120 are in a substantially closed battery or other enclosure. In this way, one or more than one oxidizing additives in the battery 100 can be added to the battery 100 and / or removed from the battery 100.

[0061] Figure 2 The closed battery system 200 is shown in FIG. Figure 1 Conceptual diagram of battery 100 in FIG. Figure 2 The description of only one embodiment is provided and does not imply any limitation on the conditions under which the different embodiments can be implemented. A person skilled in the art may make various modifications to the conditions without departing from the scope of the invention as described in the claims.

[0062] The closed battery system 200 may include a battery that contains the battery 100 during operation of the battery 100, a battery used to manufacture the battery 100, or both. For example, the closed battery system 200 may include a battery available from Swagelok, Solon, Ohio, under the trade name SWAGELOK, and may be used to manufacture the battery 100. In an embodiment, the closed battery system 200 may include an inlet tube 210 and / or an outlet tube 220. The inlet tube 210 and the outlet tube 220 may be used to introduce oxidizing additives into and remove them from the closed battery system 200, including but not limited to air, oxygen, nitric oxide, nitrogen dioxide, mixtures thereof, and combinations thereof.

[0063] Figure 3 is a conceptual diagram illustrating an example dissolved phase hybrid cathode battery (hereinafter referred to as a battery and generally designated 300 ) in accordance with at least one embodiment of the present invention. Figure 3 The description of only one embodiment is provided and does not imply any limitation on the conditions under which the different embodiments can be implemented. A person skilled in the art may make various modifications to the conditions without departing from the scope of the invention as described in the claims.

[0064] The battery 300 includes a negative electrode current collector 310, a negative electrode 312, an electrolyte 314, a separator 316, a positive electrode 318, and a positive electrode current collector 320. The battery 300 operates through a reduction-oxidation (redox) reaction. For example, the battery 300 utilizes different oxidation states and different redox reactions of one or more components or elements to charge and discharge the battery 300.

[0065] The negative electrode current collector 310 may include a material with suitable conductivity, which collects electrons generated by the redox reaction during the discharge of the battery 300 and provides a conductive path to the external circuit to which the battery is connected. Similarly, during the recharging of the battery 300, the negative electrode current collector 310 provides a conductive path between the external voltage source and the electrolyte 314, thereby providing voltage for another redox reaction, thereby charging the battery 300. The negative electrode current collector 310 may be formed of any material that is stable or passivated at the corresponding electrochemical potential of the negative electrode 312. In an embodiment, the negative electrode current collector 310 may include woven or non-woven metal fibers, metal foams, metal foils, or woven or non-woven carbon fibers. In an embodiment, the negative electrode current collector 310 may additionally or alternatively include a stainless steel mesh, a copper (Cu) mesh, a nickel (Ni) foam, and / or carbon paper. For example, the negative electrode current collector 310 may include a stainless steel mesh on which carbon nanoparticles are deposited. In another embodiment, the negative electrode current collector 310 may be a conductive porous material.

[0066] The negative electrode 312 absorbs metal ions from the electrolyte 314 during charging and releases metal ions into the electrolyte 314 during discharging. The negative electrode 312 can be any negative electrode material. For example, the negative electrode 312 can be composed of, but not limited to, lithium, magnesium, sodium, or any possible combination thereof. In some embodiments, the negative electrode 312 is essentially composed of elemental lithium, elemental magnesium, or elemental sodium, or a lithium alloy, magnesium alloy, or sodium alloy formed with one or more than one other element. In an embodiment, the negative electrode 312 is lithium metal.

[0067] The electrolyte 314 includes at least one solvent and at least one halogen-containing compound serving as an active positive electrode conversion material. In some embodiments, at least one solvent of the electrolyte 314 can be selected from, but not limited to, carbonate compounds, heterocyclic compounds, ethers, esters, cyclic ethers, cyclic esters, nitriles, and mixtures thereof and combinations thereof. In some embodiments, at least one solvent of the electrolyte 314 can also be selected from, for example, non-aqueous organic solvents, such as ethers, ethylene glycol dimethyl ether, carbonates, nitriles, amides, amines, organic sulfur solvents, organic phosphorus solvents, organic silicon solvents, fluorinated solvents, adiponitrile (ADN), propylene carbonate (PC), dioxolanes, dimethoxyethane (DME), and mixtures thereof and combinations thereof. In embodiments, the electrolyte 314 includes equal parts of solvents containing 1,3-dioxolanes and 1,2-dimethoxyethane. In embodiments, the electrolyte 314 also includes lithium salts, such as lithium bis(trifluoromethanesulfonyl)imide or LiTFSI.

[0068] At least one halogen-containing compound of the electrolyte 314 acts as an active positive conversion material. For example, the halogen-containing compound of the electrolyte 314 can receive, store and release metal ions for halogen redox reactions during the charging and discharging of the battery 300. In this way, the battery 300 can include a positive electrode having only a positive electrode embedded material positive electrode without a dedicated positive conversion material. It should be understood that by having an electrolyte containing a halogen-containing compound that acts as an active positive conversion material, the battery 300 can make the manufacturing cost cheaper, lighter, have a higher energy density, a higher power density, or a combination thereof. For example, the high power density of the electrolyte 314 containing a halogen-containing compound that acts as an active positive conversion material can enable the battery 300 to have a higher energy density and charge significantly faster than other batteries that do not have an electrolyte containing a halogen-containing compound that acts as an active positive conversion material.

[0069] In some embodiments, the halogen-containing compound of the electrolyte 314 acting as an active positive conversion material is a halogen molecule. For example, the halogen molecule can be selected from, but not limited to, F2, Cl2, Br2, and I2. In some embodiments, the halogen-containing compound of the electrolyte 314 acting as an active positive conversion material is a metal halide salt (e.g., MX, where M is a metal element and X is a halogen element). In an embodiment, the metal halide can be dissolved in a solvent and dissociated into a corresponding metal ion and a corresponding halide ion. In an embodiment, the metal ion can be selected from, but not limited to, Li + 、Al 3+ Mg 2+ Or Na + At least one of (for example, M may be Li, Al, Mg or Na), and the halide ions may include but are not limited to I - Br - , Cl- or F - In other embodiments, the halogen-containing compound of the electrolyte 314 serving as the active positive electrode conversion material is an organic halide salt (e.g., AX, where A is a positively charged organic species and X is a negatively charged halogen element). In embodiments, the organic halide salt can be dissolved in a solvent and dissociated into a corresponding organic cation and a corresponding halide anion. In embodiments, the organic cation can be selected from, but not limited to, ammonium, alkylammonium, imidazole, or pyrrolidine At least one of the following, and the halide anion may include but is not limited to I - Br - , Cl - or F - At least one of the ions (eg, X may be I, Br, Cl, or F).

[0070] In some embodiments, the electrolyte 314 also includes one or more oxidizing gases. In embodiments, the electrolyte 314 may be in the presence of an oxidizing gas, and the phrase "comprising an oxidizing gas" is intended to include such a configuration. In embodiments, one or more oxidizing gases may be dissolved in a solvent comprising at least one salt and at least one lithium-containing compound of the electrolyte 314. In embodiments, the oxidizing gas may include, but is not limited to, at least one of air, oxygen, nitric oxide, nitrogen dioxide, or a mixture thereof and a combination thereof. The oxidizing gas helps to cause the redox reaction of the battery 300 as described above, and helps to achieve a highly reversible redox reaction, which can contribute to the enhanced electrochemical performance of the battery 300. It should be noted that although the oxidizing gas can help to cause such a redox reaction, the oxidizing gas will not be consumed or generated during the use of the battery 300 (i.e., the oxidizing gas does not participate in the redox reaction of the battery 300).

[0071] The separator 316 forces the electrons to pass through the external circuit to which the battery 300 is connected, which prevents the electrons from passing through the battery 300 (e.g., through the electrolyte 314 of the battery 300), while the metal ions can still flow through the battery 300 during charging and discharging. In various embodiments, the separator 316 can be coated with the electrolyte 314, soaked with the electrolyte 314, placed in the electrolyte 314, or surrounded / immersed in the electrolyte 314. In an embodiment, the separator 316 includes a non-conductive material to prevent the electrons from moving through the battery 300, which allows the electrons to move through the external circuit instead. For example, the separator 316 can include glass, non-woven fibers, polymer films, or rubber.

[0072] The positive electrode 318 includes a lithium ion intercalation host. In an embodiment, the lithium ion intercalation host is a metal oxide or a metal phosphate compound. For example, the lithium ion intercalation host of the positive electrode 318 can be selected from, but not limited to, lithium cobalt oxide (LCO) (e.g., LiCoO2), nickel cobalt aluminum (NCA) (e.g., LiNi x Co y Al z O2、LiNi 0.8 Co 0.15 Al 0.05 O2), lithium manganese oxide (LMO) (e.g. LiMn2O4), lithium nickel manganese cobalt oxide (NMC) (e.g. LiNiMnCoO2), nickel cobalt manganese oxide (NCM) (e.g. LiNi x Co y Mn z O2、LiNi 0.33 Co 0.33 Mn 0.33 O2), lithium iron phosphate (LFP, such as LiFePO4), and mixtures and combinations thereof.

[0073] In some embodiments, in addition to the lithium ion intercalation host, the positive electrode 318 also includes a halogen-containing compound that acts as an active positive conversion material. In some embodiments, a portion of the lithium ion intercalation host of the positive electrode 318 (e.g., nickel or cobalt if the intercalation host is NMC, and cobalt if the intercalation host is LCO) is replaced by the halogen-containing compound that acts as an active positive conversion material. In other embodiments, the halogen-containing compound that acts as an active positive material is added to the positive electrode 318 without replacing a portion of the lithium ion intercalation host of the positive electrode 318.

[0074] In an embodiment, the halogen-containing compound of the positive electrode 318 that serves as the active positive conversion material is the same as the halogen-containing compound of the electrolyte 314 that also serves as the active positive conversion material. In an embodiment, the halogen-containing compound included in the positive electrode 318 that serves as the positive conversion material is different from the halogen-containing compound included in the electrolyte 314 that also serves as the active positive conversion material. It should be understood that by including the active positive conversion material in both the electrolyte 314 and the positive electrode 318, a hybrid energy storage device with increased energy density is achieved.

[0075] In an embodiment, the lithium ion insertion host of the positive electrode 318 is a metal oxide or a metal phosphate compound. For example, the lithium ion insertion host of the positive electrode 318 can be selected from, but not limited to, lithium cobalt oxide (LCO) (e.g., LiCoO2), nickel cobalt aluminum (NCA) (e.g., LiNi x Co y Al z O2、LiNi 0.8Co 0.15 Al 0.05 O2), lithium manganese oxide (LMO) (e.g. LiMn2O4), lithium nickel manganese cobalt oxide (NMC) (e.g. LiNiMnCoO2), nickel cobalt manganese oxide (NCM) (e.g. LiNi x Co y Mn z O2、LiNi 0.33 Co 0.33 Mn 0.33 O2), lithium iron phosphate (LFP, such as LiFePO4), and mixtures and combinations thereof.

[0076] The positive electrode 318 is in electrochemical contact and / or physical contact with the positive current collector 320. In some embodiments, the positive electrode 318 of the battery 300 is in a viscous state or a slurry state. In other embodiments, the positive electrode 318 of the battery 300 is in a solid phase. In the embodiment in which the positive electrode 318 remains in a solid phase, the density of the positive electrode needs to be, but not necessarily, greater than the density of the positive current collector 320. In the embodiment, the positive electrode 318 is initially formed in a viscous state or a slurry state, is coated on at least the bottom surface of the positive current collector 320, and solidifies to form a final solid positive electrode.

[0077] The positive electrode collector 320 may include a material with suitable conductivity, which collects electrons generated by the redox reaction during the discharge of the battery 300 and provides a conductive path to the external circuit to which the battery is connected. Similarly, during the recharging of the battery 300, the positive electrode collector 320 provides a conductive path between the external voltage source and the electrolyte 314, thereby providing voltage for another redox reaction, thereby charging the battery 300. The positive electrode collector 320 may be formed of any material that is stable or passivated at the corresponding electrochemical potential of the positive electrode 318. In an embodiment, the positive electrode collector 320 may include woven or non-woven metal fibers, metal foams, metal foils, or woven or non-woven carbon fibers. In an embodiment, the positive electrode collector 320 may additionally or alternatively include a stainless steel mesh, an aluminum (Al) mesh, a nickel (Ni) foam, and / or carbon paper. For example, the positive electrode collector 320 may include a stainless steel mesh on which aluminum nanoparticles are deposited. In another embodiment, the positive electrode collector 320 may be a conductive porous material.

[0078] In some embodiments, the battery 300 has a closed volume. For example, the negative electrode current collector 310, the negative electrode 312, the electrolyte 314, the separator 316, the positive electrode 318, and the positive electrode current collector 320 are in a closed battery or other housing. In this way, one or more than one oxidizing additives in the battery 300 remain confined in the battery 300. In other embodiments, the battery 300 has a substantially closed volume. For example, the negative electrode current collector 310, the negative electrode 312, the electrolyte 314, the separator 316, the positive electrode 318, and the positive electrode current collector 320 are in a substantially closed battery or other housing. In this way, one or more than one oxidizing additives in the battery 300 can be added to the battery 300 and / or removed from the battery 300.

[0079] Figure 4 The closed battery system 400 is shown in FIG. Figure 3 4. A closed battery system 400 may include a battery that houses the battery 300 during operation of the battery 300, a battery used to manufacture the battery 300, or both. For example, the closed battery system 400 may include a battery available from Swagelok in Solon, Ohio under the trade name SWAGELOK and may be used to manufacture the battery 300. In an embodiment, the closed battery system 400 may include an inlet tube 410 and / or an outlet tube 420. The inlet tube 410 and the outlet tube 420 may be used to introduce oxidizing additives into and remove them from the closed battery system 400, the oxidizing additives including, but not limited to, air, oxygen, nitric oxide, nitrogen dioxide, mixtures thereof, and combinations thereof.

[0080] Step 1

[0081] Preparation of secondary energy storage devices with "solid-phase" hybrid cathodes

[0082] The positive electrode is prepared by first forming a slurry containing a halogen positive electrode conversion material (e.g., I2) or a metal halide positive electrode conversion material (e.g., LiI), a lithium-based intercalation positive electrode material (e.g., LFP), a conductive additive, and a binder. The slurry is then coated on a current collector and dried to produce the final positive electrode.

[0083] The electrolyte is prepared by dissolving a lithium salt (eg, LiTFSI) in one or more aprotic organic solvents (eg, a 1:1 mixture of 1,3-dioxolane / 1,2-dimethoxyethane) to achieve a desired electrolyte concentration.

[0084] Step 2

[0085] Preparation of secondary energy storage devices with "dissolved phase" hybrid cathodes

[0086] The positive electrode is prepared by forming a slurry containing an embedded positive electrode material (such as LFP), a conductive additive and a binder. The slurry is then coated onto a current collector and dried to produce the final positive electrode.

[0087] The cathode / electrolyte solution is prepared by dissolving a metal halide salt (e.g., LiI) or halogen (I2) in one or more aprotic organic solvents (e.g., a 1:1 mixture of 1,3-dioxolane / 1,2-dimethoxyethane) to achieve the desired cathode / electrolyte concentration.

[0088] Example 1

[0089] Formation of secondary energy storage devices with “solid-phase” hybrid cathodes

[0090] A secondary energy storage device with a "solid phase" hybrid positive electrode is formed by placing a wave spring on the negative electrode side of a 2032 button cell. Then, a piece of lithium foil (negative electrode) is mounted on a 0.5 mm stainless steel spacer and placed on top of the wave spring. A small amount of electrolyte prepared according to the first step is deposited on the lithium metal negative electrode, and then a polymer separator (such as Celgard 2325) is placed on it. Then, another small amount of electrolyte prepared according to the first step is deposited onto the polymer separator and then onto the hybrid positive electrode prepared according to the first step. Finally, the button cell is sealed.

[0091] Example 2

[0092] Formation of secondary energy storage devices with “dissolved phase” hybrid cathodes

[0093] A secondary energy storage device with a "dissolved phase" hybrid positive electrode is formed by placing a wave spring on the negative electrode side of a 2032 button cell. A piece of lithium foil (negative electrode) is then mounted on a 0.5 mm stainless steel spacer and placed on top of the wave spring. A small amount of the positive electrode / electrolyte solution prepared according to the second step is deposited on the lithium metal negative electrode, and a polymer separator (such as Celgard 2325) is then placed on it. Another small amount of the positive electrode / electrolyte solution prepared according to the second step is then deposited onto the polymer separator and then onto the hybrid positive electrode prepared according to the second step. Finally, the button cell is sealed.

[0094] Comparative Example 1

[0095] Areal capacity of a cell with a "dissolved phase" cathode containing only a single active conversion material (LiI)

[0096] Figure 5 is a graph of the areal capacity of a battery with a "dissolved phase" LiI positive electrode. More specifically, Figure 5Shown is the specific capacity normalized by the positive electrode area of ​​a cell formed with a lithium metal anode, a porous carbon on carbon cloth positive electrode, and 100 µL of an electrolyte containing 0.4 mM LiNO3, 1 mM LiI per 500 µL 1,3-dioxolane and 500 µL 1,2-dimethoxyethane.

[0097] Comparative Example 2

[0098] Areal capacity of a battery with a positive electrode containing only a single active intercalation material (LiFePO4)

[0099] Figure 6 is a graph of the area capacity of a battery with a LiFePO4 positive electrode. More specifically, Figure 6 Shown are the specific capacities normalized by the positive electrode area for cells formed with a lithium metal anode, a porous carbon on carbon cloth positive electrode and a lithium iron phosphate positive electrode, and 100 µL of an electrolyte containing 0.4 mM LiNO3, 1 mM LiPF6 per 500 µL 1,3-dioxolane and 500 µL 1,2-dimethoxyethane.

[0100] Working Example 1

[0101] Area capacity of the first battery with a mixed dissolved phase LiI / solid phase LiFePO4 positive electrode

[0102] Figure 7 is a graph of the area capacity of a battery with a mixed dissolved LiI / solid phase LiFePO4 positive electrode. More specifically, Figure 7 Shown are the specific capacities normalized by the positive electrode area of ​​cells formed with a lithium metal anode, a porous carbon on carbon cloth positive electrode and a lithium iron phosphate positive electrode, and 100 µL of an electrolyte containing 0.4 mM LiNO3, 1 mM LiI per 500 µL 1,3-dioxolane and 500 µL 1,2-dimethoxyethane.

[0103] Working Example 2

[0104] Area capacity of the second battery with a mixed dissolved phase LiI / solid phase LiFePO4 positive electrode

[0105] Figure 8 is a graph of the area capacity of a battery with a mixed dissolved LiI / solid phase LiFePO4 positive electrode. More specifically, Figure 8 Shown are the specific capacities normalized by the positive electrode area of ​​cells formed with a lithium metal anode, a porous carbon on carbon cloth positive electrode and a lithium iron phosphate positive electrode, and 100 µL of an electrolyte containing 0.4 mM LiNO3, 5 mM LiI per 500 µL 1,3-dioxolane and 500 µL 1,2-dimethoxyethane.

[0106] Cycle Performance Example 1

[0107] The first battery formed by a mixed dissolved phase LiI / solid phase LiFePO4 positive electrode

[0108] Fig. 9 The cycling performance of a battery formed by a mixed dissolved phase LiI / solid phase LiFePO4 positive electrode is shown. More specifically, Fig. 9 The cycling performance of a cell comprising a lithium metal anode, a porous carbon on carbon cloth cathode and a lithium iron phosphate cathode, and 100 µL of an electrolyte containing 0.4 mM LiNO3, 1 mM LiI per 500 µL 1,3-dioxolane and 500 µL 1,2-dimethoxyethane is shown. Galvanostatic cycling was performed in the voltage range of 2.7 V to 3 V, so that the iodine electrochemical reaction, rather than the LFP electrochemical reaction, contributes to the total capacity of the cell.

[0109] Cycle Performance Example 2

[0110] The second battery formed by the mixed dissolved phase LiI / solid phase LiFePO4 positive electrode

[0111] Fig.10 The cycling performance of a battery formed by a mixed dissolved phase LiI / solid phase LiFePO4 positive electrode is shown. More specifically, Fig.10 The cycling performance of a battery including a lithium metal anode, a positive electrode of porous carbon and lithium iron phosphate on a carbon cloth positive electrode, and 100 µL of an electrolyte containing 0.4 mM LiNO3, 1 mM LiI per 500 µL of 1,3-dioxolane and 500 µL of 1,2-dimethoxyethane is shown. Galvanostatic cycling was performed in the voltage range of 3 V to 3.6 V, so that the LFP electrochemical reaction, rather than the iodine electrochemical reaction, contributes to the total capacity of the battery.

[0112] Cycle Performance Example 3

[0113] The third battery formed by the mixed dissolved phase LiI / solid phase LiFePO4 positive electrode

[0114] Fig.11 The cycling performance of a battery formed by a mixed dissolved phase LiI / solid phase LiFePO4 positive electrode is shown. More specifically, Fig.11The cycling performance of a battery including a lithium metal anode, a positive electrode of porous carbon and lithium iron phosphate on a carbon cloth positive electrode, and 100µL of an electrolyte containing 0.4mM LiNO3, 1mM LiI per 500µL 1,3-dioxolane and 500µL 1,2-dimethoxyethane is shown. Galvanostatic cycling was performed in the voltage range of 2.7V to 3.6V, so that both the iodine electrochemical reaction and the LFP electrochemical reaction contribute to the total capacity of the battery.

Claims

1. A rechargeable battery comprising: negative electrode; a positive electrode, wherein the positive electrode comprises a lithium ion intercalation host; and An electrolyte, wherein the electrolyte comprises a solvent and a first halogen-containing compound that serves as an active positive electrode conversion material, and wherein the electrolyte is also in contact with the negative electrode and the positive electrode.

2. The rechargeable battery of claim 1, wherein the positive electrode further comprises a second halogen-containing compound that serves as an active positive electrode conversion material.

3. The rechargeable battery according to claim 2, wherein the first halogen-containing compound contained in the electrolyte and serving as an active positive electrode conversion material and the second halogen-containing compound contained in the positive electrode and serving as an active positive electrode conversion material are the same. 4 . The rechargeable battery according to claim 2 , wherein the first halogen-containing compound contained in the electrolyte and serving as an active positive electrode conversion material and the second halogen-containing compound contained in the positive electrode and serving as an active positive electrode conversion material are different. 5 . The rechargeable battery according to claim 1 , wherein the halogen-containing compound contained in the electrolyte serving as an active positive electrode conversion material is a metal halide.

6. The rechargeable battery according to claim 4, wherein the metal halide dissociates into corresponding halide ions and corresponding metal ions in the solvent, and wherein the halide ions include I - Br - , Cl - or F - At least one of the metal ions, and the metal ions include Li + 、Al 3+ Mg 2+ Or Na + At least one of .

7. The rechargeable battery of claim 1, wherein the lithium ion intercalation host is selected from the group consisting of lithium cobalt oxide, nickel cobalt aluminum, lithium ion manganese oxide, lithium nickel manganese cobalt oxide, nickel cobalt manganese oxide, lithium iron phosphate, and mixtures and combinations thereof.

8. The rechargeable battery according to claim 1, wherein the solvent of the electrolyte is selected from the group consisting of carbonate compounds, heterocyclic compounds, ethers, esters, cyclic ethers, cyclic esters, nitriles, mixtures thereof, and combinations thereof.

9. The rechargeable battery according to claim 1, further comprising one or more than one oxidizing gas selected from the group consisting of air, oxygen, nitric oxide, nitrogen dioxide, mixtures thereof, and combinations thereof.

10. A rechargeable battery comprising: negative electrode; a positive electrode, wherein the positive electrode comprises a halogen-containing compound serving as an active positive electrode conversion material and a lithium ion intercalation host; and An electrolyte, wherein the electrolyte comprises a solvent and a lithium-containing compound, and wherein the electrolyte is also in contact with the negative electrode and the positive electrode. 11 . The rechargeable battery according to claim 10 , wherein the halogen-containing compound contained in the positive electrode serving as an active positive electrode conversion material is a halogen or a metal halide.

12. The rechargeable battery of claim 11, wherein the metal halide comprises a corresponding halide ion and a corresponding metal ion, and wherein the halide ion comprises I - Br - , Cl - or F - At least one of the metal ions, and the metal ions include Li + 、Al 3+ Mg 2+ Or Na + At least one of .

13. The rechargeable battery according to claim 10, wherein the lithium-containing compound contained in the electrolyte is a lithium salt.

14. The rechargeable battery of claim 10, wherein the lithium ion intercalation host is selected from the group consisting of lithium cobalt oxide, nickel cobalt aluminum, lithium ion manganese oxide, lithium nickel manganese cobalt oxide, nickel cobalt manganese oxide, lithium iron phosphate, and mixtures and combinations thereof.

15. The rechargeable battery according to claim 10, wherein the solvent of the electrolyte is selected from the group consisting of carbonate compounds, heterocyclic compounds, ethers, esters, cyclic ethers, cyclic esters, nitriles, mixtures thereof, and combinations thereof.

16. The rechargeable battery according to claim 10, further comprising one or more than one oxidizing gas selected from the group consisting of air, oxygen, nitric oxide, nitrogen dioxide, mixtures thereof, and combinations thereof.

17. A method of forming a rechargeable battery, comprising: coating a slurry containing a lithium intercalation material onto a positive electrode current collector; dissolving at least one of a metal halide or a halogen in a solvent to form an electrolyte; and The negative electrode, the separator and the positive electrode current collector are stacked to form a rechargeable battery, wherein the rechargeable battery comprises: negative electrode; an electrolyte, wherein the electrolyte comprises at least one of a metal halide or a halogen that acts as an active positive electrode conversion material; Diaphragm; and A positive electrode current collector coated with the slurry.

18. The method of claim 17, further comprising adding a second halogen or a second metal halide to the cathode, wherein the second halogen or second metal halide also serves as an active cathode conversion material.

19. The method according to claim 18, wherein the second halogen or the second metal halide added to the positive electrode is the same as the halogen or the metal halide contained in the electrolyte. 20 . The method according to claim 19 , wherein the second halogen or second metal halide added to the positive electrode is different from the halogen or metal halide contained in the electrolyte.

21. The method of claim 17, further comprising replacing a portion of the lithium ion intercalation material with a second metal halide or a second halogen, wherein the second metal halide or the second halogen also serves as an active positive electrode conversion material.

22. The method according to claim 21, wherein the second metal halide or the second halogen replacing a portion of the lithium ion intercalation material is the same as the halogen or metal halide contained in the electrolyte.

23. The method according to claim 21, wherein the second metal halide or second halogen replacing a portion of the lithium ion intercalation material is different from the halogen or metal halide contained in the electrolyte.

24. A method of forming a rechargeable battery, comprising: applying a slurry comprising at least one of a halogen or a metal halide and a lithium-containing cathode intercalation material to a cathode current collector; dissolving a lithium salt in a solvent to form an electrolyte; and The negative electrode, the separator and the positive electrode current collector are stacked to form a rechargeable battery, wherein the rechargeable battery comprises: negative electrode; Electrolyte; Diaphragm; and A positive electrode current collector coated with the slurry, wherein at least one of the halogen or metal halide of the slurry serves as an active positive electrode conversion material.

Images