Rechargeable composite electrode and method thereof

Abstract

This disclosure relates to a composite cathode composition, a liquid electrolyte composition, and a rechargeable battery comprising the novel cathode composition and the electrolyte composition.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Patent Application No. 63 / 503953, filed on 23 May 2023, and U.S. Patent Application No. 63 / 650,324, filed on 21 May 2024, the entire contents of which are incorporated herein by reference.

[0002] Field of Invention The field of the present invention generally relates to batteries and battery components, and more specifically to composite cathode compositions, liquid electrolyte compositions, and the rechargeable electrochemistry of batteries having these components. [Background technology]

[0003] This background information is provided for the purpose of providing information that the applicant has considered to be potentially relevant to the present invention. Any information disclosed herein is not necessarily intended to constitute prior art to the present invention, nor should it be construed as such.

[0004] With increasing demand for electric vehicles and energy storage applications, research into new battery chemistry that can provide high energy density is urgently needed. Currently, the energy density of batteries is mainly limited by conventional layered transition metal oxide cathode materials (LiMO2, M=Ni, Co, Mn, etc.) with low capacity (<220mAh / g). X The battery offers the highest energy density (theoretical value 2189 Wh / kg), but it is not rechargeable. Extensive research has shown that CF X When it reacts with lithium, CF X It has been established that LiF is converted to carbon, as shown by the reaction equation +Li → LiF + C.

[0005] CF XTo make a battery reversible, it is necessary to drive an electrochemical reaction involving LiF. Inspired by the concept of redox bonding, cases in which LiF is combined with LiCl, LiBr, and LiI were systematically investigated. Since it is reasonably expected that the resulting interhalogen inorganic compounds (e.g., ClF, BrF, and IF) can form interhalogen compounds similar to BrCl, the energy required to drive the reaction involving LiF is significantly reduced. It is also noteworthy that LiF-based composite materials can handle higher operating voltages, which means higher energy density. From the perspective of LiF, its theoretical capacity is 1030 mAh / g, which is significantly higher than LiCl (632 mAh / g) and LiBr (309 mAh / g). [Overview of the Initiative]

[0006] This specification describes the first reversible CF with the potential to dramatically improve the operating voltage and energy density of next-generation batteries. X The chemistry is disclosed. Ex-situ XRD spectroscopy revealed that LiF is reversibly lost and formed during charging and discharging, respectively. These results indicate reversible CF X This deepens our understanding of chemistry and suggests its great potential in realizing high-energy batteries.

[0007] The following drawings form part of this specification and include for further explanation of specific aspects of the invention. The invention can be better understood by referring to one or more of these drawings in conjunction with the detailed description of the specific embodiments described herein. The patent or application documents include at least one color drawing. Copies of this patent publication or published patent publication including the color drawing are available from the Patent Office upon request and payment of the required fees. [Brief explanation of the drawing]

[0008] [Figure 1] This figure shows the XRD patterns of a LiF-LiI-graphite (FIG) electrode under various charge and discharge conditions. [Figure 2A]It is the elemental analysis imaging result showing a typical SEM image of the initial LiF-LiI-graphite (FIG) electrode. [Figure 2B] It is the elemental analysis imaging result showing the EDS mapping corresponding to element C. [Figure 2C] It is the elemental analysis imaging result showing the EDS mapping corresponding to element F. [Figure 2D] It is the elemental analysis imaging result showing the EDS mapping corresponding to element I. [Figure 2E] It is the elemental analysis imaging result showing the SEM image of the fully charged FIG electrode. [Figure 2F] It is the elemental analysis imaging result showing the EDS mapping corresponding to element C. [Figure 2G] It is the elemental analysis imaging result showing the EDS mapping corresponding to element F. [Figure 2H] It is the elemental analysis imaging result showing the EDS mapping corresponding to element I. [Figure 3A] It is a diagram showing the electrochemical performance of a CFX-LiI (CFI) || Li battery demonstrating the reversibility of LiF-based electrochemistry. [Figure 3B] It is a diagram showing the electrochemical performance of a LiF-LiI-graphite (FIG) || Li battery demonstrating the reversibility of LiF-based electrochemistry. [Figure 4] It is a diagram showing the performance of the FIG cathode in a commercial electrolyte, and the electrolyte used here is a 1M LiPF6 solution obtained by mixing ethylene carbonate and diethyl carbonate at a volume ratio of 1:1.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, specific non-limiting embodiments of the present invention will be described with reference to the accompanying drawings.

[0010] Explanation 1.0 Definitions For the purpose of facilitating the understanding of the principles of the invention, specific embodiments are referenced and specific terminology is used for their description. However, this does not limit the scope of the present invention, and it will be understood that modifications and changes to the illustrated invention, as well as further applications of the principles of the invention shown herein, are assumed herein to be possible, as would be ordinarily conceivable to a person skilled in the art relating to the invention.

[0011] Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art relating to the present invention.

[0012] In interpreting this Spec., the following definitions apply, and where appropriate, a singular term is also included in its plural form, and a plural term is also included in its singular form. If any of the following definitions conflict with the use of such term in other documents, including documents incorporated herein by reference, the following definitions shall always prevail in interpreting this Spec. and the related claims, unless the opposite meaning is explicitly intended (for example, in the document in which the term first appears).

[0013] The use of "or" means "and / or" unless otherwise specified.

[0014] In this specification, the use of indefinite articles such as "a" and "an" means "one or more" unless otherwise specified, or unless the use of "one or more" is clearly inappropriate.

[0015] The use of "comprise / comprises / comprising" and "include / includes / including" are interchangeable and not intended to be limiting. Further, when the term "comprising" is used in the description of one or more embodiments, one of ordinary skill in the art will understand that in certain situations, the embodiment can alternatively be described using the terms "consisting essentially of" and / or "consisting of".

[0016] As used herein, the term "about" refers to a variation of ±10% from a nominal value. It should be understood that such variations are always included in any given value provided herein, whether or not explicitly recited.

[0017] The recitation of numerical ranges herein is merely intended as a convenient method for referring individually to each separate value falling within the range. Unless otherwise indicated herein, each separate value is incorporated herein as if it were individually recited herein. Any range given either in absolute terms or in approximate terms is intended to cover both endpoints and all intermediate values therebetween. Any definitions used herein are for the purpose of clarification and are not intended to be limiting. Although the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as accurately as possible. In addition, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein (including all fractional and integral values).

[0018] As used herein, "CF X cathode composition" refers to a composition containing graphite that is used as the cathode of a battery, where CF X is generated in situ during charging and discharging of the battery. Further, the CF described herein XThe cathode composition is used in rechargeable batteries.

[0019] The term “composite cathode composition” refers to and is used interchangeably with the term “composite cathode.” In some embodiments, the disclosed composite cathode composition comprises, in addition to the active material, an electronically conductive additive (such as SSE) and an ionically conductive filler.

[0020] As used herein, “small-sized lithium salt” refers to a lithium salt in which the anions in such a salt are relatively small in size, for example, in the range of approximately 0.1 nm to approximately 1 nm. Examples include LiPF6 (lithium hexafluoride phosphate), LiFSI (lithium bis(fluorosulfonyl)imide), and LiTFSI (lithium bis(trifluoromethanesulfonyl)imide). Although not intended to be limited to any particular theory, PF6 - FSI - TFSI - These anions typically have a single central atom (P, N, etc.), and the carbon chain in these anions (if any) is typically limited to about 1-2 carbon atoms, which contributes to their small size.

[0021] As used herein, "large-sized anions" refers to lithium salts containing anions that are relatively large in size, for example, in the range of approximately 1 nm to 2 nm. Examples include lithium bis(nonafluorobutanesulfonyl)imide (LiNFSI), lithium tetraphenylborate tris(1,2-dimethoxyethane), lithium p-toluenesulfinate, lithium nonafluoro-1-butanesulfonate, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide, lithium 2-[(4-methylpiperazine-1-yl)methyl]benzoic acid, and lithium 4,5-dicyano-2-(trifluoromethyl)imidazole-1-oid. These salts may contain anions with elongated carbon chains or bulky substituents, which increases their molecular size.

[0022] Transition metals and transition metal compounds are typically found in commercially available batteries and can cause environmental pollution. One advantage of the present invention is that "transition metal-free" and "substantially transition metal-free" batteries can be manufactured, including the compositions disclosed herein. In this specification, the term "substantially transition metal-free" refers to a composition disclosed to contain trace amounts or less of transition metals. In this specification, the term "transition metal-free" refers to a composition disclosed to contain 0% by weight of transition metals, i.e., the absence of any detectable amount of transition metals. The detection of the presence (or absence) of transition metals may be determined using standard methods known to those skilled in the art.

[0023] As used herein, the term “substantially water-free” means that the presence of moisture is “trace” or less. In this specification, the term “moisture-free” means the absence of moisture, and the absence of any detectable amount of moisture (exceeding the humidity of the surrounding environment). The detection of the amount (or absence) of moisture may be determined using standard methods known to those skilled in the art.

[0024] General laboratory techniques for substantially removing water from solutions, solvents, or liquid components are known. Such techniques include preparing such solutions, solvents, or liquid components in a drying chamber, an anhydrous autoclave, anhydrous container filled with an inert gas, an anhydrous glove box (oxygen-free if necessary), and storing them under an activated molecular sieve.

[0025] As used herein, the term "SOC" refers to the charge state of a battery. For example, SOC 100% means the battery is fully charged, SOC 0% means the battery is fully discharged, and SOC 40% means the charge capacity is 40% of the maximum capacity. Furthermore, as used herein, "fully charged" means the battery has reached its maximum design capacity for storing electrical energy. A fully charged battery is usable and can supply the maximum design energy available as needed. Similarly, as used herein, "fully discharged" means the battery has consumed as much electrical energy as possible. A fully discharged battery has no usable energy remaining and requires charging for further use.

[0026] One aspect of this disclosure relates to a composite cathode composition, wherein the cathode composition is a. Graphite and, b. Monovalent metal fluoride or CF X The ingredients selected from and c. At least one salt selected from MCl, MBr, MI, or a combination thereof, Includes, Here, M is Li + kaNa + , K + , or other monovalent metals, where x is in the range of about 0.05 to about 1.1.

[0027] In some embodiments, x is in the range of approximately 0.2 to approximately 1.

[0028] In some embodiments, the salt is selected from MI, MBr, MCl, or a combination thereof. For example, the salt may be LiI, NaI, KI, or a combination thereof. In some embodiments, the salt may exist as particles. In such cases, the particles may have a size in the range of about 1 nm to about 100 μm, or in the range of about 10 nm to about 10 μm, or the particles may have a size of about 10 μm.

[0029] In some embodiments, the compositions disclosed herein are substantially free of transition metals. In further embodiments, the compositions disclosed herein are free of transition metals.

[0030] Another aspect of the present disclosure relates to a liquid electrolyte, the liquid electrolyte comprising a partially fluorinated solvent system, one or more salts containing large-sized anions, and one or more salt additives containing small-sized lithium salts. In some embodiments, the partially fluorinated solvent system is selected from methyl (2,2,2-trifluoroethyl) carbonate, ethyl (2,2,2-trifluoroethyl) carbonate, fluoroethylene carbonate, bis(2,2,2-trifluoroethyl) ether, 1,2-bis(2-fluoroethoxy)ethane, methyl 3,3,3-trifluoropionate, methyl difluoroacetate, methyl 2,2-difluoro-2-(fluorosulfonyl) acetate, ethyl difluoroacetate, or a combination thereof. In other embodiments, one or more salts containing the large-sized anion are selected from lithium bis(nonafluorobutanesulfonyl)imide (LiNFSI), lithium tetraphenylborate tris(1,2-dimethoxyethane), lithium p-toluenesulfinate, lithium nonafluoro-1-butanesulfonate, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide, lithium 2-[(4-methylpiperazine-1-yl)methyl]benzoic acid, lithium 4,5-dicyano-2-(trifluoromethyl)imidazole-1-ide, or a combination thereof. In further embodiments, the one or more salt additives comprising the small-sized lithium salt are selected from LiPF6, lithium bis(fluorosulfonyl)imide (LiFSI), lithium difluorophosphate (LiDFP), lithium tetrafluoroborate (LiBF4), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium trifluoromethanesulfonate, or a combination thereof. In some embodiments, the electrolyte disclosed herein is substantially water-free. In further embodiments, the electrolyte disclosed herein is water-free.

[0031] In some embodiments, the concentrations of the one or more salts and the one or more salt additives are in the range of about 0.05 M to about 7 M, or in the range of about 0.05 M to about 2 M, or in the range of about 3 M to about 7 M, or about 2 M.

[0032] An additional aspect of this disclosure relates to a battery, wherein the battery is a composite CF as described above. X The present invention comprises a cathode composition, an anode, and the aforementioned liquid electrolyte. In some embodiments, the anode is selected from Li metal, Li foil, Li alloy foil, or a combination thereof. The Li alloy foil may contain Li and additional elements selected from Al, Si, Mg, Sn, and Bi. The additional elements may be present in the alloy in an amount ranging from about 20% to 70% by weight.

[0033] In some embodiments, the battery is rechargeable. The inventors have surprisingly discovered that batteries utilizing the cathode compositions of the present disclosure are rechargeable. This is typically the case with CF X This is impossible with batteries.

[0034] In other embodiments, the battery has a charge capacity in the range of approximately 200 mAh / g to approximately 500 mAh / g. In other embodiments, the battery has a discharge capacity in the range of approximately 200 mAh / g to approximately 500 mAh / g.

[0035] Another aspect of this disclosure relates to a method for assembling a battery, the method comprising the step of stacking the cathode composition, separator material, anode, and electrolyte disclosed herein. In some embodiments, the battery is a coin cell / pouch cell / full battery, etc.

[0036] Another aspect of this disclosure relates to a power supply method, the method comprising the step of supplying a voltage in the range of about 2V to about 5V using the battery disclosed herein. The inventors have also surprisingly found that a battery utilizing the cathode composition disclosed herein, in the presence of the liquid electrolyte disclosed herein, can supply a voltage in the range of about 2V to about 5V. Similar commercially available batteries typically achieve a voltage output of up to 4.5V. However, the battery of this disclosure can reach up to 5V. Furthermore, a person skilled in the art would recognize that a difference of 0.5V in voltage output, such as between 4.5V and 5.0V, is a significant difference that cannot be easily overcome except by the present invention.

[0037] 2.0 Non-limiting embodiments List of embodiments The following is a list of non-limiting embodiments. 1. A composite cathode composition, wherein the composition is a. Graphite and, b. Monovalent metal fluoride or CF X The ingredients selected from and c. At least one salt selected from MCl, MBr, MI, or a combination thereof, Includes, M is Li + kaNa + , K + , or other monovalent metals, x is in the range of approximately 0.05 to approximately 1.1. A composite cathode composition. 2. The composition according to Embodiment 1, wherein x is in the range of about 0.2 to 1. 3. The composition according to Embodiment 1, wherein the salt is selected from MI, MBr, MCl, or a combination thereof. 4. The composition according to Embodiment 3, wherein the salt is LiI, NaI, KI, MBr, or a combination thereof. 5. The composition according to Embodiment 3, wherein the salt is in the form of particles. 6. The composition according to Embodiment 5, wherein the particles have a size in the range of about 1 nm to about 100 μm. 7. The composition according to Embodiment 5, wherein the particles have a size in the range of about 10 nm to about 10 μm. 8. The composition according to Embodiment 5, wherein the particles have a size of about 10 μm. The composite electrode composition is substantially free of transition metals or free of transition metals, as described in Embodiment 1. In some embodiments, the cathode composition described in any one of the embodiments further comprises one or more electronically conductive additives and one or more ion-conductive fillers, such as SSE. 9. A liquid electrolyte comprising a partially fluorinated solvent system, one or more salts containing large-sized anions, and one or more salt additives containing small-sized lithium salts. 10. The liquid electrolyte according to Embodiment 10, wherein the partially fluorinated solvent system is selected from methyl (2,2,2-trifluoroethyl) carbonate, ethyl (2,2,2-trifluoroethyl) carbonate, fluoroethylene carbonate, bis(2,2,2-trifluoroethyl) ether, 1,2-bis(2-fluoroethoxy)ethane, methyl 3,3,3-trifluoropionate, methyl difluoroacetate, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate, ethyl difluoroacetate, or a combination thereof. 11. The liquid electrolyte according to Embodiment 10, wherein one or more salts containing the large-sized anion are selected from lithium bis(nonafluorobutanesulfonyl)imide (LiNFSI), lithium tetraphenyl borate tris(1,2-dimethoxyethane), lithium p-toluenesulfinate, lithium nonafluoro-1-butanesulfonate, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide, lithium 2-[(4-methylpiperazine-1-yl)methyl]benzoic acid, lithium 4,5-dicyano-2-(trifluoromethyl)imidazole-1-ide, or a combination thereof. 12. The liquid electrolyte according to Embodiment 10, wherein the one or more salt additives include small-sized lithium salts and are selected from LiPF6, lithium bis(fluorosulfonyl)imide (LiFSI), lithium difluorophosphate (LiDFP), lithium tetrafluoroborate (LiBF4), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium trifluoromethanesulfonate, or a combination thereof. 13. The liquid electrolyte according to Embodiment 10, wherein the concentration of one or more types of salts and one or more types of salt additives is in the range of about 0.05 M to about 7 M, or in the range of about 0.05 M to about 2 M, or in the range of about 3 M to about 7 M, or about 2 M. 14. The liquid electrolyte according to Embodiment 10, wherein the liquid electrolyte is substantially free of water. 15. A battery comprising a cathode composition according to any one of Embodiments 1 to 8. 16. The battery according to embodiment 16, wherein the battery further comprises a liquid electrolyte according to any one of embodiments 9 to 14. 17. The battery according to embodiment 17, wherein the battery further includes an anode. 18. The battery according to any one of embodiments 15 to 17, wherein the battery comprises a cathode composition according to any one of embodiments 1 to 8, a liquid electrolyte according to any one of embodiments 9 to 14, and an anode. 19. The battery according to any one of embodiments 15 to 18, wherein the anode is selected from Li metal, Li foil, Li alloy foil, or a combination thereof. 20. The battery according to Embodiment 20, wherein the Li alloy foil comprises Li and an additional element selected from Al, Si, Mg, Sn, and Bi. In some embodiments, the additional element is present in the alloy in an amount ranging from about 20% by weight to about 70% by weight. 21. The battery is rechargeable, as described in any one of embodiments 15 to 20. 22. The battery according to Embodiment 16, wherein the battery has a charging capacity in the range of approximately 200 mAh / g to approximately 500 mAh / g. 23. The battery according to Embodiment 16, wherein the battery has a discharge capacity in the range of approximately 200 mAh / g to approximately 500 mAh / g. 24. A method for assembling a battery, the method comprising the step of stacking cathode compositions according to any one of Embodiments 1 to 8. In a further embodiment, the method comprises the step of stacking cathode compositions according to any one of Embodiments 1 to 8, separator material, anode, and electrolyte according to any one of Embodiments 9 to 14. In some embodiments, the battery is a coin cell / pouch cell / full battery, etc. 25. A power supply method, the method comprising the step of supplying a voltage in the range of about 2V to about 5V using a battery described in any one of embodiments 15 to 23.

[0038] 3.0 Example The following examples are provided solely for illustrative purposes of the present invention and are not intended to limit the scope of the rights of the present invention as described herein.

[0039] Example 1. Reversible fluorine chemistry To investigate the reaction mechanism of the designed LiF-LiI-graphite (FIG) electrode, X-ray diffraction (XRD) spectra were acquired ex-situ (Figure 1). In the initial FIG electrode, a major LiF peak was observed in addition to the characteristic graphite peak. As charging progressed, the LiF peak gradually attenuated and almost disappeared at 100% state of charge (SOC). This suggests the conversion of LiF with the assistance of LiI. Upon complete discharge, the LiF peak was observed again, indicating the reversible conversion of LiF.

[0040] Details regarding the evolution of the FIG electrode were revealed by SEM and EDS images. In the early FIG electrode, LiF particles up to approximately 10 μm can be observed (Figures 2a-2d). On the other hand, in the case of 100% SOC, no micron-sized LiF particles were observed; instead, a uniform distribution of elements I and F was present. This phenomenon suggests that micron-sized LiF particles are completely converted into interhalogen compounds during the charging process. XRD and SEM results indicate that the electrochemical reaction of LiF via redox bonding with LiI is successful.

[0041] Example 2: Electrochemical performance CF X The electrochemical performance of the -LiI(CFI) electrode was evaluated in a CFI||Li coin cell. As shown in Figure 3a, when the battery was initially discharged, the discharge capacity in the first cycle reached a maximum of 150 mAh / g, which corresponds to CF X This corresponds to the redox reaction of +Li → LiF + C. Primary CF X Unlike conventional electrodes, these CFI electrodes are rechargeable. When the battery is charged to a higher voltage (>4.8V), the subsequent discharge capacity reaches approximately 430mAh / g, exhibiting a high discharge flat of approximately 4.5V. Additionally, the electrochemical performance of the LiF-LiI-graphite (FIG) electrode was also evaluated in a FIG||Li coin cell. According to Figure 3b, after charging to 4.5V, the discharge capacity in the first cycle reaches a maximum of 180mAh / g, corresponding to the redox reaction of LiI / I2. When the battery is charged to a higher voltage (>4.8V), the discharge capacity reaches approximately 400mAh / g, exhibiting a high discharge flat of approximately 4.6V, which corresponds to the IF X This suggests the formation of [something]. Looking closely at the charging curve, the reaction involves [something]. - / I 0 (Approximately 3.0V) and I 0 / I + An oxidation reaction (approximately 3.5V) is involved, and these exhibit voltage curves similar to those of the CFI electrode system.

[0042] Due to its low electronic and ionic conductivity, LiF has been considered an electrochemically inert material at room temperature. For pure LiF, the calculated decomposition voltage is 6.1V, which exceeds the electrochemical stability window of almost all non-aqueous electrolytes. In this study, we found that the presence of LiI activates the conversion of LiF via redox bonding, lowering the oxidation potential required for LiF conversion (approximately 4.6V vs. LiI). + (Li). Furthermore, by adjusting the electrolyte composition and optimizing the electrode material, other redox bonding systems such as LiF-LiBr-G and LiF-LiCl-G can also be realized.

[0043] Example 3. Comparison with commercially available electrolytes Figure 4 shows the voltage-capacitance curve of the FIG cathode in a commercially available electrolyte (1M LiPF6 (50:50 weight ratio) in EC-DEC). During charging, only a voltage flat and capacitance from LiI are observed. After the battery is charged to above 4V and the LiI capacity is fully utilized, the battery cannot be charged to the design cutoff voltage after a long voltage flat. After manually switching to the discharge step, no high voltage flat is observed, and only a portion of the LiI capacity is reversibly discharged. This indicates that the electrode of this disclosure cannot achieve reversible charge and discharge with commercially available electrolytes. Only by combining this electrode with a properly designed electrolyte can all active materials function reversibly and thus achieve a high energy density.

[0044] All publications described herein are incorporated herein by reference to the extent that they support the present invention.

[0045] References In the foregoing, numerous patents and publications have been cited to provide a more detailed description and disclosure of the present invention and the technical field to which the present invention relates. Complete citation information for these references is provided below. Each of these references is incorporated herein by reference in whole to the same extent as when an individual reference is explicitly cited as being specifically and individually invoked by reference. [Reference 1] Winter, M.; Barnett, B.; Xu, K., Before Li ion batteries. Chemical reviews 2018, 118, 11433-11456. [Reference 2] Recham, N.; Chotard, J.-N.; Dupont, L.; Delacourt, C.; Walker, W.; Armand, M.; Tarascon, J.-M., A 3.6 V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries. Nature materials 2010, 9, 68-74. [Reference 3] Okubo, M.; Ko, S.; Dwibedi, D.; Yamada, A., Designing positive electrodes with high energy density for lithium-ion batteries. Journal of Materials Chemistry A 2021, 9, 7407-7421. [Reference 4] Amatucci, G. G.; Pereira, N., Fluoride based electrode materials for advanced energy storage devices. Journal of Fluorine Chemistry 2007, 128, 243-262. [Reference 5] Sayahpour, B.; Hirsh, H.; Bai, S.; Schorr, N. B.; Lambert, T. N.; Mayer, M.; Bao, W.; Cheng, D.; Zhang, M.; Leung, K., Revisiting discharge mechanism of CF Xas a high energy density cathode material for lithium primary batteries. Advanced Energy Materials 2022, 12, 2103196. [Table 6]Han, SS; You, TH; Merinov, BV; Van Duin, AC; Yazami , R. ; Goddard III, WA, Unraveling Structural Models of Graphite Fluorides by Density Functional Theory Calculations. Chemistry of Materials 2010, 22, 2142–2154. [CrossRef]Watanabe, N.; Nakajima, T.; Touhara, H., Graphite fluorides. Elsevier : 2013 . [Table 8]Xu, J.; Pollard , TP ; Yang, C.; Dandu, NK; Tan , S. ; Zhou, J.; Wang, J.; He, X.; Zhang, X.; Li, A.-M., Lithium halide cathodes for Li metal batteries. Joules 2023, 7, 83–94.

Claims

1. A composite cathode composition, wherein the composition is a. Graphite and, b. Monovalent metal fluoride or CF Ｘ The ingredients selected from and c. At least one salt selected from MCl, MBr, MI, or a combination thereof, Includes, M is Li ＋ Na ＋ _K ＋ , or other monovalent metals, x is in the range of approximately 0.05 to approximately 1.

1. A composite cathode composition.

2. The composition according to claim 1, wherein x is in the range of about 0.2 to 1.

3. The composition according to claim 1 or 2, wherein the at least one salt is selected from MI, MBr, MCl, or a combination thereof.

4. The composition according to any one of claims 1 to 3, wherein the salt is LiI, NaI, KI, or a combination thereof.

5. The composition according to any one of claims 1 to 4, wherein the salt comprises particles.

6. The composition according to any one of claims 1 to 5, wherein the particles have a size in the range of about 1 nm to about 100 μm.

7. The composite electrode composition is the composition according to any one of claims 1 to 6, wherein the composite electrode composition is substantially free of transition metals.

8. A liquid electrolyte comprising a partially fluorinated solvent system, one or more salts containing large-sized anions, and one or more salt additives containing small-sized lithium salts.

9. The liquid electrolyte according to claim 8, wherein the partially fluorinated solvent system is selected from methyl (2,2,2-trifluoroethyl) carbonate, ethyl (2,2,2-trifluoroethyl) carbonate, fluoroethylene carbonate, bis(2,2,2-trifluoroethyl) ether, 1,2-bis(2-fluoroethoxy)ethane, methyl 3,3,3-trifluoropionate, methyl difluoroacetate, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate, ethyl difluoroacetate, or a combination thereof.

10. The liquid electrolyte according to claim 8, wherein one or more salts containing the large-sized anion are selected from LiNFSI, lithium tetraphenylborate tris(1,2-dimethoxyethane), lithium p-toluenesulfinate, lithium nonafluoro-1-butanesulfonate, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide, lithium 2-[(4-methylpiperazine-1-yl)methyl]benzoic acid, lithium 4,5-dicyano-2-(trifluoromethyl)imidazole-1-oid, or a combination thereof.

11. The aforementioned additive is LiPF ６ , LiFSI, LiDFP, LiBF ４ , LiTFSI, LiNO ３ The liquid electrolyte according to claim 8, selected from lithium trifluoromethanesulfonate, or a combination thereof.

12. The liquid electrolyte according to claim 8, wherein the concentration of the one or more types of salts and the one or more types of salt additives is in the range of about 0.05 M to about 7 M.

13. The liquid electrolyte according to any one of claims 8 to 12, wherein the liquid electrolyte is substantially free of water or contains no water.

14. A battery comprising a cathode composition according to any one of claims 1 to 7 and a liquid electrolyte according to any one of claims 8 to 13.

15. The battery according to claim 14, wherein the battery further includes an anode.

16. The battery according to claim 15, wherein the anode is selected from Li metal, Li foil, and Li alloy foil.

17. The battery according to any one of claims 14 to 16, wherein the Li alloy foil comprises Li and an additional element selected from Al and Si.

18. The battery according to any one of claims 14 to 17, wherein the additional element is present in the Li alloy in an amount of about 20% to about 70% by weight.

19. The battery is rechargeable, as described in any one of claims 14 to 18.

20. The battery according to any one of claims 14 to 19, wherein the battery has a charging capacity of approximately 200 mAh / g to approximately 500 mAh / g.

21. The battery according to any one of claims 14 to 20, wherein the battery has a discharge capacity in the range of about 200 mAh / g to about 500 mAh / g.

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