Homogeneous-heterogeneous synergistic catalyst, low-temperature lithium-dioxide-carbon battery and preparation method thereof

Abstract

The embodiment of the present application provides a homogeneous heterogeneous synergistic catalyst, a low-temperature lithium-carbon dioxide battery and a preparation method thereof, the homogeneous heterogeneous synergistic catalyst is applied to the low-temperature lithium-carbon dioxide battery, the homogeneous heterogeneous synergistic catalyst comprises a homogeneous catalyst and a heterogeneous catalyst, the homogeneous catalyst comprises a molybdenum carbide / carbon nanowire self-supporting electrode material, and the heterogeneous catalyst comprises a phthalocyanine substance added in an electrolyte. In the embodiment of the present application, through the synergistic effect of the homogeneous catalyst and the heterogeneous catalyst, the overpotential in the charging and discharging process of the battery can be complementarily reduced, the electrochemical performance and the cycle stability of the battery are improved, and the battery has good rate performance and cycle performance.

Description

Technical Field

[0001] This application relates to the field of lithium-carbon dioxide battery technology, specifically to a homogeneous-heterogeneous synergistic catalyst, a low-temperature lithium-carbon dioxide battery, and a method for preparing the same. Background Technology

[0002] In recent years, global warming caused by the increase of the greenhouse gas carbon dioxide has become a major problem. Therefore, lithium-carbon dioxide batteries, which can both capture carbon dioxide and provide electricity for energy conversion and storage, have attracted widespread attention. Due to their ultra-high theoretical specific capacity (1876 Wh / kg) compared to lithium-ion batteries, lithium-carbon dioxide batteries are considered a strong contender to replace lithium-ion batteries in the future market for portable electronics such as electric vehicle electrification and smart grids. Especially in Mars exploration, considering that the Martian atmosphere contains 96% CO2, lithium-carbon dioxide batteries are a feasible energy storage device to meet the operational requirements of Mars rovers. More importantly, the good solubility of CO2 at low temperatures greatly improves the stability and reliability of lithium-carbon dioxide batteries, making them a promising candidate for lightweight energy storage devices in Mars exploration.

[0003] Lithium-carbon dioxide batteries still face many challenges in practical applications: the discharge product, lithium carbonate, is difficult to completely decompose below a potential of 4.0V; furthermore, the discharge products are difficult to dissolve in organic electrolytes and tend to accumulate on the electrode surface during charging and discharging, gradually blocking the pores of the positive electrode material, increasing battery polarization, raising the overpotential, reducing energy efficiency, and worsening cycle stability. Another pressing issue is electrolyte decomposition. Excessively high overpotentials cause side reactions, accelerating electrolyte degradation, especially in low-temperature environments where electrolyte conductivity decreases and electrode reaction kinetics slow down, leading to increased discharge / charge overpotentials and shortened cycle life.

[0004] Currently, catalysts used in lithium-carbon dioxide batteries mainly include carbon materials, transition metals and their composites, and noble metal materials. However, most research on these catalysts focuses on operating environments at room temperature or higher. Only reported lithium-carbon dioxide batteries operating at low temperatures use noble metals as catalysts, which involve complex fabrication processes and generally lower performance levels, further increasing the cost of low-temperature lithium-carbon dioxide batteries. Therefore, there is an urgent need to develop catalytic materials for lithium-carbon dioxide batteries operating at low temperatures to facilitate the development of novel ultra-low temperature lithium-carbon dioxide batteries that are low-cost, high-energy-density, and compatible with the extreme environment of Mars. Summary of the Invention

[0005] In view of this, embodiments of this application provide a homogeneous-heterogeneous synergistic catalyst, a low-temperature lithium-carbon dioxide battery and its preparation method, in order to solve the problem that in the prior art, lithium-carbon dioxide batteries operating under low-temperature conditions use precious metals and other materials as catalysts, resulting in cumbersome manufacturing processes and generally low performance levels.

[0006] In a first aspect, embodiments of this application provide a homogeneous-heterogeneous synergistic catalyst, which is applied to a low-temperature lithium-carbon dioxide battery. The homogeneous-heterogeneous synergistic catalyst includes a homogeneous catalyst and a heterogeneous catalyst. The homogeneous catalyst includes a molybdenum carbide / carbon nanowire self-supporting electrode material, and the heterogeneous catalyst includes phthalocyanine substances added to the electrolyte.

[0007] In one possible implementation, the phthalocyanine substances include one or more of the following: iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine, and manganese phthalocyanine.

[0008] Secondly, embodiments of this application provide a low-temperature lithium-carbon dioxide battery, including the homogeneous and heterogeneous synergistic catalyst described in the first aspect, wherein the homogeneous catalyst is used as the positive electrode of the low-temperature lithium-carbon dioxide battery; and the heterogeneous catalyst is used to be added to the electrolyte of the low-temperature lithium-carbon dioxide battery.

[0009] In one possible implementation, the electrolyte comprises an organic ether electrolyte with added lithium salt.

[0010] In one possible implementation, the lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide; the organic ether comprises one or more of epoxypentane, diethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

[0011] Thirdly, embodiments of this application provide a method for preparing a homogeneous catalyst, comprising:

[0012] Sodium molybdate and / or zinc molybdate are mixed with an aqueous solution containing aniline to obtain a mixture;

[0013] An inorganic acid was added to the mixture to adjust the pH until a white precipitate was obtained.

[0014] Carbon nanotubes were added to the mixture, and the mixture was stirred evenly in a constant temperature water bath. The product was then washed multiple times with deionized water and ethanol, filtered, and dried to obtain a membrane material.

[0015] The film material was calcined under a protective atmosphere to obtain a molybdenum carbide / carbon nanowire self-supporting electrode material.

[0016] In one possible implementation, the molar ratio of aniline to molybdenum atoms in sodium molybdate and / or zinc molybdate is 5.0-1.0:1.

[0017] In one possible implementation, the addition of an inorganic acid to the mixture to adjust the pH until a white precipitate is obtained includes:

[0018] Add an inorganic acid to the mixture to adjust the pH to 4-5 until a white precipitate is obtained.

[0019] In one possible implementation, the mass ratio of the carbon nanotubes to the white precipitate is 5%–10%.

[0020] In one possible implementation, the calcination temperature of the film material is 720℃–745℃.

[0021] In this embodiment, a homogeneous-heterogeneous catalyst synergistic catalysis method is employed. On one hand, the homogeneous catalyst, molybdenum carbide, exhibits a noble metal-like electronic structure and catalytic behavior due to its unique d-orbital hybridization. When applied to lithium-carbon dioxide batteries, it can regulate the electronic structure of the product surface, forming an amorphous solid lithium oxalate intermediate, effectively preventing the formation of recalcitrant lithium carbonate. On the other hand, the heterogeneous catalyst, a redox mediator of phthalocyanines, can promote the capture and reduction of CO2 through a solution-phase catalytic reaction mechanism, reducing overpotential and significantly improving battery reaction kinetics. The synergistic effect of these two catalysts complements each other, reducing overpotential during battery charging and discharging, improving the battery's electrochemical performance and cycle stability, and exhibiting excellent rate performance and cycle performance. Attached Figure Description

[0022] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 A schematic flowchart illustrating a method for preparing a homogeneous catalyst provided in an embodiment of this application;

[0024] Figure 2 Physical images and SEM images of the molybdenum carbide / carbon nanowire self-supporting electrode sheet provided in the embodiments of this application;

[0025] Figure 3 XRD pattern of the molybdenum carbide / carbon nanowire self-supporting electrode sheet provided in the embodiments of this application;

[0026] Figure 4 Cycle life diagram of a lithium-carbon dioxide battery using a homogeneous and heterogeneous synergistic catalyst at -60°C, provided as an embodiment of this application;

[0027] Figure 5 The image shows the cycle life of a lithium-carbon dioxide battery using a homogeneous-heterogeneous synergistic catalyst at a low temperature of -80°C, as provided in the embodiments of this application. Detailed Implementation

[0028] To better understand the technical solution of this application, the embodiments of this application will be described in detail below with reference to the accompanying drawings.

[0029] It should be understood that the described embodiments are merely some, not all, of the embodiments in this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application without inventive effort are within the scope of protection of this application.

[0030] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0031] It should be understood that the term "and / or" used in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. Additionally, the character " / " in this article generally indicates that the preceding and following related objects have an "or" relationship.

[0032] To address the problems of existing lithium-carbon dioxide batteries operating at low temperatures, which use precious metals as catalysts and suffer from cumbersome manufacturing processes and generally low performance, this application provides a homogeneous-heterogeneous synergistic catalyst. This homogeneous-heterogeneous synergistic catalyst is applied to low-temperature lithium-carbon dioxide batteries. The catalyst comprises a homogeneous catalyst and a heterogeneous catalyst. The homogeneous catalyst includes a molybdenum carbide / carbon nanowire self-supporting electrode material; the heterogeneous catalyst includes phthalocyanine substances added to the electrolyte.

[0033] In one possible implementation, phthalocyanine substances include one or more combinations of phthalocyanine iron, phthalocyanine cobalt, phthalocyanine nickel, phthalocyanine copper, and phthalocyanine manganese.

[0034] In this embodiment, a homogeneous-heterogeneous catalyst synergistic catalysis method is employed. On one hand, the homogeneous catalyst molybdenum carbide, due to its unique d-orbital hybridization, exhibits a noble metal-like electronic structure and catalytic behavior. When applied to lithium-carbon dioxide batteries, it can regulate the electronic structure of the product surface, forming an amorphous solid lithium oxalate intermediate, effectively preventing the formation of recalcitrant lithium carbonate. On the other hand, the heterogeneous catalyst phthalocyanine redox mediator can promote the capture and reduction of CO2 through a solution-phase catalytic reaction mechanism, reducing overpotential and significantly improving battery reaction kinetics. The synergistic effect of these two catalysts complements each other, reducing overpotential during battery charging and discharging, improving the battery's electrochemical performance and cycle stability, and exhibiting excellent rate performance and cycle performance.

[0035] Corresponding to the above embodiments, this application also provides a method for preparing homogeneous and heterogeneous synergistic catalysts. The preparation methods for homogeneous catalysts and heterogeneous catalysts are described below.

[0036] Preparation method of homogeneous catalyst:

[0037] See Figure 1 This is a schematic flowchart illustrating a method for preparing a homogeneous catalyst according to an embodiment of this application. Figure 1 As shown, it mainly includes the following steps.

[0038] Step S101: Mix sodium molybdate and / or zinc molybdate with an aqueous solution containing aniline to obtain a mixture.

[0039] Specifically, the molar ratio of aniline to molybdenum atoms in sodium molybdate and / or zinc molybdate is 5.0-1.0:1. A value higher than this range leads to a higher carbon content in the homogeneous catalyst, reducing its performance. A value lower than this range results in the presence of residual precursors sodium molybdate and / or zinc molybdate in the catalyst. Therefore, limiting the ratio to this range yields optimal results. For example, the molar ratio of aniline to molybdenum atoms can be 5.0:1, 4.0:1, 3.0:1, 2.0:1, 1.0:1, etc. Those skilled in the art can adaptively select within this range according to actual needs. This application embodiment provides specific limitations in this regard.

[0040] Step S102: Add inorganic acid to the mixture to adjust the pH until a white precipitate is obtained.

[0041] Specifically, an inorganic acid is added to the mixture to adjust the pH to 4-5. For example, an inorganic acid is added to the mixture to adjust the pH to 4, 4.2, 4.5, 4.8, 5, etc. Those skilled in the art can make adaptive selections within this range according to actual needs, and the embodiments of this application impose specific limitations in this regard. It should be noted that if the pH value is lower than the above range, a blocky or sheet-like morphology of molybdenum carbide material will be obtained, and if it is higher than the above range, nanowires cannot be formed, both of which are not conducive to subsequent filtration and membrane formation.

[0042] Step S103: Add carbon nanotubes to the mixture, heat in a constant temperature water bath and stir until homogeneous, wash the product multiple times with deionized water and ethanol, filter and dry the product to obtain a membrane material.

[0043] Specifically, the mass ratio of carbon nanotubes to the white precipitate is 5%–10%. Below this range, the resulting white precipitate exhibits poor mechanical properties, which is detrimental to subsequent filtration and film formation. Above this range, the catalytic performance of the catalyst is reduced. Therefore, limiting the ratio to this range yields optimal results. For example, the mass ratio of carbon nanotubes to the white precipitate can be 5%, 6%, 7%, 8%, 9%, 10%, etc. Those skilled in the art can adaptively select within this range according to actual needs. This application embodiment provides specific limitations in this regard.

[0044] In one possible implementation, after obtaining the film-like material, it can be cut into a circle to facilitate its subsequent use as a positive electrode. For example, the film-like material can be cut into a circle of 11 mm or 16 mm.

[0045] Step S104: Calcine the film material under a protective atmosphere to obtain a molybdenum carbide / carbon nanowire self-supporting electrode material.

[0046] Specifically, the calcination temperature of the film-like material is 720℃–745℃. Temperatures below this range will result in the formation of molybdenum oxide, while temperatures above this range will result in the formation of elemental molybdenum, preventing the formation of the target product, molybdenum carbide. Therefore, limiting the temperature to this range yields optimal results. For example, the calcination temperature of the film-like material can be 720℃, 725℃, 730℃, 735℃, 740℃, 745℃, etc. Those skilled in the art can make adaptive selections within this range according to actual needs, and the embodiments of this application impose specific limitations in this regard.

[0047] It is understandable that if the film material is cut into a circle in step S103, then by calcining the circular film material in this step, a self-supporting circular electrode of molybdenum carbide / carbon nanowires can be directly obtained.

[0048] In this embodiment, the desired positive electrode sheet can be directly prepared by filtering the product into a thin film and then directly carburizing it in a tube furnace. This eliminates the need for binders, conductive agents, and other materials, and avoids hazardous atmosphere treatment. This not only significantly reduces battery assembly process steps and lowers costs, but also avoids side reactions caused by binders and conductive agents during battery operation. Molybdenum carbide / carbon, as a catalyst, can regulate the electronic structure of the product and promote the formation of amorphous lithium oxalate instead of lithium carbonate during discharge, thereby reducing charging overpotential and increasing battery cycle life.

[0049] Preparation methods of heterogeneous catalysts:

[0050] The heterogeneous catalysts involved in this application include phthalocyanine substances added to an electrolyte. The preparation method includes dissolving the phthalocyanine substance in the electrolyte to prepare a saturated, uniformly dispersed solution. The phthalocyanine substance includes one or more combinations of iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine, and manganese phthalocyanine. The electrolyte includes an organic ether electrolyte with added lithium salt, wherein the organic ether includes one or more combinations of epoxypentane, diethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

[0051] In one possible implementation, the components, such as phthalocyanines and the electrolyte, are preferably dried separately before preparation. For example, but not limited to, drying the phthalocyanines in a drying oven, or adding heated molecular sieves to the electrolyte for dehydration. The mixing of the components can be carried out under a protective atmosphere or environment, such as in a glove box where the water and oxygen levels are both less than 0.01 ppm. After weighing the reagents and electrolyte to the required concentration, the phthalocyanines are fully dissolved on a magnetic stirrer, and the supernatant after 48 hours is the electrolyte with the desired saturation concentration.

[0052] In the embodiments of this application, the heterogeneous catalyst first undergoes its own reduction reaction during discharge, then captures carbon dioxide free radicals and promotes their reduction. During charging, on the one hand, it first transforms into an oxidized state to promote the rapid transfer of electrons in the product and promote its decomposition; on the other hand, it can also capture superoxide ions generated by side reactions, thus reducing the attack of superoxide ions on the electrolyte, maintaining better stability of the electrolyte, and also helping to adjust the morphology of the discharge products, making them easier to decompose.

[0053] The synergistic effect between homogeneous and heterogeneous catalysts endows ultra-low temperature lithium-carbon dioxide batteries with good electrochemical performance; for example, at a low temperature of -60℃, the lithium-carbon dioxide battery maintains a discharge specific capacity of 2000 μAh cm⁻¹. –2 Under the condition of a voltage range of 2.2 V–4.5 V, the current density is set to 50 μA cm⁻¹. –2The capacity is limited to 250 μAh cm –2 The battery has a cycle life exceeding 165 cycles, demonstrating excellent cycle performance.

[0054] Corresponding to the above embodiments, this application also provides a low-temperature lithium-carbon dioxide battery, which includes the homogeneous and heterogeneous synergistic catalysts described in the above embodiments, wherein the homogeneous catalyst is used as the positive electrode of the low-temperature lithium-carbon dioxide battery; and the heterogeneous catalyst is used to be added to the electrolyte of the low-temperature lithium-carbon dioxide battery.

[0055] The low-temperature lithium-carbon dioxide battery provided in this application embodiment can achieve high-current charge and discharge at low temperatures, has low polarization voltage, and exhibits excellent cycle performance. Here, "low temperature" refers to an operating temperature below -20°C, especially stable operation at -60°C, and normal operation even at -80°C.

[0056] Corresponding to the above embodiments, this application also provides a method for preparing a low-temperature lithium-carbon dioxide battery, specifically including: assembling the lithium-carbon dioxide battery positive electrode, the electrolyte, and the lithium negative electrode as described above into a lithium-carbon dioxide battery. In specific implementation, a Swagelok mold or a CR2032 type air battery casing is used as the battery shell to assemble the lithium-carbon dioxide battery.

[0057] For ease of understanding, the technical solutions provided in this application will be described in detail below with reference to specific embodiments. Example 1:

[0058] Preparation of homogeneous catalysts:

[0059] 3.09 g of sodium molybdate was dissolved in 50 mL of deionized water, and 3.2 g of aniline was added to obtain a mixture. 1 M hydrochloric acid was added to the mixture to adjust the pH to 4-5 until a white precipitate was obtained. 0.3 g of carbon nanotubes were added to the mixture. The mixture was heated in a constant temperature water bath at 50 °C for 4 h with stirring. The product was washed multiple times with deionized water and ethanol, filtered, and dried, controlling the weight of the membrane material during filtration. The dried membrane material was cut into circular electrodes with a diameter of 11 mm and calcined under a nitrogen atmosphere at a heating rate of 5 °C / min, a calcination temperature of 745 °C, and a calcination time of 5 h, yielding self-supported molybdenum carbide / carbon nanowire cathode electrodes with a diameter of 11 mm and an average weight of 9 mg per electrode.

[0060] See Figure 2 The images shown are physical photos and SEM images of the molybdenum carbide / carbon nanowire self-supporting electrode sheet provided in the embodiments of this application. Figure 2As shown, the electrode is composed of nanowires with a diameter of tens of nanometers and a length of several micrometers; the electrode has a diameter of 11 mm and a weight of 9 mg.

[0061] See Figure 3 The image shown is an XRD pattern of the molybdenum carbide / carbon nanowire self-supporting electrode sheet provided in an embodiment of this application. Figure 3 As shown, the XRD pattern of the molybdenum carbide / carbon nanowire self-supporting electrode sheet prepared in Example 1 is consistent with the standard card, proving that the molybdenum carbide / carbon material was successfully synthesized.

[0062] Preparation of heterogeneous catalysts:

[0063] Measure 5 mL of 1,3-epoxypentane electrolyte containing 1 M lithium bis(trifluoromethanesulfonyl)imide into a glass bottle; weigh 0.02 g of iron phthalocyanine powder and add it to the above electrolyte, stir for 24 h, let stand for 48 h, and take the supernatant as the electrolyte containing the heterogeneous catalyst.

[0064] The molybdenum carbide / carbon nanowire self-supporting electrode obtained in the above steps is used as the positive electrode, and an electrolyte containing phthalocyanine iron is used as the electrolyte to assemble an ultra-low temperature lithium-carbon dioxide battery.

[0065] See Figure 4 This is a cycle life diagram of a lithium-carbon dioxide battery using a homogeneous-heterogeneous synergistic catalyst provided in an embodiment of this application at a low temperature of -60°C. See also... Figure 5 This is a cycle life diagram of a lithium-carbon dioxide battery using a homogeneous-heterogeneous synergistic catalyst provided in an embodiment of this application at a low temperature of -80°C. Figure 4 and combined Figure 5 As shown, the battery is set to a current density of 50 μA cm⁻¹ under conditions of -60°C and a voltage range of 2.2 V–4.5 V. –2 The capacity is limited to 250 μAh cm –2 The battery has a cycle life exceeding 165 cycles, demonstrating excellent cycle performance. It can still cycle normally 35 times at an ultra-low temperature of -80℃. Example 2:

[0066] The difference between this embodiment and Embodiment 1 is that the added phthalocyanine substance is cobalt phthalocyanine. Example 3:

[0067] The difference between this embodiment and Embodiment 1 is that the added phthalocyanine substance is nickel phthalocyanine. Example 4:

[0068] The difference between this embodiment and Embodiment 1 is that the added phthalocyanine substance is copper phthalocyanine. Example 5:

[0069] The difference between this embodiment and Embodiment 1 is that the added phthalocyanine substance is manganese phthalocyanine.

[0070] Comparative Example 1:

[0071] The difference between this embodiment and Embodiment 1 is that a conventional carbon nanotube film is used as the positive electrode.

[0072] Comparative Example 2:

[0073] The difference between this embodiment and Embodiment 1 is that a conventional electrolyte that does not contain phthalocyanine substances is used as the battery electrolyte.

[0074] Comparative Example 3:

[0075] The difference between this embodiment and Embodiment 1 is that a conventional carbon nanotube film is used as the positive electrode, and an electrolyte containing only lithium bis(trifluoromethanesulfonyl)imide without phthalocyanine substances is used as the electrolyte for assembling the battery.

[0076] The homogeneous and heterogeneous catalysts prepared in the above examples were used to assemble lithium-ion batteries, and the electrochemical performance was tested as follows. The test results are shown in Table 1.

[0077] Cyclic performance testing: The manufactured battery was tested on the LAND battery testing system at a low temperature of -60℃. The safe charge / discharge voltage range was set to 2.2 V-4.5 V, and the current density was set to 50 μA cm⁻¹. –2 The capacity is limited to 250 μAh cm –2 .

[0078] Table 1:

[0079]

[0080] As shown in Table 1, without using any of the catalysts prepared in Example 1, the first charge-discharge cycle exceeded the safe voltage range. When only phthalocyanine heterogeneous catalysts were used, the battery failed after 50 cycles due to the formation of difficult-to-decompose lithium carbonate at the cathode. When the homogeneous-heterogeneous synergistic catalyst prepared in Example 1 was used as the catalyst for the low-temperature lithium-carbon dioxide battery, the phthalocyanine materials could accelerate the reduction of carbon dioxide, and the molybdenum carbide / carbon nanowire self-supporting cathode could stabilize the product in lithium oxalate instead of the more difficult-to-decompose lithium carbonate. Therefore, a smaller charge-discharge polarization voltage and better cycle performance could be obtained.

[0081] The above description is merely a specific embodiment of this application. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the protection scope of this application. The protection scope of this application should be determined by the protection scope of the claims.

Claims

1. A low temperature lithium-carbon dioxide battery, characterized by, The battery includes a homogeneous and heterogeneous synergistic catalyst, which comprises a homogeneous catalyst and a heterogeneous catalyst, wherein the homogeneous catalyst is used as the positive electrode of the low-temperature lithium-carbon dioxide battery; and the heterogeneous catalyst is used to be added to the electrolyte of the low-temperature lithium-carbon dioxide battery. The homogeneous catalyst includes a molybdenum carbide / carbon nanowire self-supporting electrode material, and the heterogeneous catalyst includes phthalocyanine substances added to the electrolyte. The homogeneous catalyst and the heterogeneous catalyst work synergistically to reduce the overpotential during battery charging and discharging, and improve the electrochemical performance and cycle stability of the battery. The phthalocyanine substances include one or more of iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine, and manganese phthalocyanine. The electrolyte includes organic ether electrolytes with added lithium salts; The lithium salt includes lithium bis(trifluoromethanesulfonyl)imide; the organic ether includes one or more of epoxypentane, diethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

2. The cryogenic lithium-carbon dioxide battery of claim 1, wherein, The preparation method of the homogeneous catalyst includes: Sodium molybdate and / or zinc molybdate are mixed with an aqueous solution containing aniline to obtain a mixture, wherein the molar ratio of aniline to molybdenum atoms in sodium molybdate and / or zinc molybdate is 5.0-1.0:1; Add an inorganic acid to the mixture to adjust the pH to 4-5 until a white precipitate is obtained; Carbon nanotubes were added to the mixture, and the mixture was stirred evenly in a constant temperature water bath. The product was then washed multiple times with deionized water and ethanol, filtered, and dried to obtain a membrane material. The mass ratio of the carbon nanotubes to the white precipitate was 5%–10%. The film material is calcined under a protective atmosphere to obtain a molybdenum carbide / carbon nanowire self-supporting electrode material. The calcination temperature of the film material is 720℃–745℃.

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