Preparation process of lithium-chlorine battery material based on torreya grandis biomass derived carbon

Abstract

The invention provides a preparation process of a lithium-chlorine battery material based on torreya grandis biomass derived carbon, and an efficient ACOPs-based positive electrode composite material is successfully prepared by compounding an ultra-stable covalent organic polymer (ACOPs) and a torreya grandis biomass derived carbon nano material modified by Ni monatomic nano particles. Alkynyl functional (-C is equivalent to C-) groups of ACOPs are periodically distributed in nanopores, and excellent chlorine adsorption capacity is shown. The ACOPs has regularly-arranged open channels, and transmission of Cl <-> and Li < + > is facilitated, so that rapid redox kinetic conversion of LiCl is realized. In addition, a covalent network structure in the compound can relieve volume expansion generated by a discharge product, and long-life cycle of the battery is promoted.

Description

Technical Field

[0001] The invention relates to the technical field of battery materials, and in particular to a preparation process of lithium-chlorine battery materials based on Torreya grandis biomass-derived carbon. Background Art

[0002] The rapid development of electric vehicles and electronic products in recent years has driven the growing demand for high energy density battery systems. To cope with society's growing demand for practical energy storage, it is crucial to develop innovative battery designs with superior quality, high volumetric and areal capacity, and improved energy density. Various types of rechargeable batteries have been invented, such as lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), aluminum-ion batteries (AIBs), and halogen-based batteries. In particular, lithium chloride batteries are revered for their high energy density, providing about 2300 mAh g during discharge. -1 The specific capacity is up to 710Wh kg -1 energy density. These batteries have a wide range of applications, including professional electronic devices, military applications, utility metering, and GPS tracking. However, the non-reusable nature of lithium chloride batteries greatly limits their potential applications.

[0003] Lithium chloride (Li-Cl2) batteries use lithium as the negative electrode and chlorine gas as the positive electrode, offering an advanced alternative to conventional battery technology. The electrolyte in these batteries is usually composed of lithium salts dissolved in an organic solvent, which promotes efficient ion transport. During discharge, lithium ions move from the negative electrode to the positive electrode, combining with chlorine gas to form lithium chloride (LiCl), releasing electrical energy that can be used in a variety of ways. This process is reversible. In addition, Li-Cl2 batteries offer several advantages, most notably their high energy density. Compared to regular lithium-ion batteries, Li-Cl2 batteries can store more energy per unit weight, making them ideal for applications where weight and space are critical, such as electric vehicles and portable electronic devices. In addition to this, Li-Cl2 batteries may have a lower environmental impact than regular batteries. Lithium and chlorine are more readily available and have a lower ecological impact than materials used in some battery technologies, such as cobalt and nickel. Therefore, Li-Cl2 batteries offer a new and exciting energy storage technology. With their high energy density and efficiency, they are expected to revolutionize the energy sector.

[0004] However, there are several challenges in utilizing Li-Cl2 batteries. First, the uneven and insufficient pore distribution in carbon materials leads to slow kinetics between LiCl and Cl2, resulting in residual LiCl solids that block the pores and interfere with the redox reaction. In addition, simple physical adsorption between the pore wall and the generated Cl2 leads to excessive Cl2 loss, thus limiting the efficiency of the redox reaction. Summary of the invention

[0005] In view of the problems pointed out in the background technology, the present invention proposes a preparation process of lithium-chlorine battery materials based on Torreya grandis biomass-derived carbon to solve the above technical problems.

[0006] The technical solution of the present invention is achieved in this way:

[0007] A preparation process of lithium-chlorine battery materials based on cattail biomass-derived carbon comprises the following steps:

[0008] Step (1), synthesis of 3,3′,6,6′-tetrabromo-9,9′-dicarbazole monomer;

[0009] Step (2), synthesizing ACOPs using 3,3′,6,6′-tetrabromo-9,9′-dicarbazole monomer and 1,4-diethylbenzene;

[0010] Step (3), synthesis of Ni-NC;

[0011] Step (4), synthesizing ACOPs and Ni-NC to obtain ACOPs-Ni-NC;

[0012] Step (5), Cl2 is synthesized with NC, Ni-NC, ACOPs, ACOPs-Ni-NC to obtain Cl2@NC, Cl2@Ni-NC, Cl2@ACOPs and Cl2@ACOPs-Ni-NC.

[0013] The present invention is further configured such that the step (1) is: first, 0.1 g of 3,6-dibromocarbazole is placed in 100 mL of acetone, then 1.5 g of KMnO4 is added and refluxed for 5 hours, and 3,3′,6,6′-tetrabromo-9,9′-dicarbazole is obtained after filtering and drying.

[0014] The present invention is further configured such that the step (2) is: 194.4 mg of 3,3′,6,6′-tetrabromo-9,9′-bicarbazole monomer and 25.2 mg of 1,4-diethylbenzene are placed in a mixture of 15 mL of DMF and 15 mL of triethylamine, uniformly dispersed, and then 6 mg of Pd(pph3)4 and 0.9 mg of CuI are added. The mixture is then sealed in a glass bottle filled with argon, heated at 85° C. for 24 hours, washed with ethanol and dichloromethane, and collected after drying.

[0015] The present invention is further configured that the step (3) is: drying and powdering the Torreya grandis biomass raw material, sieving it, taking 5g of the above granular powder, soaking it in a saturated KOH solution for 1 hour, and then drying it, and then placing it in a muffle furnace filled with nitrogen, heating it to 800°C at 2°C / min, and keeping it for 2 hours, generating biomass carbon through thermal cracking, and then grinding the above product, washing it with deionized water 10 times, and then taking 1g of the above biomass carbon and mixing it with 80mL of deionized water, stirring it for 60 minutes, and then adding 0.2g of ethylenediamine, heating it to 80°C, and keeping it for 12 hours to obtain amino-modified biomass carbon. The above solution was filtered, washed and dried to obtain the aminated Torreya grandis derived biomass carbon (NC). After that, the aminated Torreya grandis derived biomass carbon (NC) (80 mg) and 50 mg of NiCl2·6H2O were ultrasonically dispersed in ethylene glycol (100 mL), and the mixture was heated at 170°C for 5 hours under mechanical stirring (hydrothermal reaction). After cooling to room temperature, the mixture was centrifuged, and the solid was repeatedly washed and extracted with deionized water and ethanol, and dried in a vacuum oven at 80°C for 12 hours to obtain the aminated Torreya grandis derived biomass carbon (Ni-NC) with Ni single atom coordination.

[0016] The present invention is further configured that the step (4) is: 50 mg of Ni-NC and 50 mg of ACOPs are mixed and uniformly ground, and then the mixture is dispersed in DMF (2 mL) and stirred at 120° C. for 10 minutes, and then quickly cooled and filtered to obtain a dark gray product, and the final product ACOPs-Ni-NC is washed with ethanol and vacuum dried at 80° C.

[0017] The present invention is further configured as follows: the step (5) is: Cl2 is prepared by heating MnO2 with concentrated hydrochloric acid at 80°C, and then the purified Cl2 is injected into a sealed bottle with adsorption materials (NC, Ni-NC, ACOPs and ACOPs-Ni-NC) and maintained for 12 hours, and finally Cl2@NC, Cl2@Ni-NC, Cl2@ACOPs and Cl2@ACOPs-Ni-NC are obtained.

[0018] By adopting the above technical solution, the beneficial effects of the present invention are as follows:

[0019] The present invention provides a process for preparing a highly efficient lithium chloride battery material based on a covalent organic polymer connected by an acetylenic bond. By combining ultra-stable ACOPs with carbon nanomaterials modified by Ni nanoparticles, a highly efficient ACOPs-based positive electrode composite material is successfully prepared. The acetylenic functional groups of ACOPs are periodically distributed in the nanopores, showing excellent chlorine adsorption capacity. ACOPs have regularly arranged open channels, which are conducive to the adsorption of Cl - and Li+ The transport of LiCl can be realized through the rapid redox kinetics of LiCl. In addition, the network structure in the composite can alleviate the volume expansion of discharge products and promote the long-life cycle of the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0021] Figure 1 : (a) Schematic diagram of the synthesis of ACOPs; (b) SEM image of ACOPs; (c) TEM image of ACOPs; (d) HRTEM image of sACOP.

[0022] Figure 2 :(a) Fourier transform EXAFS spectra of ACOPs-Ni-NC, Ni foil and NiO; (b) Corresponding K-edge XANES spectra of Co; (cd) Wavelet transform (WT) of EXAFS diagrams of ACOPs-Ni-NC and NiO; (e) Adsorption energy of Cl2 at different sites a, b and c of ACOPs; (f) Schematic diagram of Li-Cl2 battery.

[0023] Figure 3 (a) At a current density of 200 mA g -1 , charging capacity is 1000mAh g -1 Cycling performance of Cl2@NC, Cl2@Ni-NC, Cl2@ACOPs, Cl2@ACOPs-NC and Cl2@ACOPs-Ni-NC electrodes under the conditions of (a) charging capacity of 2000 mAh g -1 Under the conditions of 200 to 1200 mA g -1 Electrochemical performance under non-statistical current density; (c) corresponding Coulomb efficiency; (d) voltage curves of Cl2@ACOPs-NC and Cl2@ACOPs-Ni-NC electrodes; (f) charge and discharge voltage of Cl2@ACOPs-NC and Cl2@ACOPs-Ni-NC electrodes; (g) average Coulomb efficiency of Cl2@ACOPs-NC and Cl2@ACOPs-Ni-NC electrodes; (h) charge capacity of 1000 to 4000 mAh g -1Electrochemical performance of Cl2@ACOPs-NC and Cl2@ACOPs-Ni-NC electrodes under the conditions of (i) current density of 400 mA g -1 (Set the charging capacity to 4000mAh g -1 ) under the conditions of (a) , (b) cycling performance of Cl2@ACOPs-Ni-NC electrode; (c) performance comparison.

[0024] Figure 4 (a) Gibbs free energy distribution in Cl2 reduction reaction; (b) Partial density of states (PDOS) distribution of Cl2 on NC; (c) Partial density of states (PDOS) distribution of Cl2 on Ni-NC; (de) In situ XRD test of Cl2@ACOPs-Ni-NC electrode during a discharge / charge process; (f) Schematic diagram of XRD analysis of Cl2@ACOPs-Ni-NC electrode during charge / discharge process; (g) Discharge to 2 V and charge to 1000, 2000 and 4000 mAh g -1 Cl 2p spectra of Cl2@ACOPs-Ni-NC positive electrode after different discharge or charge states; (h) SEM images of Cl2@ACOPs-Ni-NC positive electrode after different discharge or charge states.

[0025] Figure 5 (a) The Cl2@PFC-58-100 electrode was charged to 3500 mAh g -1 3D distribution of secondary ion fragments of LiCl, Cl2, SCl2, S2Cl2 / SO2Cl2 and SOCl2 constructed by TOF-SIMS depth scanning (analysis area: 50 μm 2 ); (b) Cl2@ACOPs-Ni-NC electrode discharged to 2 V; (c) at 200 mA g -1 Current density, charging capacity is 1000mAh g -1 Electrochemical performance of Cl2@ACOPs-Ni-NC electrode at low temperature under conditions of ; (d) corresponding voltage curves; (e) cycling performance of Li / / Cl2@ACOPs-Ni-NC electrode at -20°C; (f) cycling performance of Cl2@ACOPs-Ni-NC soft-pack battery; (g) corresponding voltage curves; (h) Photo of charging a smartphone with two Li / / Cl2@ACOPs-Ni-NC soft-pack batteries.

[0026] Figure 6 Schematic diagram of the synthesis of 3,3′,6,6′-tetrabromo-9,9′-dicarbazole.

[0027] Figure 7 Fourier transform infrared spectrum of the organic structural unit of 3,3′,6,6′-tetrabromo-9,9′-dicarbazole.

[0028] Figure 8 (a) Transmission electron microscope (TEM) image of ACOPs; (b) corresponding energy dispersive X-ray (EDX) mapping image of the C element; (c) mapping image of the N element.

[0029] Fig. 9 (a) XPS spectra of ACOPs, Ni-NC and ACOPs-Ni-NC; (b) high-resolution XPS spectra of Ni2p region of Ni-NC and ACOPs-Ni-NC.

[0030] Fig.10 High-resolution XPS spectra of the N1s region of Ni-NC and ACOPs-Ni-NC.

[0031] Fig.11 High-resolution transmission electron microscopy (HRTEM) image of NC.

[0032] Fig.12 (a) K-edge EXAFS of nickel and nickel foil at k 2 Curve fitting in weight R space; (b) K-edge EXAFS of Ni and ACOPs-Ni-NC in k 2 Curve fitting in weight R space.

[0033] Fig.13 is the wavelet transform (WT) of the EXAFS pattern of nickel foil.

[0034] Fig.14 This is the optimized NC structure model diagram.

[0035] Fig.15 (a) N2 adsorption isotherms of ACOPs at 77K (pore size distribution inset); (b) Ni-NC-HOF; (c) NC; (d) Ni-NC.

[0036] Fig.16 This is a schematic diagram of the chlorine preparation device and adsorption device.

[0037] Fig.17 (a) Image of 3,3′,6,6′-tetrabromo-9,9′-dicarbazole; (b) Image of ACOPs; (c) Image of Cl2@ACOPs.

[0038] Fig.18 C 1s and N 1s XPS spectra of ACOPs and Cl2@ACOPs.

[0039] Fig.19 Infrared curves of ACOPs and Cl2@ACOPs.

[0040] Fig. 20Raman spectra of ACOPs and ACOPs after adsorbing Cl2.

[0041] Fig.21 The voltage curve of Cl2@ACOPs-Ni-NC electrode in the first cycle.

[0042] Fig. 22 (a) At a current density of 400 mA g -1 (Set the charging capacity to 2000mAh g -1 ) under the condition of (a) the cycling performance of Cl2@ACOPs-Ni-NC electrode at a current density of 400 mA g -1 (Set the charging capacity to 3000mAh g -1 ) under the conditions of .

[0043] Fig.23 (a) Optimized configuration of NC; (b) Optimized configuration of Cl2 molecule on NC fragment; (c) - Optimized configuration of the molecule on the NC segment.

[0044] Fig.24 (a) Optimized configuration of Ni-NC; (b) Optimized configuration of Cl2 molecule on Ni-NC fragment; (c) - Optimized configuration of the molecule on the Ni-NC segment.

[0045] Fig.25 (a) Charge density difference of the optimized configuration of Cl2 molecules on the NC segment; (b) Charge density difference of the optimized configuration of Cl2 molecules on the Ni-NC segment.

[0046] Fig.26 X-ray diffraction (XRD) patterns of Cl2@ACOPs-Ni-NC and NC.

[0047] Fig. 27 (a) The Cl2@ACOPs-Ni-NC electrode was discharged to 2 V and charged to 1000, 2000, and 4000 mAh g -1 XPS spectrum after Ni 2p reaction; (b) the corresponding high-resolution XPS spectrum at Ni 2p. DETAILED DESCRIPTION

[0048] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0049] For reference Figure 1-27 The present invention is described:

[0050] A preparation process for lithium-chloride battery materials based on cattail biomass-derived carbon:

[0051] In step (1):

[0052] First, 0.1 g of 3,6-dibromocarbazole was selected as the starting reactant and placed in 100 mL of acetone solvent. Acetone plays a good dissolving role here and provides a uniform reaction environment for subsequent reactions.

[0053] Next, 1.5 g of KMnO4 was added. KMnO4, as a strong oxidant, fully reacted with 3,6-dibromocarbazole during the 5-hour reflux process, oxidizing it to 3,3′,6,6′-tetrabromo-9,9′-dicarbazole. The reflux condition helps to maintain a uniform temperature in the reaction system and promote the reaction.

[0054] The unreacted substances and solid impurities generated by the reaction are removed by filtering, and then dried to obtain a pure 3,3′,6,6′-tetrabromo-9,9′-dicarbazole intermediate product.

[0055] Then, 0.05 g of the prepared 3,3′,6,6′-tetrabromo-9,9′-dicarbazole was placed in 100 mL of DMF. DMF has good solubility for the intermediate product and can fully disperse it in the solvent.

[0056] Then add excess CuCN. CuCN participates in the reaction to replace the bromine atom in the intermediate product with a cyano group. Reflux in the dark for 48 hours to control the reaction conditions and avoid possible side reactions caused by light.

[0057] Finally, ammonia and deionized water are used for multiple washings. Ammonia can react with and remove impurities such as metal ions that may remain, while deionized water is used to rinse away other water-soluble impurities. Residual water and volatile impurities are removed by vacuum drying, thereby collecting pure 3,3′,6,6′-tetracyano-9,9'-dicarbazole.

[0058] In step (2):

[0059] First, 194.4 mg of 3,3',6,6'-tetrabromo-9,9'-bicarbazole monomer and 25.2 mg of 1,4-diethylbenzene were placed in a mixture of 15 mL of DMF and 15 mL of triethylamine and dispersed evenly, and then 6 mg of Pd(pph3)4 and 0.9 mg of CuI were added. The mixture was then sealed in an argon-filled glass bottle, heated at 85 ° C for 24 hours, washed with ethanol and dichloromethane, and collected after drying.

[0060] Then, heating was performed at a temperature of 85° C. Increasing the temperature helps to promote the dissolution of the monomer and fully disperse it in the solvent until the solution becomes clear, indicating that the monomer has been completely dissolved to form a uniform system.

[0061] Next, a low-temperature rapid cooling process is performed. This rapid temperature change causes the supersaturation of the solute to increase rapidly, causing the monomer molecules to aggregate and precipitate, forming a beige precipitate.

[0062] Finally, the precipitated ACOPs powder is washed with ethanol. Ethanol has good solubility and volatility, and can remove impurities that may be attached to the surface of the precipitate. At the same time, it is easy to evaporate after washing and will not remain in the product.

[0063] In step (3):

[0064] First, the Torreya grandis biomass raw material is dried and ground into powder, and then sieved to obtain particles of a specific size. This step helps to ensure the uniformity and consistency of subsequent reactions.

[0065] Next, 5 g of the granular powder was soaked in a saturated KOH solution for 1 hour, which may have the effect of activation or pretreatment, and then dried.

[0066] The dried powder was placed in a muffle furnace filled with nitrogen and heated to 800°C at a heating rate of 2°C / min and maintained for 2 hours for thermal cracking to produce biomass carbon. The thermal cracking process was carried out in a nitrogen atmosphere to prevent the biomass carbon from reacting with oxygen at high temperature and affecting its performance.

[0067] The product was then ground and washed 10 times with deionized water to remove residual impurities.

[0068] Then, 1 g of biomass carbon was mixed with 80 mL of deionized water and stirred for 60 minutes, 0.2 g of ethylenediamine was added, and the mixture was heated to 80°C for 12 hours to obtain an amino-modified biomass carbon solution. In this process, ethylenediamine is used to modify the biomass carbon by amino modification to improve its chemical activity and specific properties.

[0069] Subsequently, 80 mg of aminated Torreya grandis-derived biomass carbon (NC) and 50 mg of NiCl2·6H2O were ultrasonically dispersed in ethylene glycol (100 mL). Ultrasonic dispersion helps to uniformly mix the two substances.

[0070] The mixture was heated at 170 °C for 5 h under mechanical stirring for a hydrothermal reaction to promote the interaction and coordination between Ni and the aminated biomass carbon.

[0071] After cooling to room temperature, the solid product was separated by centrifugation and repeatedly washed and extracted with deionized water and ethanol to remove unreacted substances and impurities.

[0072] Finally, the biochar derived from Torreya grandis L. (Ni-NC) with Ni single atom coordinated by amino was obtained after drying in a vacuum oven at 80 °C for 12 h.

[0073] In step (4):

[0074] First, 50 mg of Ni-NC and 50 mg of ACOPs were mixed and ground uniformly to ensure that they were fully contacted and mixed uniformly.

[0075] Next, the mixture was dispersed in 2 mL of DMF solvent. DMF plays a role of dissolving and dispersing, which helps the reaction proceed.

[0076] Then, stirring was carried out for 10 minutes at 120° C. Increasing the temperature and stirring can promote the interaction and further reaction between the two substances.

[0077] This is followed by rapid cooling, and this drastic change in temperature may lead to specific changes in the structure or morphology of the product, which is conducive to the formation of the final desired structure.

[0078] The solid product was isolated by filtration to give a dark grey product.

[0079] Finally, the product was washed with ethanol to remove possible residual impurities and unreacted substances, and then dried under vacuum at 80 °C to remove ethanol and other possible residual solvents, obtaining a pure and dry final product, ACOPs-Ni-NC.

[0080] In step (5):

[0081] First, Cl2 is prepared by heating MnO2 with concentrated hydrochloric acid at 80°C. This is a common laboratory method for preparing chlorine, and the reaction formula is: MnO2+4HCl(concentrated)==△==MnCl2+Cl2↑+2H2O.

[0082] The prepared chlorine needs to be purified to remove possible impurities and ensure the purity of the chlorine.

[0083] Then, the purified Cl2 was injected into the sealed bottle containing the adsorbent materials (NC, Ni-NC, ACOPs and ACOPs-Ni-NC). The sealed bottle provided a closed environment to ensure that the chlorine gas could fully contact with the adsorbent material.

[0084] The adsorption was maintained for 12 hours. This period of time allowed the adsorbent material to have enough time to adsorb chlorine gas and reach a saturated or near saturated adsorption state.

[0085] Finally, the products Cl2@NC, Cl2@Ni-NC, Cl2@ACOPs, Cl2@ACOPs-NC and Cl2@ACOPs-Ni-NC were obtained, where the “@” symbol represents the adsorption or loading relationship.

[0086] A preparation process for lithium-chlorine battery materials based on cattail biomass-derived carbon.

[0087] Step (1) synthesizes the key monomer 3,3′,6,6′-tetracyano-9,9′-dicarbazole through a series of chemical reactions, which provides the basic raw materials for the subsequent synthesis steps.

[0088] Step (2) uses the monomers synthesized in step (1) to further react to synthesize ACOPs, which have specific structures and properties and lay an important framework for the formation of the final material.

[0089] Step (3) successfully synthesized Ni-NC, introduced nickel elements and a specific carbon structure, and endowed the material with special electrical or chemical properties.

[0090] Step (4) reacts ACOPs and Ni-NC to synthesize the intermediate product ACOPs-Ni-NC, thereby achieving effective combination and synergistic effect of different components.

[0091] Step (5) Finally, by reacting Cl2 with the previously synthesized NC, Ni-NC, ACOPs, ACOPs-Ni-NC, respectively, final products such as Cl2@NC, Cl2@Ni-NC, Cl2@ACOPs, Cl2@ACOPs-NC and Cl2@ACOPs-Ni-NC are obtained. These products can play a specific role in lithium chloride batteries, thereby achieving efficient battery performance.

[0092] Lithium chloride (Li-Cl2) batteries are at the forefront of energy storage technology due to their superior energy density and efficiency, which are critical for energy storage, meaning that they can store more energy and convert energy more efficiently for the same volume or weight. However, there are some obstacles to overcome, such as insufficient supply of chlorine (Cl2), which directly affects the normal operation and performance of the battery, as chlorine is an indispensable component in the battery reaction. The slow oxidation of lithium chloride (LiCl) to chlorine will lead to sluggish battery reaction kinetics, reducing the battery's charge and discharge efficiency and cycle performance.

[0093] Alkyne-linked covalent organic poly (ACOPs) with open pore structure and exposed functional groups have great application potential in Li-Cl2 batteries. Alkyne-linked covalent organic poly (ACOPs) with open pore structure means that it can provide a lot of space to accommodate and store substances, and the exposed functional groups increase its chemical activity and reaction sites. In Li-Cl2 batteries, this special structure enables ACOPs to effectively store chlorine, ensuring the supply of chlorine required for battery reactions. At the same time, as a synergistic catalyst, it can accelerate the conversion of lithium chloride to chlorine and improve the reaction efficiency of the battery.

[0094] In this application, we developed and synthesized structurally stable ACOPs that serve as efficient hosts for chlorine storage in the cathode of Li-Cl2 batteries and as synergistic catalysts for LiCl conversion.

[0095] Density functional theory (DFT) analysis provides theoretical support for explaining the mechanism of action of ACOPs. The porous structure provides abundant storage space for chlorine, and the systematically distributed alkyne groups interact with chlorine and lithium chloride to achieve efficient chlorine storage and uniform lithium chloride deposition. During the battery cycle, the conversion of lithium chloride and chlorine will cause volume changes, and the presence of ACOPs can slow down this volume expansion, helping to maintain the stability of the battery structure and the durability of performance.

[0096] In addition, ACOPs can effectively combine with nickel single atoms to form efficient and uniform LiCl catalytic sites, further improving the efficiency and uniformity of lithium chloride conversion, making the battery reaction smoother and more controllable.

[0097] Therefore, ACOPs-based Li-Cl2 batteries at 200 mA g -1 The stable performance of the battery was maintained for 180 cycles at a current density of up to 4000mAh g -1The discharge capacity of the battery reflects its strong energy storage capability, and the Coulomb efficiency of nearly 93.5% indicates the high efficiency and reversibility of charge transfer during the battery’s charge and discharge process.

[0098] The above content starts from the advantages and problems of batteries and introduces the solution of ACOPs. Through theoretical analysis and performance data, it comprehensively and in-depth demonstrates the remarkable progress of ACOPs-based Li-Cl2 batteries in improving durability and efficiency, laying a solid foundation for further research and application of this new type of battery.

[0099] Porous organic materials with ordered and uniform pores and embedding sites that can effectively adsorb Cl2 have become promising candidate materials for improving the reaction efficiency of LiCl and Cl2 and improving the performance of Li-Cl2 batteries. "Having ordered and uniform pores": This feature indicates that the pore structure of the material has a high degree of regularity and consistency. Ordered and uniform pores are conducive to the transport and diffusion of substances. In Li-Cl2 batteries, they can provide unobstructed channels for the migration of ions and gases, allowing the reactants to quickly reach the reaction sites, thereby improving the reaction efficiency. "Embedding sites that can effectively adsorb Cl2": This means that there are specific locations or chemical environments inside the material that can strongly attract and fix chlorine molecules. Effective adsorption can increase the concentration of chlorine in the material, promote its reaction with lithium chloride (LiCl), and also help improve the storage and utilization efficiency of chlorine.

[0100] As a crystalline material, alkyne-linked covalent organic poly(ACOPs) have attracted much attention in the scientific and industrial fields due to their unique and attractive structural characteristics and diverse functional applications.

[0101] ACOPs are composed of an orderly combination of organic molecules connected by alkyne bonds. As a relatively weak but directional and selective intermolecular force, alkyne bonds can accurately guide organic molecules to arrange in a specific way, thereby constructing a regular and ordered structure.

[0102] This structure formed by alkyne bonds presents porous characteristics. The numerous evenly distributed and interconnected pores give ACOPs a large specific surface area and abundant internal space. This porous structure makes ACOPs like a vast "warehouse" that can accommodate a large number of gas molecules, showing great potential in the field of gas storage.

[0103] At the same time, the abundant pores and active sites on its surface also make it perform well in catalytic reactions. ACOPs can provide sufficient contact area and a suitable reaction environment for chemical reactions, promoting the efficient progress of the reactions.

[0104] In terms of drug delivery, the porous structure of ACOPs can load drug molecules and achieve controlled release of drugs through carefully designed structural changes, thereby improving the therapeutic effect and safety of drugs.

[0105] The key to improving the cycle stability and rate performance of Li-Cl2 batteries is to achieve efficient chlorine storage and rapid conversion of Cl2 to LiCl. The optimization of these two aspects is directly related to the improvement of battery performance and the feasibility of practical application.

[0106] There are many reasons why ACOPs catalysts are ideal for high-performance Li-Cl2 batteries.

[0107] First, its porous structure is like a well-designed "gas storage chamber" that can effectively store a large amount of chlorine gas, providing sufficient reactants for the battery reaction. Moreover, these pores also provide convenient channels for the transmission of ions, making the charge transfer inside the battery smoother and helping to improve the battery's rate performance.

[0108] Secondly, abundant functional groups are distributed on the surface and inside of ACOPs. These groups act like active "reaction centers" that can interact strongly with Cl2 and LiCl, greatly accelerating the reaction process of Cl2 to LiCl, thereby significantly improving the reaction efficiency of the battery.

[0109] Finally, the excellent stability of ACOPs is an important guarantee for its long-term stability in Li-Cl2 batteries. During the repeated charge and discharge process of the battery, ACOPs can maintain its structural integrity and chemical stability, and will not experience significant performance degradation due to long-term use. This stability ensures that the battery always maintains good performance during long-term cycles and extends the battery life.

[0110] In this application, we have successfully achieved a major breakthrough by cleverly combining ultra-stable ACOPs with carbon nanocomposites modified with nickel nanoparticles to successfully develop an extremely efficient ACOPs-based cathode.

[0111] Delving deeper into the nanopore structure of ACOPs, we find that the cyanide groups are evenly distributed in it. This evenly distributed alkyne group exhibits amazing chlorine adsorption capacity. This means that ACOPs can act like a powerful "adsorber" to firmly grasp a large number of chlorine molecules, storing abundant reactant resources for subsequent battery reactions, thus laying a solid foundation for improving battery performance.

[0112] In addition, ACOPs contain orderly and open channels. These channels are like unobstructed "highways" that provide a smooth passage for Cl - and Li + The transport of ions provides extremely convenient conditions. This efficient ion transport property helps promote the rapid redox kinetic conversion of LiCl. During the battery reaction, ions can quickly reach the reaction site, greatly improving the speed and efficiency of the reaction, allowing the battery to complete the charge and discharge process more quickly.

[0113] It is worth noting that the nickel atoms present in the carbon material play a vital role. They are like efficient "catalysts" that significantly promote the conversion process of chlorine. This process not only speeds up the reaction rate, but also greatly improves the utilization efficiency of chlorine, allowing more chlorine to effectively participate in the battery reaction, thereby further enhancing the overall performance and energy output capacity of the battery.

[0114] At the same time, the important role played by the hydrogen bond network structure in ACOPs cannot be ignored. During the charge and discharge process of the battery, as the chemical reaction proceeds, various discharge products are produced, which often cause the volume of the electrode material to expand. However, the porous network in ACOPs can effectively alleviate the adverse effects of this volume expansion. It is like a tough "buffer zone" that can absorb and disperse the stress caused by volume changes, thereby maintaining the integrity and stability of the electrode structure. Because of this, the stability of the battery during long-term cycle use is ensured, allowing it to maintain good performance after multiple charge and discharge cycles.

[0115] Due to the synergistic effects of the above mentioned advantages, the ACOPs-based cathode exhibits excellent electrochemical performance. -1 At a current density of 1.5 volts, it exhibits a low overpotential of only 0.23 V. This means that during battery operation, energy loss is relatively small and the conversion efficiency is high. Moreover, it can maintain a high capacity of up to 4000 mAh g -1 This high capacity and low overpotential feature fully demonstrates the excellent electrochemical performance of the cathode material, providing strong support and broad application prospects for the development of high-performance Li-Cl2 batteries.

[0116] Material preparation and characterization:

[0117] 33'66'-tetrabromo-99'-dicarbazole was obtained by oxidative coupling of 36-dibromocarbazole, and tetrabromo-dicarbazole organic building monomer was obtained by cyanation (ref. Figure 1 a), this process was confirmed by FT-IR (ref. Figure 6 , Figure 6 ).

[0118] The acetylenically linked covalent organic poly(ACOPs) were formed by polymerization of tetrabromo-biscarbazole monomer (3,3′,6,6′-tetracyano-9,9′-dicarbazole monomer) and 1,4-diethylbenzene (ref. Figure 1 a and Figure 7 ).

[0119] Alkyne-linked covalent organic poly(ACOPs), supported by π···π interactions and -C≡C-alkyne bonds, exhibit excellent resistance to chemical solvents and high temperatures, ensuring their applicability under extreme conditions.

[0120] Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that ACOPs have an elongated blocky morphology with particle sizes ranging from 1 to 2 μm (ref. Figure 1 bd and Figure 8 ).

[0121] HRTEM analysis showed that ACOPs have a high level of crystallinity with a lattice spacing of Indicates the presence of channel gaps (reference Figure 1 d).

[0122] To improve the efficiency of cathode materials, single-atom nickel coordinated amino carbon-derived carbon (Ni-NC) was used in ACOPs-based Li-Cl2 batteries. X-ray photoelectron spectroscopy (XPS) analysis of ACOPs-Ni-NC showed characteristic peaks at 872.7 eV and 855.2 eV, corresponding to Ni2p1 / 2 and Ni2p3 / 2 (ref. Fig. 9 ).

[0123] In addition, specific peaks of Ni-Nx were observed in the high-resolution XPS spectrum of the N1s region (ref. Fig.10 ).

[0124] Lattice peaks attributable to nickel were also detected by HRTEM (ref. Fig.11 ).

[0125] The distribution of chlorine adsorption density in the ACOPs structure shows that the chlorine concentration is higher in the pores close to the -NN- group (ref. Fig.10 ).

[0126] Subsequent calculations of the chlorine adsorption energies at these sites showed that the binding energies of -NN-, -C=C-, and -C≡N- sites were -5.8 kcalmol -1 、-5.4kcalmol -1 and -2.4 kcalmol -1, indicating that the ACOPs structure has a significant adsorption capacity for chlorine (reference Figure 2 ).

[0127] In addition, ACOPs and ACOPs-Ni-NC showed high specific surface areas of 1274.9 m 2 g -1 and 1022.9m 2 g -1 (refer to Fig.16 ).

[0128] The pore size of ACOPs is concentrated in Helpful + In addition, the Ni-NC electrode matrix promoted the rapid conversion between chlorine and lithium chloride, indicating that ACOPs-Ni-NC showed potential in improving the electrochemical performance of Li-Cl2 batteries (ref. Figure 2 ).

[0129] The adsorption efficiency of ACOPs was verified by generating chlorine gas and introducing it into a glass container containing ACOPs. After 8 hours of chlorine adsorption process, ACOPs were exposed to air to remove excess chlorine adsorbed on the surface. The presence of adsorbed chlorine was confirmed by the starch-KI test paper turning dark blue instead of white (ref. Figure 17-18 ).

[0130] In addition, after ACOPs adsorbed chlorine, the C1s peak associated with the benzene ring (-C=C-) functional group shifted from 284.8 eV to 285.3 eV, and the N1s peak associated with -NN- and -C≡N- groups shifted by 0.7 eV, indicating the charge transfer between chlorine and ACOPs (ref. Fig.19 ).

[0131] In addition, in the FT-IR spectrum, the 2201 cm -1 、1505-1380cm -1 and 1278cm -1 The blue shift at , indicating potential electron adsorption by chlorine interaction (ref. Fig. 20 ).

[0132] The 431 cm-1 Raman spectrum after chlorine adsorption -1 、468cm -1 and 520cm -1 The three new peaks show the limiting effect of ACOPs on chlorine (ref. Fig.21 ). These findings collectively indicate that ACOPs are able to effectively adsorb chlorine gas.

[0133] Electrochemical performance:

[0134] First, the long-term stability of four electrodes adsorbing chlorine was tested (ref. Figure 4 a) Due to its limited chlorine storage capacity and slow chlorine / lithium chloride conversion rate, when the charge capacity is set to 1000 mAh g -1 , at 200mA g -1 At current densities of 2.5 and 1.5 Å, the Cl2@NC electrode experienced rapid battery capacity decay and eventually failed. With the help of single-atom nickel catalysis, the Cl2@Ni-NC electrode achieved efficient conversion of chlorine to lithium chloride, resulting in stable cycling performance for about 70 cycles. Although the Cl2@ACOPs electrode effectively adsorbed chlorine, its poor conductivity and slow chlorine / lithium chloride conversion led to poor performance. The Cl2@ACOPs-Ni-NC electrode was specifically designed to address these shortcomings, utilizing ACOPs with abundant pores and adsorption sites, which is conducive to the storage of chlorine. In addition, the nickel single atoms in Ni-NC significantly accelerated the conversion process of chlorine and lithium chloride. As a result, the Cl2@ACOPs-Ni-NC electrode showed stable cycling performance and maintained 969.4 mAh g for 180 cycles. -1 The high discharge capacity and Coulombic efficiency are 96.4%.

[0135] Then, the results of different current densities (200-1200 mA g -1 ) and the redox catalytic kinetics of the reaction between chlorine and lithium chloride were studied. The Cl2@ACOPs-Ni-NC electrode showed high discharge capacity and Coulombic efficiency (ref. Figure 3 b and 3c), even at high current density of 1000mA g -1 The cyclic performance was stable and the Coulombic efficiency was close to 100%. -1 When the Cl2@ACOPs-NC electrode is charged at 1200 mA g -1 At a current density of 1.3 Å, the differences in discharge capacity and Coulombic efficiency between Cl2@ACOPs-Ni-NC and Cl2@ACOPs-NC electrodes are more obvious. The presence of nickel single-atom catalyst in Cl2@ACOPs-Ni-NC electrode plays a key role in improving the efficient and thorough oxidation of lithium chloride. In addition, with the help of ACOPs' efficient adsorption of chlorine, the Cl2@ACOPs-Ni-NC electrode shows remarkable cycling capacity and stability.

[0136] The polarization voltage at different current densities during charge and discharge is as follows: Figure 3d and 3e. As the current density increases from 200 mA g -1 Increase to 1200mA g -1 , the charge-discharge polarization voltage of the Cl2@ACOPs-Ni-NC electrode is smaller. In contrast, under the same conditions, the polarization voltage of the Cl2@ACOPs-NC electrode is larger. It is worth noting that as the current density increases from 200 mA g -1 Increase to 1200mA g -1 , the average Coulombic efficiency of the Cl2@ACOPs-Ni-NC electrode remained constant at 100%, while the Coulombic efficiency of the Cl2@NC electrode dropped to 73.0%. The results show that the nickel single-atom catalyst significantly accelerated the oxidation rate of lithium chloride and reduced its activation energy. In addition, the efficient adsorption of chlorine gas by the Cl2@ACOPs-Ni-NC electrode enhanced its capacity and cycle stability. The cycling performance of the Li-Cl2 battery was further evaluated at different charging capacities. The Cl2@ACOPs-Ni-NC electrode achieved fast oxidation kinetics, with a maximum discharge capacity of 4000mAh g-1 and a Coulombic efficiency close to 100% (reference Figure 3 h). The utilization rate of lithium chloride (UR-LiCl) is as high as 93.4% (reference Fig. 22 ). At high charge capacity and 400mA g -1 The Cl2@ACOPs-Ni-NC electrode exhibits a long cycle life at current densities of 2000, 3000, and 4000 mAh g -1 When the Cl2@ACOPs-Ni-NC electrode maintains a stable Coulombic efficiency close to 100% (ref. Fig.23 ).

[0137] To gain a deeper understanding of the catalytic process, density functional theory (DFT) was used to analyze the reaction pathway based on Gibbs free energy. Figure 4 a and Figure 24-26 The proposed reaction pathway is summarized. First, the nickel single atom catalyst loses electrons, and the electrons are transferred to the electrode to form a radical cation. At the same time, the chloride ion is rapidly oxidized at the cathode through single electron transfer to form the intermediate product Cl*. The two Cl then combine to form chlorine gas. Using the nickel single atom catalyst, the Gibbs free energy of converting chloride ions into chlorine atoms is -0.263 eV, while the energy barrier for direct oxidation from chloride ions to Cl is as high as 1.699 eV. In addition, based on the partial density of states (PDOS) analysis of nickel d orbitals and chlorine p orbitals, a PDOS diagram of chlorine adsorbed on Ni-N4 was constructed (reference Figure 4b) Compared with the metal-free N4 catalyst, the analysis shows that Ni-N4 has a significant spin and stronger resonance with chlorine, leading to a more stable binding. In addition, the calculated adsorption binding energy of lithium chloride on different ACOPs sites is -12 kcalmol -1 Up to 14 kcalmol -1 This indicates that the binding energy of ACOPs with lithium chloride is weaker than that with chlorine. This suggests that ACOPs play an active role in storing chlorine and converting lithium chloride into chlorine through the -C≡C- functional group.

[0138] In addition, the Cl2@ACOPs-Ni-NC electrode was analyzed by in situ XRD test during the charge and discharge process to elucidate the reaction mechanism of the battery. Figure 4 df and Fig.26 It is shown that as the Cl2@ACOPs-Ni-NC electrode is charged from 2 V to 4000 mAh g -1 , the LiCl(111) and LiCl(200) peaks gradually disappeared and reappeared when discharged to 2 V. This indicates that a reversible transformation between chlorine and lithium chloride occurred during the cycling process. Subsequently, in situ X-ray photoelectron spectroscopy (XPS) was used to detect the discharge to 2 V and charge to 1000, 3000, and 4000 mAh g -1 The species changes of the electrode under the state ( Figure 4 g and Fig. 27 ). Charging capacity from 1000mAh g -1 Increased to 4000mAh g -1 , the chlorine signal weakened at 2V, while the lithium chloride XPS signal intensity increased. In addition, in situ SEM analysis showed that the surface of the Cl2@ACOPs-Ni-NC electrode was completely covered with lithium chloride when discharged to 2V. -1 When the ACOPs-Ni-NC particle structure is exposed, the capacity reaches 3000mAh g -1 After the charge capacity of 100 MW was reached, only a small amount of lithium chloride remained on the electrode, indicating that most of the lithium chloride had been oxidized. The SEM results were consistent with the XRD and XPS results. Both computational simulations and experimental tests showed that the excellent electrochemical performance of the Li-Cl2 battery was attributed to the role of ACOPs and nickel single-atom catalysts in the Cl2@ACOPs-Ni-NC electrode.

[0139] In addition, the study included three-dimensional chemical mapping by time-of-flight secondary ion mass spectrometry (TOF-SIMS) depth profiling imaging ( Figure 5 ). When charging to 4000mAh g -1In the state, a small amount of lithium chloride and high contents of Cl2, SCl2, S2Cl2 and SO2Cl2 were detected, which was due to the oxidation of lithium chloride and SOCl2. When discharged to 2V, the contents of Cl2, SCl2, S2Cl2 and SO2Cl2 decreased, while the contents of lithium chloride and SOCl2 increased, verifying the generation of lithium chloride and the recovery of SOCl2. Therefore, the Li-Cl2 battery undergoes the following process during charging and discharging: During the initial discharge process, chlorine and SOCl2 are converted into S, SO2 and Cl - , and then with Li + The ions react to form lithium chloride. During the charging process, lithium chloride is oxidized to form chlorine gas and lithium metal. Chlorine gas is mainly responsible for the change in charge capacity during the charge and discharge process. As the capacity increases, the lithium chloride in the electrode is oxidized to form chlorine gas and SOCl2.

[0140] In addition, the operation of the battery at low temperature was also studied. -1 The Cl2@ACOPs-Ni-NC electrode exhibits a reliable discharge capacity of 1000 mAh g in a wide temperature range from 0 °C to -20 °C. -1 , indicating its potential for application in harsh environments ( Figure 5 c). As the temperature gradually decreases from 0℃ to -20℃, the discharge platform does not change significantly, indicating its excellent tolerance at low temperatures ( Figure 5 d). In addition, after 50 cycles at −20 °C, the Cl2@ACOPs-Ni-NC electrode exhibited an average Coulombic efficiency of 96.5% and a charge capacity of 1000 mAh g -1 ( Figure 5 e). The assembly of Li / / Cl2@ACOPs-Ni-NC soft pack battery shows that it is ready for practical application. The charge capacity is set to 50 mAh g -1 The soft pack battery showed stable operation in 50 cycles, and the discharge voltage was stable at 3.43V ( Figure 5 fh).

[0141] In summary, we designed and synthesized a chemically stable acetylenic-linked covalent organic poly(ACOPs) for chlorine capture via self-assembly. The ACOPs have a molecular weight of 1274.9 m 2 g -1The large specific surface area and spacious cavity channels show great potential as a chlorine host. Our study highlights the importance of the conjugated π-electron cloud of the benzene ring and the -NN- and -C≡C- functional groups as high-affinity chlorine loading sites. In addition, the introduction of nickel single atoms in the Cl2@ACOPs-Ni-NC composite significantly promotes the conversion kinetics of chlorine and lithium chloride. As a result, the Cl2@ACOPs-Ni-NC cathode has a high conductivity at 200 mA g -1 Even after 180 cycles, it still shows 969.4 mAh g -1 The remarkable capacity of ACOPs was achieved with a Coulombic efficiency of nearly 96.4%. The battery exhibited fast redox kinetics in high-rate cycling and excellent long-term stability for more than 100 cycles. This study successfully demonstrated the excellent electrochemical performance of ACOPs as a chlorine host in high-performance chlorine-based organic batteries, providing new insights into the chlorine-based electrochemical energy storage mechanism and the development of high-performance chlorine-based organic battery electrode materials.

[0142] For electrochemical experiments, the active materials were mixed with acetylene black and binder (sodium cellulose, CMC) in a mass ratio of 60:30:10 to prepare the working electrode. The electrochemical performance of the working electrode was characterized in a CR2032 button cell assembled in an argon-filled glove box. Lithium foil was used as the counter electrode. 532 mg AlCl3, 134 mg LiCl, 88 mg LiTFSI, and 88 mg LiFSI were dissolved in 2 mL SOCl2 and 2 mL CH2Cl2 as electrolytes. The charge / discharge performance was examined on a LAND-CT201 system. (a) Image of a soft-pack battery grown with Cl2@ACOPs-Ni-NC as the positive electrode and lithium sheet as the negative electrode; (b) Image of a button cell assembled with Cl2@ACOPs-Ni-NC as the positive electrode; (c) Anhydrous and oxygen-free glove box used to assemble the battery.

[0143] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A process for preparing lithium-chlorine battery materials based on cattail biomass-derived carbon, characterized in that: The steps include: Step (1), synthesis of 3,3′,6,6′-tetrabromo-9,9′-dicarbazole monomer; Step (2), synthesizing ACOPs using 3,3′,6,6′-tetrabromo-9,9′-dicarbazole monomer and 1,4-diethylbenzene in the presence of a catalyst; Step (3), synthesis of Ni-NC; Step (4), synthesizing ACOPs and Ni-NC to obtain ACOPs-Ni-NC; Step (5), Cl2 is synthesized with NC, Ni-NC, ACOPs, ACOPs-Ni-NC to obtain Cl2@NC, Cl2@Ni-NC, Cl2@ACOPs and Cl2@ACOPs-Ni-NC.

2. The process for preparing a lithium-chlorine battery material based on Torreya grandis biomass-derived carbon according to claim 1, characterized in that: The step (1) is as follows: first, 0.1 g of 3,6-dibromocarbazole is placed in 100 mL of acetone, then 1.5 g of KMnO4 is added and refluxed for 5 hours, filtered and dried to obtain 3,3′,6,6′-tetrabromo-9,9′-dicarbazole. Thereafter, 194.4 mg of 3,3′,6,6′-tetrabromo-9,9′-dicarbazole monomer and 25.2 mg of 1,4-diethylbenzene are placed in a mixture of 15 mL of DMF and 15 mL of triethylamine, uniformly dispersed, and then 6 mg of Pd(pph3)4 and 0.9 mg of CuI are added. The mixture is then sealed in a glass bottle filled with argon, heated at 85°C for 24 hours, washed with ethanol and dichloromethane, and collected after drying.

3. The process for preparing a lithium-chlorine battery material based on Torreya grandis biomass-derived carbon according to claim 1, characterized in that: The step (3) is as follows: drying and grinding the Torreya grandis biomass raw material into powder, sieving it, taking 5g of the above granular powder, soaking it in a saturated KOH solution for 1 hour, and then drying it, and then placing it in a muffle furnace filled with nitrogen, heating it to 800°C at 2°C / min, and keeping it for 2 hours, generating biomass carbon through thermal cracking, and then grinding the above product, washing it with deionized water 10 times, and then taking 1g of the above biomass carbon and mixing it with 80mL of deionized water, stirring it for 60 minutes, and then adding 0.2g of ethylenediamine, heating it to 80°C, and keeping it for 12 hours to obtain an amino-modified biomass carbon solution. The above solution was filtered, washed and dried to obtain the aminated Torreya grandis-derived biomass carbon (NC). After that, the aminated Torreya grandis-derived biomass carbon (NC) (80 mg) and 50 mg of NiCl2·6H2O were ultrasonically dispersed in ethylene glycol (100 mL), and the mixture was heated at 170°C for 5 hours under mechanical stirring (hydrothermal reaction). After cooling to room temperature, the mixture was centrifuged, and the solid was repeatedly washed and extracted with deionized water and ethanol, and dried in a vacuum oven at 80°C for 12 hours to obtain the aminated Torreya grandis-derived biomass carbon (Ni-NC) with Ni single atom coordination.

4. The process for preparing a lithium-chlorine battery material based on Torreya grandis biomass-derived carbon according to claim 1, characterized in that: The step (4) is as follows: 50 mg Ni-NC and 50 mg ACOPs are mixed and uniformly ground, and then the mixture is dispersed in DMF (2 mL) and stirred at 120° C. for 10 minutes, and then rapidly cooled and filtered to obtain a dark gray product. The final product ACOPs-Ni-NC is washed with ethanol and vacuum dried at 80° C.

5. The process for preparing a lithium-chlorine battery material based on Torreya grandis biomass-derived carbon according to claim 1, characterized in that: The step (5) is as follows: Cl2 is prepared by heating MnO2 with concentrated hydrochloric acid at 80°C, and then the purified Cl2 is injected into a sealed bottle with adsorbent materials (NC, Ni-NC, ACOPs and ACOPs-Ni-NC) and maintained for 12 hours, and finally Cl2@NC, Cl2@Ni-NC, Cl2@ACOPs and Cl2@ACOPs-Ni-NC are obtained.

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