A room temperature sodium-sulfur battery and a preparation method thereof

By using Co-N2O2/MOFc composite material as sulfur storage material in room temperature sodium-sulfur batteries, the problems of poor conductivity and shuttle effect were solved, the electrochemical performance of the battery was improved, more efficient polysulfide conversion and stable battery structure were achieved, and the commercial application of the battery was promoted.

CN118099560BActive Publication Date: 2026-07-24YUNNAN NORMAL UNIV
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
YUNNAN NORMAL UNIV
Filing Date
2024-02-01
Publication Date
2026-07-24

AI Technical Summary

Technical Problem

Room temperature sodium-sulfur batteries suffer from poor conductivity, shuttle effect, and sulfur volume expansion, resulting in unstable electrochemical performance and making commercial application difficult.

Method used

A single-atom catalyst Co-N2O2/MOFc composite material was synthesized using metal-organic framework (MOF) materials as precursors as sulfur storage material. By introducing oxygen atoms to regulate the single-atom catalyst, the conversion efficiency of polysulfides was improved and the shuttle and loss of polysulfides were suppressed.

Benefits of technology

It significantly improves the electrochemical performance of room temperature sodium-sulfur batteries, enhances the cycle stability and energy storage capacity of the batteries, improves the conversion efficiency of polysulfides, suppresses the shuttle effect and volume expansion, and extends battery life.

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Abstract

The application discloses a room-temperature sodium-sulfur battery and a preparation method thereof. The battery is assembled by using a CR2025 battery shell, and a button cell is sequentially installed in the order of a positive electrode shell, a sulfur positive electrode sheet, a diaphragm, an electrolyte, a sodium sheet, a gasket, an elastic sheet and a negative electrode shell. The battery positive electrode material of the sulfur positive electrode sheet is a single-atom catalyst Co / MOFc composite material. The composite material is represented as Co-N2O2 / MOFc, is a catalyst synthesized by a single-atom cobalt and a coordination form Co-N2O2 of two N and two O, and takes metal organic framework material MOF as a precursor. The metal organic framework compound derived carbon material accounts for 98.85-99.04 wt.%, Co accounts for 0.96-1.15 wt.%, and the molar ratio of Co:N:O is 1:2:2. The battery positive electrode material of the application takes metal organic framework MOF as a precursor, designs and synthesizes a catalyst of a coordination form (Co-N2O2) of a single-atom cobalt and two N and two O, and first applies the catalyst as a sulfur storage material in a room-temperature sodium-sulfur battery positive electrode, thereby effectively improving the electrochemical performance of the room-temperature sodium-sulfur battery.
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Description

Technical Field

[0001] This invention relates to a room temperature sodium-sulfur battery and its preparation method, belonging to the technical field of room temperature sodium-sulfur batteries (RT Na-S). Background Technology

[0002] Room temperature sodium-sulfur batteries (RT Na-S) hold promise as a potential alternative to lithium-ion batteries due to their low cost and high energy density. However, despite these advantages, research on RT Na-S batteries is still in its early stages, and several pressing issues hinder their electrochemical performance. These issues primarily include the following: 1-3 :

[0003] (1) Poor conductivity: The sulfur, the starting material of the positive electrode reaction in RT Na-S batteries, and the short-chain sodium polysulfide, a discharge product, have poor conductivity, resulting in low electronic and ionic conductivity in the positive electrode. Simultaneously, the long-chain sodium polysulfide Na2S generated during the discharge process... x (4≤x≤8) The intermediate has high solubility in organic electrolytes and can pass through the membrane to the negative electrode with the electrolyte. This eventually leads to the deposition of some insulating Na2S products on the surface of the negative electrode metallic sodium, forming an insulating interface and reducing the conductivity of the negative electrode.

[0004] (2) Shuttle effect: sulfur and Na + The reaction intermediate, long-chain sodium polysulfide (Na2S), x (4≤x≤8) can dissolve in organic electrolytes and pass smoothly through the membrane, freely shuttling between the positive and negative electrodes. Upon reaching the negative electrode, the long-chain sodium polysulfide reacts directly with metallic Na, being reduced to short-chain sodium polysulfide Na₂S. x (1≤x<4). As the reaction proceeds, only a portion of the short-chain sodium polysulfides can shuttle back to the sulfur cathode and be oxidized to long-chain sodium polysulfides. This process occurs repeatedly with battery cycling and is called the "shuttle effect." Since only a portion of the long-chain sodium polysulfides that "shuttle" to the negative electrode can be oxidized again to participate in the electrochemical reaction after reduction, the remainder cannot participate in the electrochemical cycle as an active material. This leads to the gradual loss of active materials during charge and discharge, causing the battery capacity to decay during electrochemical cycling and significantly reducing the cycle stability of the RT Na-S battery.

[0005] (3) Volume expansion of elemental sulfur: Due to the large density difference between elemental sulfur and the final product of the electrochemical cycle (Na2S) (2.36 g / cm³, respectively) 3 and 1.86 g / cm 3Therefore, elemental sulfur expands significantly in volume during discharge and gradually returns to its original volume during charging. This expansion and contraction occurs repeatedly at the positive electrode during electrochemical cycling, easily leading to the collapse and damage of the positive electrode material structure, thus significantly deteriorating battery performance.

[0006] To address the aforementioned problems with RT Na-S batteries, researchers have actively explored and improved upon them. The main existing strategy involves using different types of conductive carbon materials (such as carbon nanotubes, hollow carbon spheres, and porous carbon) as sulfur-carrying materials to composite with the active sulfur, thereby enhancing the conductivity of the sulfur cathode. 4-7 Meanwhile, by encapsulating and confining elemental sulfur with porous materials, the volume change of elemental sulfur can be effectively mitigated, stabilizing the structure of the RT Na-S cathode. Some porous materials have a certain adsorption capacity for long-chain sodium polysulfides, which is also very beneficial for reducing the "shuttle effect" of RT Na-S batteries. For example, Wang et al. designed a mesoporous hollow carbon nanosphere sulfur carrier (iMCHS), whose hollow structure can provide sufficient space for sulfur storage and help mitigate the volume change of elemental sulfur during charge and discharge. At the same time, the outer carbon shell can restrict the dissolution of polysulfides, thereby mitigating the influence of the "shuttle effect". Therefore, as the cathode of RT Na-S batteries, S@iMCHS exhibits good cycle stability at 100 mA g -1 The capacity retention rate after 200 cycles at a given current density is ~88.8%. However, due to the limited physical constraints of carbon materials on sodium polysulfides, simply using carbon materials is insufficient to solve the problem of sodium polysulfide dissolution. 8 .

[0007] Introducing catalysts to accelerate the conversion rate of long-chain sodium polysulfides and reduce their residence time in the electrolyte is also an effective way to solve the "shuttle effect." The slow reaction kinetics of the conversion process of long-chain sodium polysulfides lead to their long residence time in the electrolyte, which further exacerbates their dissolution in the electrolyte. Related studies have shown that incorporating catalytic components such as metal nitrides, metal sulfides, metal oxides, metal nanoclusters, and single-atom metals into carbon supports can effectively reduce the energy barrier of reaction intermediates in the conversion of long-chain sodium polysulfides and significantly improve the electrochemical reaction kinetics. 9-14 For example, Qi et al. introduced Fe3N catalyst into a nitrogen-doped carbon network and used it as a sulfur-supporting material. Their results showed that Fe3N effectively promoted the conversion of polysulfides, reduced the battery's "shuttle effect," and improved the battery's cycle stability. The battery achieved a cycle stability of 8375 mAg. -1 It can still maintain a high capacity after 2800 cycles under certain conditions. 15Lai et al. synthesized a series of single-atom catalysts (Pt, Ru, Fe, Ni, Ge, Mn) by modifying polypyrrole (PPy) with sodium toluenesulfonate and applied these "single-atom / carbon" composites to RT Na-S batteries. The results showed that these catalysts can significantly reduce the reaction energy barrier during the conversion of long-chain sodium polysulfides and decrease their solubility in the electrolyte. 16 .

[0008] These improvements have mitigated the problems of RT Na-S batteries to varying degrees. However, further enhancing their electrochemical performance and ultimately achieving commercial application remains a challenging task for researchers.

[0009] References:

[0010] 【1】Wang, NN; Wang, YX; Bai, ZC; Fang, ZW; Zhang, X.; Xu, ZF; Ding, Y.; Xu, X.; Du, Y.; Dou, SX; Yu, GH conversion.Energ.Environ.Sci.2020,13(2),562-570.

[0011] 【2】Steudel, R.; Chivers, T., The role of polysulfide dianions and radicalanions in the chemical, physical and biological sciences, including sulfur-based batteries. Chem.Soc.Rev.2019,48(12),3279-3319.

[0012] 【3】Liu,H.W.;Lai,W.H.;Lei,Y.J.;Yang,H.L.;Wang,N.N.;Chou,S.L.;Liu,H.K.;Dou,S.X.;Wang,Y.X.,Electrolytes / Interphases:Enabling Distinguishable SulfurRedox Processes in Room-Temperature Sodium-Sulfur Batteries.Adv.EnergyMater.2022,12(6),26.

[0013] 【4】Wu,C.;Lei,Y.J.;Simonelli,L.;Tonti,D.;Black,A.;Lu,X.X.;Lai,W.H.;Cai,X.L.;Wang,Y.X.;Gu,Q.F.;Chou,S.L.;Liu,H.K.;Wang,G.X.;Dou,S.X.,ContinuousCarbon Channels Enable Full Na-Ion Accessibility for Superior Room-Temperature Na-S Batteries.Adv.Mater.2022,34(8),2108363.

[0014] 【5】Ye,X.;Ruan,J.F.;Pang,Y.P.;Yang,J.H.;Liu,Y.F.;Huang,Y.Z.;Zheng,S.Y.,Enabling aStable Room-Temperature Sodium-Sulfur Battery Cathode byBuilding Heterostructures in Multichannel Carbon Fibers.ACS Nano 2021,15(3),5639-5648.

[0015] 【6】Mou,J.R.;Li,Y.J.;Liu,T.;Zhang,W.J.;Li,M.;Xu,Y.T.;Zhong,L.;Pan,W.H.;Yang,C.H.;Huang,J.L.;Liu,M.L.,Metal-Organic Frameworks-Derived Nitrogen-Doped Porous Carbon Nanocubes with Embedded Co Nanoparticles as EfficientSulfur Immobilizers for Room Temperature Sodium-Sulfur Batteries.SmallMethods 2021,5(8),10.

[0016] 【7】Wang,Y.;Yang,J.;Lai,W.;Chou,S.;Gu,Q.;Liu,H.;Zhao,D.;Dou,S.,Achieving High-Performance Room-Temperature Sodium Sulfur Batteries With S@Interconnected Mesoporous Carbon Hollow Nanospheres.J.Am.Chem.Soc.2016,138(51),16576-16579.

[0017] 【8】Yan,Z.C.;Xiao,J.;Lai,W.H.;Wang,L.;Gebert,F.;Wang,Y.X.;Gu,Q.F.;Liu,H.;Chou,S.L.;Liu,H.K.;Dou,S.X.,Nickel sulfide nanocrystals on nitrogen-dopedporous carbon nanotubes with high-efficiency electrocatalysis for room-temperature sodium-sulfur batteries.Nat.Commun.2019,10,8.

[0018] 【9】Tian,H.;Song,A.L.;Tian,H.J.;Liu,J.;Shao,G.J.;Liu,H.;Wang,G.X.,Single-atom catalysts for high-energy rechargeable batteries.Chem.Sci.2021,12(22),7656-7676.

[0019]

[10] Wang,Y.X.;Lai,Y.Y.;Chu,J.;Yan,Z.C.;Wang,Y.X.;Chou,S.L.;Liu,H.K.;Dou,S.X.;Ai,X.P.;Yang,H.X.;Cao,Y.L.,Tunable Electrocatalytic Behavior ofSodiated MoS2 Active Sites toward Efficient Sulfur Redox Reactions in Room-Temperature Na-S Batteries.Adv.Mater.2021,33(16),10.

[0020]

[11] Ye,C.;Jin,H.Y.;Shan,J.Q.;Jiao,Y.;Li,H.;Gu,Q.F.;Davey,K.;Wang,H.H.;Qiao,S.Z.,A Mo5N6 electrocatalyst for efficient Na2S electrodeposition inroom-temperature sodium-sulfur batteries.Nat.Commun.2021,12(1),7195.

[0021]

[12] Luo,S.N.;Ruan,J.F.;Wang,Y.;Hu,J.M.;Song,Y.;Chen,M.;Wu,L.M.,Flower-Like Interlayer-Expanded MoS 2-x Nanosheets Confined in Hollow CarbonSpheres with High-Efficiency Electrocatalysis Sites for Advanced Sodium-Sulfur Battery.Small 2021,17(37),10.

[0022]

[13] Aslam,M.K.;Hussain,T.;Tabassum,H.;Wei,Z.;Tang,W.W.;Li,S.;Bao,S.J.;Zhao,X.S.;Xu,M.W.,Sulfur encapsulation into yolk-shell Fe2N@nitrogendoped carbon for ambient-temperature sodium-sulfur batterycathode.Chem.Eng.J.2022,429,11.

[0023]

[14] Huang,Z.P.;Song,B.;Zhang,H.;Feng,F.;Zhang,W.L.;Lu,K.;Chen,Q.W.,High-Capacity and Stable Sodium-Sulfur Battery Enabled by ConfinedElectrocatalytic Polysulfides Full Conversion.Adv.Funct.Mater.2021,31(17),8.

[0024]

[15] Qi,Y.R.;Li,Q.J.;Wu,Y.K.;Bao,S.J.;Li,C.M.;Chen,Y.M.;Wang,G.X.;Xu,M.W.,A Fe3N / carbon composite electrocatalyst for effective polysulfidesregulation in room-temperature Na-S batteries.Nat.Commun.2021,12(1),6347.

[0025]

[16] Lai,WH;Wang,H.;Zheng,LR;Jiang,Q.;Yan,ZC;Wang,L.;Yoshikawa,H.;Matsumura,D.;Sun,Q.;Wang,YX;Gu,QF;Wang,JZ;Liu,HK;Chou,SL;Dou,SX Room-Temperature Na-S Batteries.Angew.Chem.,Int.Ed.2020,59(49),22171-22178. Summary of the Invention

[0026] The purpose of this invention is to provide a room temperature sodium-sulfur battery and its preparation method.

[0027] This invention uses metal-organic framework (MOF) materials as precursors to synthesize a novel single-atom catalyst Co / MOFc composite material, which is then applied for the first time as a sulfur storage material in a room-temperature sodium-sulfur battery. Electrochemical tests show that the composite material of this invention can efficiently catalyze the conversion of polysulfides, prevent polysulfide shuttle and loss, change the slow kinetics of multi-step reactions, and improve the energy storage performance of sodium-sulfur batteries.

[0028] The technical solution of this invention is as follows:

[0029] A room-temperature sodium-sulfur battery is disclosed, which is assembled using a CR2025 type battery case. The button cell is installed sequentially in the following order: positive electrode case, sulfur positive electrode sheet, separator, electrolyte, sodium sheet, gasket, spring sheet, and negative electrode case. The sulfur positive electrode sheet of this room-temperature sodium-sulfur battery uses a single-atom catalyst Co / MOFc composite material, denoted as Co-N2O2 / MOFc. This composite material is synthesized using a metal-organic framework (MOF) as a precursor, and is a catalyst synthesized from single-atom cobalt in a coordination form of Co-N2O2 with two N atoms and two O atoms. The metal-organic framework compound-derived carbon material accounts for 98.85–99.04 wt.%, Co accounts for 0.96–1.15 wt.%, and the molar ratio of Co:N:O is 1:2:2.

[0030] Furthermore, a sodium sheet was used as the negative electrode, and the electrolyte was 1.0 M NaCF3SO3 dissolved in 100 Vol% diethylene glycol dimethyl ether (DEGDME), with a Whatman glass fiber diaphragm used.

[0031] A method for preparing a room-temperature sodium-sulfur battery includes the following steps:

[0032] (1) Place the positive electrode shell on the assembly platform and place the sulfur positive electrode sheet in the center of the positive electrode shell;

[0033] (2) Place the diaphragm evenly on the sulfur positive electrode and add a certain amount of electrolyte;

[0034] (3) After placing the sodium negative electrode, gasket, and spring, put the negative electrode shell on;

[0035] (4) Place the button cell into a manual sealing machine and seal it under a certain pressure to form a button cell.

[0036] (5) After the battery is packaged, wipe the surface clean with anhydrous ethanol, and then let the coin cell stand in a constant temperature and humidity environment for 12 hours before testing its electrochemical performance.

[0037] Furthermore, the button cells were prepared and packaged in a glove box protected by a high-purity argon atmosphere, where the contents of H2O and O2 were both below 0.01 ppm.

[0038] The mechanism and beneficial effects of this invention include:

[0039] This invention uses metal-organic frameworks (MOFs) as precursors to synthesize a novel single-atom catalyst Co-N₂O₂ / MOFc composite material, and applies it as a sulfur storage material in a room-temperature sodium-sulfur battery for the first time. The principle of preparing the single-atom catalyst Co-N₂O₂ / MOFc composite material in this invention is as follows: Figure 1 As shown. Electrochemical tests show that the composite material of this invention can efficiently catalyze the conversion of polysulfides, prevent polysulfide shuttle and loss, change the slow kinetics of multi-step reactions, and improve the energy storage performance of sodium-sulfur batteries.

[0040] Currently reported single-atom catalysts mainly anchor the single-atom active center through the coordination of N. The room-temperature sodium-sulfur battery cathode material of this invention introduces oxygen to regulate the first shell of the single-atom catalyst. Utilizing the different electronegativity and electron configurations of various heteroatoms, the material is modified from multiple angles. Using a metal-organic framework (MOF) as a precursor, a catalyst with a single-atom cobalt coordinated to two N atoms and two O atoms (Co-N₂O₂) was designed and synthesized. This catalyst was then used for the first time as a sulfur storage material in the cathode of a room-temperature sodium-sulfur battery, effectively improving the electrochemical performance of the battery. Attached Figure Description

[0041] Figure 1 : Schematic diagram of the principle of preparing single-atom catalyst Co / MOFc composite material according to the present invention.

[0042] Figure 2Example 1: X-ray powder diffraction (XRD) pattern of the single-atom catalytic material prepared.

[0043] Figure 3 Scanning electron microscope (SEM) image of the single-atom catalytic material prepared in Example 1.

[0044] Figure 4 Example 1: High-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) image of the single-atom catalytic material prepared.

[0045] Figure 5 Example 1: Synchrotron radiation absorption spectrum fitting diagram of the single-atom catalytic material prepared.

[0046] Figure 6 Thermogravimetric analysis (TGA) diagram of the room temperature sodium-sulfur battery cathode material (Co-N2O2 / MOFc / S) prepared in Example 3.

[0047] Figure 7 Example 5: Test and analysis of room temperature sodium-sulfur battery cathode materials (Co-N2O2 / MOFc / S), Example 2 (Co / MOFc), and Comparative Example 1 (MOFc / S) at 0.1 A·g -1 Cyclic performance at current density.

[0048] Figure 8 Example 5: Test and analysis of the rate performance of room temperature sodium-sulfur battery cathode materials (Co-N2O2 / MOFc / S) and Example 2 (Co / MOFc) at different current densities. Detailed Implementation

[0049] Example 1

[0050] A method for preparing a single-atom catalyst Co-N2O2 / MOFc composite material includes the following steps:

[0051] (1) Weigh 0.736 g of 4,4-dimethyl-2,2-bipyridine and 1.032 g of 4,4-diphenyl ether dicarboxylic acid and disperse them in 130 mL of ethanol and 72 mL of NaOH (0.1 mol / L). After ultrasonic treatment, solution A is obtained.

[0052] (2) Dissolve 0.8g of Zn(NO3)2 and 0.4g of Co(NO3)2 in 20mL of ethanol to obtain solution B;

[0053] (3) Place solution A in a round-bottom flask, heat to boiling point, then add solution B, reflux for 30 minutes, and filter under reduced pressure to obtain pink Co-Zn MOF;

[0054] (4) Place the above Co-Zn MOF in a quartz boat, and then carbonize it in a tube furnace at 600°C under argon protection;

[0055] (5) Take out the contents of the 20mL hydrothermal reactor liner and add the prepared dilute hydrochloric acid (4mL HCl + 8mL H2O). Tighten the hydrothermal reactor and place it in an electric thermostatic drying oven at 85℃ for 5 hours to remove ZnO and unfixed Co. After the reaction, filter and dry to obtain Co-N2O2 / MOFc. This composite material is a catalyst synthesized from a metal-organic framework (MOF) material as a precursor, using a coordination form of single-atom cobalt with two N and two O atoms (Co-N2O2). The metal-organic framework compound-derived carbon material accounts for 99.04 wt.%, Co accounts for 0.96 wt.%, and the molar ratio of Co:N:O is 1:2:2.

[0056] like Figure 2 As stated above, within the 10-60° diffraction peak range, Co-N2O2 / MOFc only exhibits obvious diffraction peaks of graphitic carbon at around 23° and 45°, without any Co metal peaks. This indicates that no Co metal is present, thus concluding that Co has high dispersion in the Co-N2O2 / MOFc material.

[0057] like Figure 3 As shown, the SEM images indicate that the Co-N2O2 / MOFc material has the morphology of a three-dimensional nanomaterial resembling a lychee shell.

[0058] like Figure 4 As shown, HAADF-STEM testing indicates that Co in the Co-N2O2 / MOFc composite material is distributed in the carbon matrix in the form of single atoms with a size of approximately 0.2 nm. Figure 5 Synchrotron radiation fitting data for Co-N2O2 / MOFc composite materials.

[0059] from Figure 5 The results show that the main peak has a high degree of fit, and the fitting effect is highly reliable.

[0060] Table 1 shows the fitting results, which indicate that Co and O / N exist in a tetracoordinate form.

[0061] The fitting of the constrained coordination environment shows that the coordination mode of Co with 2 N and 2 O is a reasonable result (see Table 2).

[0062] Table 1. Synchrotron Radiation Fitting Results

[0063]

[0064] Table 2. Fitting results of synchrotron radiation on the Co coordination environment

[0065]

[0066] Example 2

[0067] A method for preparing a single-atom catalyst Co / MOFc composite material includes the following steps:

[0068] (1) Weigh 0.736 g of 4,4-dimethyl-2,2-bipyridine and 1.032 g of 4,4-diphenyl ether dicarboxylic acid and disperse them in 130 mL of ethanol and 72 mL of NaOH (0.1 mol / L). After ultrasonic treatment, solution A is obtained.

[0069] (2) Dissolve 2 mmol of Zn(NO3)2 and 1 mmol of Co(NO3)2 in 20 mL of ethanol to obtain solution B;

[0070] (3) Place solution A in a round-bottom flask, heat to boiling point, then add solution B, reflux for 30 minutes, and filter under reduced pressure to obtain pink Co-Zn MOF;

[0071] (4) Place the above Co-Zn2 MOF in a quartz boat and then carbonize it in a tube furnace at 600°C;

[0072] (5) Take out the 20mL hydrothermal reactor liner and add the prepared dilute hydrochloric acid (4mL HCl + 8mL H2O). After tightening the hydrothermal reactor, put it into an electric thermostatic drying oven and keep it at 85℃ for 5h to remove ZnO. Filter and dry to obtain a single-atom Co / MOFc catalyst with a Co content of 0.5wt%.

[0073] Example 3

[0074] A method for preparing a room-temperature sodium-sulfur battery cathode material includes:

[0075] (1) Grind the sulfur powder and Co-N2O2 / MOFc material in a quartz mortar in a certain ratio (1:1) by mass for a period of time to make them fully mixed and uniform;

[0076] (2) Then add it to a small test tube, sonicate it in an ultrasonic instrument for 10 min, then put it in an oven at 60℃ for 12 h, take it out and put it in an eggplant bottle, heat it to 155℃ and keep it warm for 12 h under argon protection.

[0077] (3) After being removed, it is heated at 700°C for a period of time in a tube furnace under an argon atmosphere to obtain a sulfur-carbon composite material;

[0078] (4) The prepared sulfur-carbon composite material, the binder polyvinylidene fluoride (PDVF) and acetylene black are mixed in a ratio of 7:1.5:1.5, and the solvent N-methylpyrrolidone (NMP) is added. The mixture is stirred in a quartz mortar to form a uniform slurry. The slurry is uniformly coated on copper foil and dried in a vacuum drying oven at 60°C for 12 hours to obtain the positive electrode of the sodium-sulfur battery.

[0079] (5) After cooling, remove the electrode sheet and use a stamping machine to prepare a sulfur-carbon positive electrode sheet (Co-N2O2 / MOFc / S) with a diameter of 12mm. Weigh it using an electronic balance and set it aside for later use.

[0080] like Figure 6 As shown, the weight loss of the Co-N2O2 / MOFc / S cathode material under N2 is mainly concentrated between 200-300℃, which can be attributed to the loss of S. Therefore, the S content in this cathode material can be determined to be 60wt%.

[0081] Example 4

[0082] An assembly of a room-temperature sodium-sulfur battery, comprising:

[0083] The coin cells were prepared and packaged in a glove box under a high-purity argon atmosphere, where the H2O and O2 contents were both below 0.01 ppm. A sodium sheet was used as the negative electrode, and the electrolyte was 1.0 M NaCF3SO3 dissolved in 100 vol% diethylene glycol dimethyl ether (DEGDME). A Whatman glass fiber separator was used. The battery was assembled using a CR2025 battery case, with the coin cell installed in the following order: positive electrode case, carbon-sulfur composite positive electrode sheet, separator, electrolyte, sodium sheet, gasket, spring, and negative electrode case. First, the positive electrode case was placed on the assembly platform, with the sulfur positive electrode sheet in the center. Then, the separator was evenly placed on the sulfur positive electrode, and a certain amount of electrolyte was added. Next, the sodium negative electrode, gasket, and spring were placed, and then the negative electrode case was attached. Finally, the coin cell was placed in a manual sealing machine and sealed under pressure to form a coin cell. The coin cell was then allowed to stand in a constant temperature and humidity environment for a period of time. Then, the relevant electrochemical performance was tested in a constant temperature room at 25°C to determine the catalytic ability of different single atoms in sodium-sulfur batteries.

[0084] Example 5

[0085] This embodiment characterizes the electrochemical performance of the cathode material for room temperature sodium-sulfur batteries.

[0086] Electrostatic charge-discharge (GCD) measurements were performed on Co-N2O2 / MOFc / S and Co / MOFc / S cathode materials.

[0087] like Figure 7 As shown, Co-N2O2 / MOFc / S at 0.1 A·g -1The initial discharge specific capacity under the conditions is 807 mA h·g -1 (or calculated based on sulfur mass as 1345 mA h·g) -1 The first-cycle coulombic efficiency (CE) was 84.3%, indicating high sulfur utilization. After 100 cycles, the Co-N2O2 / MOFc / S capacity remained at 590 mA h·g. -1 The capacity is higher than that of Co / MOFc / S (535mAh·g). -1 This demonstrates that a high loading of single-atom Co is more conducive to catalyzing the conversion of sodium polysulfides and immobilizing them, thereby suppressing the "shuttle effect." Meanwhile, in contrast, the capacity of control sample 1 rapidly decayed in the first 20 cycles, with a reversible capacity of only 405 mA h·g at the 100th cycle. -1 This demonstrates that the Co single-atom catalyst plays an effective catalytic role in the conversion reaction of sodium polysulfide.

[0088] like Figure 8 As shown, the rate performance of the Co-N2O2 / MOFc / S cathode is also higher than that of Co / MOFc / S, at 0.1, 0.2, 0.5, 1, 2, 5 and 10 A·g -1 The average capacities at the following values ​​were 649, 612, 578, 521, 464, 429, and 370 mA h·g, respectively. -1 .

[0089] Comparative Example 1

[0090] Unlike Example 1, Comparative Example 1 uses carbon materials without the introduction of a single-atom catalyst. Specifically, following the method of Example 1, only 1 mmol of Zn(NO3)2 was added to prepare a Zn-MOF. The Zn-MOF was then heat-treated with HCl at 120°C for 12 hours to remove the Zn portion, yielding the MOFc material. Then, following the method of Example 3, sulfur was introduced into the MOFc material to prepare the MOFc / S cathode material.

Claims

1. A room-temperature sodium-sulfur battery, wherein the room-temperature sodium-sulfur battery is assembled using a CR2025 type battery casing, and a button cell is sequentially installed in the following order: positive electrode casing, sulfur positive electrode sheet, separator, electrolyte, sodium sheet, gasket, spring sheet, and negative electrode casing; characterized in that, The sulfur cathode material used in this room-temperature sodium-sulfur battery includes a single-atom catalyst Co / MOFc composite material, referred to as Co-N2O2 / MOFc. This composite material is synthesized from a metal-organic framework material MOF as a precursor, using a single-atom cobalt coordinated with two N and two O atoms in the form of Co-N2O2. The derived carbon material in the single-atom catalyst Co / MOFc composite material accounts for 98.85~99.04 wt.%, Co accounts for 0.96~1.15 wt.%, and the molar ratio of Co:N:O is 1:2:

2.

2. The room temperature sodium-sulfur battery according to claim 1, characterized in that: Sodium sheet was used as the negative electrode, and the electrolyte was 1.0 M NaCF3SO3 dissolved in 100 Vol % diethylene glycol dimethyl ether (DEGDME). Whatman glass fiber membrane was used.

3. A method for preparing a room-temperature sodium-sulfur battery as described in claim 2, characterized in that, Includes the following steps: (1) Place the positive electrode shell on the assembly platform and place the sulfur positive electrode sheet in the center of the positive electrode shell; (2) Place the diaphragm evenly on the sulfur positive electrode and add a certain amount of electrolyte; (3) After placing the sodium sheet, gasket, and spring sheet, put the negative electrode shell on; (4) Place the button cell into a manual sealing machine and seal it under a certain pressure to form a button cell; (5) After the battery is packaged, wipe the surface clean with anhydrous ethanol, and then let the coin cell stand in a constant temperature and humidity environment for 12 hours before testing its electrochemical performance.

4. The method for preparing a room-temperature sodium-sulfur battery according to claim 3, characterized in that: Button cells were prepared and packaged in a glove box protected by a high-purity argon atmosphere, where the contents of H2O and O2 were both below 0.01 ppm.