Preparation method of polypentaphenyl tetraketone sulfide / molybdenum ditelluride composite material for negative electrode of sodium-ion battery
By preparing PPTS@MoTe2 composite material, the problem of poor circulation stability of MoTe2 in sodium ion batteries is solved, high conductivity and good circulation performance are achieved, and the energy storage performance of sodium ion batteries is improved.
Patent Information
- Application Number
- CN202510456585.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-12
- Publication Date
- 2025-07-29
AI Technical Summary
The negative electrode material of sodium ion battery MoTe2 has mechanical stress and volume effects problems during the multiple deintercalation of sodium ions, resulting in poor cyclic stability. The layer spacing of existing graphite materials cannot meet the requirements of sodium ion embedding and has low capacity.
Prepare the sodium ion battery negative electrode polypentasylene sulfide/molytetradene ditelluride composite PPTS@MoTe2, and form a conductive polymer PPTS on the surface of MoTe2 to form a continuous conductive network, absorb mechanical stress, inhibit volume expansion, and provide pseudocapacitance capacity through redox reactions to achieve coordinated energy storage.
It improves the cycle stability and conductivity of sodium ion batteries, improves the rate performance and cycle life, and maintains a high reversible specific capacity.
Smart Images
Figure CN120389007A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of sodium-ion batteries, and specifically refers to a preparation method of a composite material of pentacene tetrone thioether / molybdenum ditelluride for the negative electrode of a sodium-ion battery. Background Art
[0002] As the next-generation commercial secondary battery with great commercial prospects, sodium-ion batteries are receiving unprecedented attention. However, at present, the negative electrode materials of sodium-ion batteries face problems such as low capacity and short cycle life. If the commercial graphite material in lithium-ion batteries is directly applied to sodium-ion batteries, its sodium storage capacity is very low, only providing a specific capacity of about 35 mAh g -1 . This is mainly because the interlayer spacing of graphite is relatively small, which is 3.4 Å, and the radius of sodium ions is larger than that of lithium ions (Li + is 0.76 Å; Na + is 1.02 Å), resulting in that sodium ions cannot be fully embedded into the graphite interlayer. Even if some are embedded, it will cause the destruction of the graphite layer structure and cannot be fully removed, so it shows poor electrochemical performance.
[0003] In contrast, transition metal chalcogenides, as two-dimensional layered materials, their chemical formula can generally be expressed as MX2, where M is generally a transition metal element, mainly including elements such as Mo, Sn, Ti, Zr, W, V, etc.; and X is generally a chalcogen element such as S, Te, Se, etc. As a typical representative of transition metal chalcogenides, the interlayer spacing of MoTe2 reaches 6.99 Å (higher than 6.15 Å of MoS2 and 0.646 Å of MoSe2), far exceeding 3.4 Å of graphite, which can provide rich sites for the insertion and extraction of sodium ions.
[0004] However, due to problems such as mechanical stress and volume effect during the multiple insertion and extraction of sodium ions in MoTe2, it cannot provide a very stable cycle life. Therefore, improving the cycle stability of MoTe2 is an urgent problem to be solved for its application as the negative electrode material of sodium-ion batteries. Summary of the Invention
[0005] The purpose of the present invention is to provide a preparation method of a composite material of pentacene tetrone thioether / molybdenum ditelluride for the negative electrode of a sodium-ion battery. This composite material has various characteristics such as stable structure, high conductivity, and synergistic energy storage, and has good performance in the energy storage of sodium-ion batteries.
[0006] The present invention can be realized through the following technical solutions:
[0007] The invention discloses a preparation method of a composite material of pentacene tetrone thioether / molybdenum ditelluride as the anode of a sodium ion battery. Molybdenum ditelluride is dispersed in N-methylpyrrolidone, and then 2,9-dichloropentacene-5,7,12,14-tetrone and sodium sulfide nonahydrate are added. After being evenly dispersed, the mixture is stirred at a high temperature until the reaction ends and then cooled to room temperature. The product is collected by filtration. After the product is purified and dried, PPTS@MoTe2 can be obtained. The feeding ratio of molybdenum ditelluride, 2,9-dichloropentacene-5,7,12,14-tetrone, sodium sulfide nonahydrate and N-methylpyrrolidone is (0.042-0.084 g):(0.204-0.408 g):(0.132-0.264 g):(5-10 mL). Among them, 2,9-dichloropentacene-5,7,12,14-tetrone and sodium sulfide nonahydrate are mainly used to prepare pentacene tetrone thioether (PPTS). If the two are in excess, the MoTe2 flakes will be completely covered by the polymer, and the active sites will decrease, resulting in a reduction in electrochemical performance. If the two are too little, the coverage of PPTS will be less, and the effective coverage area cannot be achieved, and the improvement of electrochemical performance is limited.
[0008] The preparation method of 2,9-dichloroperylene-5,7,12,14-tetrone is as follows: Add 2,5-bis(4-chlorobenzoyl)terephthalic acid into a mixed solution of trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride, and after the mixture is reacted under temperature control in a protective atmosphere and cooled to room temperature, collect the solid, wash and dry it to obtain 2,9-dichloroperylene-5,7,12,14-tetrone; among them, the feeding ratio of 2,5-bis(4-chlorobenzoyl)terephthalic acid, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride is (14 - 28 g):(140 - 280 g):(0.5 - 1.0 g). Among them, 2,5-bis(4-chlorobenzoyl)terephthalic acid, as the construction unit of the core skeleton, provides aromatic rings and carboxylic acid groups, and may form a polycyclic structure through cyclization or coupling reactions, usually being the main raw material of the reaction; trifluoromethanesulfonic anhydride can activate the carboxylic acid group, convert it into a highly reactive mixed anhydride or acyl trifluoromethanesulfonate, and promote subsequent electrophilic substitution or cyclization reactions. If the trifluoromethanesulfonic anhydride is insufficient, the activation will be incomplete, resulting in low reaction efficiency and decreased yield. If the trifluoromethanesulfonic anhydride is excessive, side reactions (such as over-sulfonation or decomposition) may be triggered, and waste and purification difficulties need to be avoided; trifluoromethanesulfonic acid, as a strong acid catalyst, promotes cyclization, condensation, or Friedel-Crafts type reactions. If the trifluoromethanesulfonic acid is insufficient, the reaction rate will be slow, and the cyclization may not be completed. If the trifluoromethanesulfonic acid is excessive, it will have too strong acidity, which may lead to side reactions (such as dechlorination, decomposition, or over-cyclization). The ideal ratio of 2,5-bis(4-chlorobenzoyl)terephthalic acid, trifluoromethanesulfonic anhydride, and trifluoromethanesulfonic acid can maximize the activation efficiency and catalytic effect, and improve the yield of 2,9-dichloroperylene-5,7,12,14-tetrone.
[0009] The preparation method of 2,5-bis(4-chlorobenzoyl)terephthalic acid is as follows: Mix pyromellitic dianhydride, chlorobenzene, and aluminum chloride evenly. After the temperature-controlled reaction is completed, cool it to room temperature. Take out the reactant and quench it in a pre-cooled 36% hydrochloric acid solution. Filter the solid and dissolve it in a sodium bicarbonate solution, then filter to collect the filtrate, wash it, and acidify it to obtain the precipitate 2,5-bis(4-chlorobenzoyl)terephthalic acid. Among them, the feeding ratio of pyromellitic dianhydride, chlorobenzene, and aluminum chloride is (20 - 40 g):(200 - 400 g):(50 - 100 g). Among them, pyromellitic dianhydride provides an acyl group, which is introduced into the aromatic ring of chlorobenzene through the Friedel-Crafts acylation reaction. If it is insufficient, the main product will be monosubstituted products and the yield of the target product will be low. If it is excessive, polysubstituted by-products or isomers (such as ortho- and meta-substitutions) may be produced, increasing the separation difficulty. Chlorobenzene serves as an aromatic hydrocarbon reactant, providing the benzene ring skeleton. If it is insufficient, the reaction will be incomplete, and the unreacted acylating agent may decompose or cause side reactions. If it is excessive, it will produce a solvent dilution reaction, which may slow down the reaction rate. Aluminum chloride, as a Lewis acid catalyst, activates the acylating agent and promotes electrophilic substitution. If it is insufficient, the reaction rate will be low, the acylation will be incomplete, and the yield will decrease. If it is excessive, side reactions (such as over-acylation and isomerization of the aromatic ring) will be aggravated, increasing the difficulty of post-treatment (aluminum chloride is easily hydrolyzed to form a precipitate).
[0010] The preparation method of molybdenum ditelluride is as follows: Mix molybdenum powder and tellurium powder evenly by grinding, put them into a quartz test tube and conduct vacuum sealing tube treatment, and perform high-temperature calcination for alloying reaction. After cooling, MoTe2 powder can be obtained. Among them, the feeding ratio of molybdenum powder and tellurium powder is (0.656 - 1.912 g):(1.276 - 2.552 g). Taking the quantitative amount of Mo powder as an example, if the amount of Te powder is excessive, there will be excess Te powder in the product, resulting in difficulty in separating the product from Te powder. If the amount of Te powder is insufficient, a heterogeneous phase of Mo6Te8 with insufficient Te will be generated.
[0011] In the preparation method of molybdenum ditelluride, the conditions for high-temperature calcination are as follows: The heating rate is 3 - 6 °C / minute, the calcination temperature is 750 - 850 °C, and the holding time is 24 - 48 hours. If the calcination temperature is too low, Te cannot be completely vaporized, and the Te reaction cannot proceed smoothly or the reaction is incomplete. If the temperature is too high, MoTe2 may decompose and lose Te, generating heterogeneous phases.
[0012] In the preparation method of 2,5-bis(4-chlorobenzoyl)terephthalic acid, the conditions for temperature-controlled reaction are as follows: The reaction temperature is 65 - 70 °C, and the reaction time is 4 - 6 hours. If the temperature is too low, the reaction rate will be significantly reduced, and the reaction may not be completed, requiring an extended reaction time. If the temperature is too high, chlorobenzene may undergo dechlorination or decomposition, generating by-products (such as biphenyl or tar), and the acylating agent or intermediate decomposes, reducing the yield of the target product.
[0013] In the preparation method of 2,9-dichloropentacene-5,7,12,14-tetrone, the conditions for the temperature-controlled reaction are as follows: the heating temperature is 140-160 °C, and the heat preservation time is 12 hours. If the temperature is too low, the activation rate is low, which may lead to incomplete formation of the intermediate (acyl trifluoromethanesulfonate), affecting the subsequent cyclization efficiency; if the temperature is too high, side reactions of dechlorination (breaking of the C-Cl bond) may be triggered, generating chlorine-free by-products or tarry substances.
[0014] In the high-temperature stirring reaction conditions of the mixture in the step of preparing MoTe2@PPTS, the reaction temperature is 160-240 °C, and the stirring time is 10-14 hours. If the temperature is too low, the reaction rate will be slow, the conversion rate will be low, and low-molecular-weight oligomers are easily formed; if the temperature is too high, the polymer will degrade, the main chain will break or cyclize, resulting in a decrease in molecular weight. And side reactions will occur, and the thioether bond may be oxidized to sulfoxide or sulfone, changing the properties of the product.
[0015] The present invention provides a preparation method of a sodium-ion battery negative electrode poly(pentacene tetrone thioether) / molybdenum ditelluride composite material, which has the following beneficial effects:
[0016] 1. As a conductive polymer, PPTS can form a continuous conductive network on the surface and between the layers of MoTe2, improving the overall conductivity of the composite material, reducing battery polarization, and thus improving the rate performance and cycle stability;
[0017] 2. When sodium ions are repeatedly deintercalated and intercalated, pure MoTe2 will undergo obvious volume expansion, leading to the collapse of its structure and the pulverization failure of the electrode. However, the flexible chain segments of PPTS in the PPTS@MoTe2 composite material can absorb mechanical stress, inhibiting the volume expansion and crack propagation of the active material;
[0018] 3. MoTe2 provides the capacity for sodium ion insertion / extraction reactions, while PPTS can provide pseudocapacitance capacity through redox reactions, forming a synergistic energy storage mechanism. Description of the Drawings
[0019] Figure 1 It is the XRD pattern of MoTe2 prepared in Example 1.
[0020] Figure 2 It is the SEM image of MoTe2 prepared in Example 1.
[0021] Figure 3 It is the SEM image of PPTS@MoTe2 prepared in Example 1.
[0022] Figure 4 It is the cycle performance graph of PPTS@MoTe2 prepared in Example 1 as the negative electrode of a sodium-ion battery.
[0023] Figure 5 Cycling performance graph of MoTe2 prepared in Comparative Example 1 as the anode of a sodium-ion battery.
[0024] Figure 6 SEM image of PPTS@MoTe2 prepared in Comparative Example 2.
[0025] Figure 7 Cycling performance graph of PPTS@MoTe2 prepared in Comparative Example 2 as the anode of a sodium-ion battery.
[0026] Figure 8 Specific capacity comparison of the products prepared in Examples 1 - 6 and Comparative Examples 1 - 2 after 100 cycles as the anode materials of sodium-ion batteries. Detailed implementation manners
[0027] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the products of the present invention will be further described in detail below in conjunction with the examples.
[0028] The present invention discloses a preparation method of a pentacenequinone thioether / molybdenum disulfide composite as the anode of a sodium-ion battery. Molybdenum disulfide is dispersed in N-methylpyrrolidone, and then 2,9-dichloropentacene-5,7,12,14-tetrone and sodium sulfide nonahydrate are added. After uniform dispersion, the mixture is stirred at high temperature until the reaction is completed and cooled to room temperature. The product is collected by filtration, and after purification and drying, PPTS@MoTe2 is obtained. The feeding ratio of molybdenum disulfide, 2,9-dichloropentacene-5,7,12,14-tetrone, sodium sulfide nonahydrate and N-methylpyrrolidone is (0.042 - 0.084 g):(0.204 - 0.408 g):(0.132 - 0.264 g):(5 - 10 mL).
[0029] The preparation method of 2,9-dichloropentacene-5,7,12,14-tetrone is as follows: 2,5-bis(4-chlorobenzoyl)terephthalic acid is added to a mixed solution of trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride, and the mixture is reacted under a protective atmosphere at a controlled temperature. After the reaction is completed, the mixture is cooled to room temperature, and the solid is collected, washed and dried to obtain 2,9-dichloropentacene-5,7,12,14-tetrone. Among them, the feeding ratio of 2,5-bis(4-chlorobenzoyl)terephthalic acid, trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride is (14 - 28 g):(140 - 280 g):(0.5 - 1.0 g).
[0030] The preparation method of 2,5-bis(4-chlorobenzoyl)terephthalic acid is as follows: Mix pyromellitic dianhydride, chlorobenzene, and aluminum chloride evenly, control the temperature during the reaction, cool to room temperature after the reaction, take out the reactant and quench it in a pre-cooled 36% hydrochloric acid solution, filter the solid and dissolve it in sodium bicarbonate solution, then filter to collect the filtrate, wash it, and acidify it to obtain the precipitate 2,5-bis(4-chlorobenzoyl)terephthalic acid; wherein, the feeding ratio of pyromellitic dianhydride, chlorobenzene, and aluminum chloride is (20-40 g):(200-400 g):(50-100 g).
[0031] The preparation method of molybdenum ditelluride is as follows: Mix molybdenum powder and tellurium powder evenly by grinding, put them into a quartz test tube and perform vacuum sealing tube treatment, carry out alloying reaction by high-temperature calcination, and obtain MoTe2 powder after cooling; wherein, the feeding ratio of molybdenum powder and tellurium powder is (0.656-1.912 g):(1.276-2.552 g).
[0032] In the preparation method of molybdenum ditelluride, the conditions of high-temperature calcination are: heating rate 3-6 °C / minute, calcination temperature 750-850 °C, and heat preservation time 24-48 hours.
[0033] In the preparation method of 2,5-bis(4-chlorobenzoyl)terephthalic acid, the conditions of temperature-controlled reaction are: reaction temperature 65-70 °C, and reaction time 4-6 hours.
[0034] In the preparation method of 2,9-dichloropentacene-5,7,12,14-tetrone, the conditions of temperature-controlled reaction are: heating temperature 140-160 °C, and heat preservation time 12 hours.
[0035] In the preparation method of MoTe2@PPTS, the conditions of high-temperature stirring reaction of the mixture are: reaction temperature 160-240 °C, and stirring time 10-14 hours.
[0036] Example 1
[0037] This example relates to a composite material of poly(pentacene tetrone thioether) / molybdenum ditelluride for the negative electrode of a sodium-ion battery, and its in-situ polymerization preparation method includes the following steps:
[0038] S1. Prepare molybdenum ditelluride (MoTe2) using tellurium powder and molybdenum powder as raw materials. Weigh 0.656 g of molybdenum powder and 1.276 g of tellurium powder, place them in a mortar and grind them evenly, and then put the mixed powder into a quartz test tube. Subsequently, perform vacuum tube sealing treatment. While evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination treatment. Heat it to 800 °C at a heating rate of 5 °C per minute and hold for 24 hours. Wait for the reactants to complete the alloying reaction completely. After the muffle furnace cools to room temperature, obtain gray powder MoTe2. Its XRD pattern is as shown in Figure 1 Therefore, the prepared MoTe2 is a pure phase without other impurities, corresponding to the standard card PDF#71-2157. Its SEM pattern is as shown in Figure 2 It can be seen that the prepared MoTe2 is a lamellar structure with a smooth surface.
[0039] S2. Prepare 2,5-bis(4-chlorobenzoyl)terephthalic acid using pyromellitic dianhydride, chlorobenzene, aluminum chloride, sodium bicarbonate, etc. as raw materials. Mix 20 g of pyromellitic dianhydride, 200 g of chlorobenzene and 50 g of aluminum chloride evenly in a round-bottom flask, heat it to 65 °C and react for 4 hours, and then cool to room temperature and stir for 6 hours. Pour the mixture in the flask into a pre-cooled 36% hydrochloric acid solution to quench it, filter the solid and dissolve it in a sodium bicarbonate solution, and then filter to collect the filtrate. Wash the filtrate three times with dichloromethane, and then acidify it with concentrated hydrochloric acid to obtain a white precipitate of 2,5-bis(4-chlorobenzoyl)terephthalic acid.
[0040] S3. Prepare 2,9-dichloroperylene-5,7,12,14-tetrone using the product 2,5-bis(4-chlorobenzoyl)terephthalic acid from S2, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as raw materials. Add 140 mL of trifluoromethanesulfonic acid and 0.5 mL of trifluoromethanesulfonic anhydride to 14 g of 2,5-bis(4-chlorobenzoyl)terephthalic acid, and heat the mixture to 150 °C in argon and hold for 12 hours. Wait for the mixture to cool to room temperature, collect the solid and wash it with deionized water until the pH value of the filtrate is 5.0. Finally, dry the solid in a vacuum oven at 100 °C for 12 hours to obtain 2,9-dichloroperylene-5,7,12,14-tetrone.
[0041] S4. Using the product of S1, molybdenum ditelluride, the product of S3, 2,9-dichloropentacene-5,7,12,14-tetrone, sodium sulfide nonahydrate, etc. as raw materials, prepare poly(pentacene tetrone thioether) intercalated / coated molybdenum ditelluride (PPTS@MoTe2). Disperse 0.042 g of molybdenum ditelluride in 5 mL of N-methylpyrrolidone and ultrasonically disperse for 30 minutes. Then add 0.204 g of 2,9-dichloropentacene-5,7,12,14-tetrone and 0.132 g of sodium sulfide nonahydrate, ultrasonically disperse it completely, and then stir the mixture at 200 °C for 12 hours. After the reaction is completed and cooled to room temperature, filter to collect the product, wash the product with NMP, hot water, deionized water, ethanol, and acetone multiple times, and after drying the product, the obtained brownish-black powder is PPTS@MoTe2, and its SEM micro-morphology is as Figure 3 shown. Its surface is not smooth, but is coated with a layer of polymer PPTS, and the inside is MoTe2.
[0042] When the obtained PPTS@MoTe2 material is used as the negative electrode of a sodium-ion battery, its cycling performance is as Figure 4 shown. PPTS@MoTe2 can still maintain a reversible specific capacity of about 283.5 mAh / g after cycling 100 weeks at a current density of 100 mA / g.
[0043] Example 2
[0044] This example relates to a poly(pentacene tetrone thioether) / molybdenum ditelluride composite material for the negative electrode of a sodium-ion battery, and its in-situ polymerization preparation method includes the following steps:
[0045] S1. Using tellurium powder and molybdenum powder as raw materials, prepare molybdenum ditelluride (MoTe2). Weigh 0.1912 g of molybdenum powder and 2.552 g of tellurium powder, place them in a mortar and grind them evenly, and place the mixed powder in a quartz test tube. Then perform vacuum tube sealing treatment. While evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination treatment. Heat it to 800 °C at a heating rate of 5 °C per minute and keep it for 24 hours. Wait for the reactants to complete the alloying reaction completely. After the muffle furnace cools to room temperature, obtain gray powder MoTe2.
[0046] S2. Prepare 2,5-bis(4-chlorobenzoyl)terephthalic acid using pyromellitic dianhydride, chlorobenzene, aluminum chloride, sodium bicarbonate, etc. as raw materials. Mix 240 g of pyromellitic dianhydride, 400 g of chlorobenzene and 100 g of aluminum chloride evenly in a round-bottom flask, heat it to 68 °C and react for 5 hours, then cool it to room temperature and stir for 6 hours. Pour the mixture in the flask into a pre-cooled 36% hydrochloric acid solution to quench, filter the solid and dissolve it in a sodium bicarbonate solution, and then filter to collect the filtrate. Wash the filtrate three times with dichloromethane, and then acidify it with concentrated hydrochloric acid to obtain the white precipitate 2,5-bis(4-chlorobenzoyl)terephthalic acid.
[0047] S3. Prepare 2,9-dichloroperylene-5,7,12,14-tetrone using the product 2,5-bis(4-chlorobenzoyl)terephthalic acid from S2, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as raw materials. Add 280 mL of trifluoromethanesulfonic acid and 1.0 mL of trifluoromethanesulfonic anhydride to 28 g of 2,5-bis(4-chlorobenzoyl)terephthalic acid, and heat the mixture to 200 °C in argon and keep it for 12 hours. Wait for the mixture to cool to room temperature, collect the solid and wash it with deionized water until the pH value of the filtrate is 5.0. Finally, dry the solid in a vacuum oven at 100 °C for 12 hours to obtain 2,9-dichloroperylene-5,7,12,14-tetrone.
[0048] S4. Prepare molybdenum ditelluride intercalated / coated with polyperylene tetrone thioether (PPTS@MoTe2) using the product molybdenum ditelluride from S1, the product 2,9-dichloroperylene-5,7,12,14-tetrone from S3, sodium sulfide nonahydrate, etc. as raw materials. Disperse 0.084 g of molybdenum ditelluride in 10 mL of N-methylpyrrolidone and ultrasonically disperse it for 30 minutes. Then add 0.408 g of 2,9-dichloroperylene-5,7,12,14-tetrone and 0.264 g of sodium sulfide nonahydrate, ultrasonically disperse it until it is completely dispersed, and then stir the mixture at 200 °C for 12 hours. After the reaction is completed and cooled to room temperature, filter to collect the product, wash the product with NMP, hot water, deionized water, ethanol, acetone for many times, and after drying the product, the obtained brownish-black powder is PPTS@MoTe2.
[0049] When the obtained PPTS@MoTe2 material is used as the negative electrode of a sodium-ion battery, it can maintain a reversible specific capacity of about 278.6 mAh / g after cycling 100 weeks at a current density of 100 mA / g.
[0050] Example 3
[0051] This example relates to a composite material of polyperylene tetrone thioether / molybdenum ditelluride for the negative electrode of a sodium-ion battery, and its in-situ polymerization preparation method includes the following steps:
[0052] S1. Prepare molybdenum ditelluride (MoTe2) using tellurium powder and molybdenum powder as raw materials. Weigh 0.656 g of molybdenum powder and 1.276 g of tellurium powder, place them in a mortar and grind them evenly. Then put the mixed powder into a quartz test tube. Subsequently, perform vacuum sealing on the test tube. While evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is in a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination. Heat it at a heating rate of 4 °C per minute to 750 °C and keep it for 24 hours. Wait until the reactants completely complete the alloying reaction. After the muffle furnace cools to room temperature, obtain the gray powder MoTe2.
[0053] S2. Prepare 2,5-bis(4-chlorobenzoyl)terephthalic acid using pyromellitic dianhydride, chlorobenzene, aluminum chloride, sodium bicarbonate, etc. as raw materials. Mix 20 g of pyromellitic dianhydride, 200 g of chlorobenzene and 50 g of aluminum chloride evenly in a round-bottom flask, and heat it to 65 °C and react for 4 hours. Cool to room temperature and stir for 6 hours. Pour the mixture in the flask into a pre-cooled 36% hydrochloric acid solution to quench it. Filter the solid and dissolve it in a sodium bicarbonate solution, and then filter to collect the filtrate. Wash the filtrate three times with dichloromethane, and then acidify it with concentrated hydrochloric acid to obtain the white precipitate 2,5-bis(4-chlorobenzoyl)terephthalic acid.
[0054] S3. Prepare 2,9-dichloroperylene-5,7,12,14-tetrone using the product 2,5-bis(4-chlorobenzoyl)terephthalic acid from S2, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as raw materials. Add 140 mL of trifluoromethanesulfonic acid and 0.5 mL of trifluoromethanesulfonic anhydride to 14 g of 2,5-bis(4-chlorobenzoyl)terephthalic acid, and heat the mixture to 160 °C in argon and keep it for 12 hours. Wait until the mixture cools to room temperature, collect the solid and wash it with deionized water until the pH value of the filtrate is 5.0. Finally, dry the solid in a vacuum oven at 100 °C for 12 hours to obtain 2,9-dichloroperylene-5,7,12,14-tetrone.
[0055] S4. Using the product molybdenum ditelluride of S1, the product 2,9-dichloroperylene-5,7,12,14-tetrone of S3, sodium sulfide nonahydrate, etc. as raw materials, prepare molybdenum ditelluride intercalated / coated with polyperyleneterone thioether (PPTS@MoTe2). Disperse 0.042 g of molybdenum ditelluride in 5 mL of N-methylpyrrolidone and ultrasonically disperse for 30 minutes. Then add 0.204 g of 2,9-dichloroperylene-5,7,12,14-tetrone and 0.132 g of sodium sulfide nonahydrate, ultrasonically disperse it completely, and then stir the mixture at 200 °C for 12 hours. After the reaction is completed and cooled to room temperature, filter to collect the product, wash the product with NMP, hot water, deionized water, ethanol, and acetone multiple times, and after drying the product, the obtained brownish-black powder is PPTS@MoTe2.
[0056] When the obtained PPTS@MoTe2 material is used as the anode of a sodium-ion battery, it can maintain a reversible specific capacity of about 281.8 mAh / g after 100 cycles at a current density of 100 mA / g.
[0057] Example 4
[0058] This example relates to a composite material of polyperyleneterone thioether / molybdenum ditelluride for the anode of a sodium-ion battery, and its in-situ polymerization preparation method includes the following steps:
[0059] S1. Using tellurium powder and molybdenum powder as raw materials, prepare molybdenum ditelluride (MoTe2). Weigh 0.984 g of molybdenum powder and 1.914 g of tellurium powder, place them in a mortar and grind them evenly, and put the mixed powder into a quartz test tube. Then perform vacuum tube sealing treatment. While evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination treatment. Heat it to 850 °C at a heating rate of 4 °C per minute and keep it for 36 hours. Wait for the reactants to complete the alloying reaction completely. After the muffle furnace cools to room temperature, obtain gray powder MoTe2.
[0060] S2. Using pyromellitic dianhydride, chlorobenzene, aluminum chloride, sodium bicarbonate, etc. as raw materials, prepare 2,5-bis(4-chlorobenzoyl)terephthalic acid. Mix 20 g of pyromellitic dianhydride, 200 g of chlorobenzene, and 50 g of aluminum chloride evenly in a round-bottom flask, heat it to 65 °C and react for 4 hours, cool to room temperature and stir for 6 hours. Pour the mixture in the flask into a pre-cooled 36% hydrochloric acid solution for quenching, filter the solid and dissolve it in a sodium bicarbonate solution, and then filter to collect the filtrate. Wash the filtrate three times with dichloromethane, and then acidify it with concentrated hydrochloric acid to obtain white precipitate 2,5-bis(4-chlorobenzoyl)terephthalic acid.
[0061] S3. Prepare 2,9-dichloropentacene-5,7,12,14-tetrone using the product of S2, 2,5-bis(4-chlorobenzoyl)terephthalic acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as raw materials. Add 140 mL of trifluoromethanesulfonic acid and 0.5 mL of trifluoromethanesulfonic anhydride to 14 g of 2,5-bis(4-chlorobenzoyl)terephthalic acid, and heat the mixture to 160 °C in argon and keep it for 12 hours. After the mixture is cooled to room temperature, collect the solid and wash it with deionized water until the pH value of the filtrate is 5.0. Finally, dry the solid in a vacuum oven at 100 °C for 12 hours to obtain 2,9-dichloropentacene-5,7,12,14-tetrone.
[0062] S4. Prepare molybdenum ditelluride intercalated / coated with poly(pentacene tetrone thioether) (PPTS@MoTe2) using the product of S1, molybdenum ditelluride, the product of S3, 2,9-dichloropentacene-5,7,12,14-tetrone, sodium sulfide nonahydrate, etc. as raw materials. Disperse 0.042 g of molybdenum ditelluride in 5 mL of N-methylpyrrolidone and ultrasonically disperse it for 30 minutes. Then add 0.204 g of 2,9-dichloropentacene-5,7,12,14-tetrone and 0.132 g of sodium sulfide nonahydrate, ultrasonically disperse it until completely dispersed, and then stir the mixture at 200 °C for 12 hours. After the reaction is completed and cooled to room temperature, filter and collect the product, wash the product with NMP, hot water, deionized water, ethanol, and acetone multiple times, and after drying the product, the obtained brownish-black powder is PPTS@MoTe2.
[0063] When the obtained PPTS@MoTe2 material is used as the negative electrode of a sodium-ion battery, it can maintain a reversible specific capacity of about 280.5 mAh / g after cycling 100 weeks at a current density of 100 mA / g.
[0064] Example 5
[0065] This example relates to a composite material of poly(pentacene tetrone thioether) / molybdenum ditelluride as the negative electrode of a sodium-ion battery, and its in-situ polymerization preparation method includes the following steps:
[0066] S1. Prepare molybdenum ditelluride (MoTe2) using tellurium powder and molybdenum powder as raw materials. Weigh 0.656 g of molybdenum powder and 1.276 g of tellurium powder, place them in a mortar and grind them evenly, and put the mixed powder into a quartz test tube. Then perform vacuum sealing treatment, while evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination treatment, heat it to 800 °C at a heating rate of 5 °C per minute and keep it for 48 hours. After the reaction is completely alloyed, after the muffle furnace is cooled to room temperature, obtain the gray powder MoTe2.
[0067] S2. Prepare 2,5-bis(4-chlorobenzoyl) using pyromellitic dianhydride, chlorobenzene, aluminum chloride, sodium bicarbonate, etc. as raw materials. Mix 20 g of pyromellitic dianhydride, 200 g of chlorobenzene and 50 g of aluminum chloride evenly in a round-bottom flask, heat it to 65 °C and react for 4 hours, then cool it to room temperature and stir for 6 hours. Pour the mixture in the flask into a pre-cooled 36% hydrochloric acid solution to quench, filter the solid and dissolve it in a sodium bicarbonate solution, and then filter to collect the filtrate. Wash the filtrate three times with dichloromethane, and then acidify it with concentrated hydrochloric acid to obtain the white precipitate 2,5-bis(4-chlorobenzoyl) terephthalic acid.
[0068] S3. Prepare 2,9-dichloroperylene-5,7,12,14-tetrone using the product 2,5-bis(4-chlorobenzoyl) terephthalic acid from S2, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as raw materials. Add 140 mL of trifluoromethanesulfonic acid and 0.5 mL of trifluoromethanesulfonic anhydride to 14 g of 2,5-bis(4-chlorobenzoyl) terephthalic acid, and heat the mixture to 150 °C in argon and keep it for 12 hours. Wait for the mixture to cool to room temperature, collect the solid and wash it with deionized water until the pH value of the filtrate is 5.0. Finally, dry the solid in a vacuum oven at 100 °C for 12 hours to obtain 2,9-dichloroperylene-5,7,12,14-tetrone.
[0069] S4. Prepare molybdenum ditelluride intercalated / coated with polyperyleneterone thioether (PPTS@MoTe2) using the product molybdenum ditelluride from S1, the product 2,9-dichloroperylene-5,7,12,14-tetrone from S3, sodium sulfide nonahydrate, etc. as raw materials. Disperse 0.0546 g of molybdenum ditelluride in 6.5 mL of N-methylpyrrolidone and ultrasonically disperse it for 30 minutes. Then add 0.2652 g of 2,9-dichloroperylene-5,7,12,14-tetrone and 0.1716 g of sodium sulfide nonahydrate, ultrasonically disperse it until it is completely dispersed, and then stir the mixture at 200 °C for 12 hours. After the reaction is completed and cooled to room temperature, filter to collect the product, wash the product with NMP, hot water, deionized water, ethanol, and acetone for multiple times, and after drying the product, the obtained brownish-black powder is PPTS@MoTe2.
[0070] When the obtained PPTS@MoTe2 material is used as the anode of a sodium-ion battery, it can maintain a reversible specific capacity of about 282.9 mAh / g after cycling 100 weeks at a current density of 100 mA / g.
[0071] Example 6
[0072] This example relates to a polyperyleneterone thioether / molybdenum ditelluride composite material for the anode of a sodium-ion battery, and its in-situ polymerization preparation method includes the following steps:
[0073] S1. Prepare molybdenum ditelluride (MoTe2) using tellurium powder and molybdenum powder as raw materials. Weigh 1.0496 g of molybdenum powder and 2.0416 g of tellurium powder, place them in a mortar and grind them evenly. Then put the mixed powder into a quartz test tube. Subsequently, perform vacuum sealing on the test tube. While evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination. Heat it at a heating rate of 4 °C per minute to 780 °C and keep it for 24 hours. Wait for the reactants to complete the alloying reaction completely. After the muffle furnace cools to room temperature, obtain the gray powder MoTe2.
[0074] S2. Prepare 2,5-bis(4-chlorobenzoyl) using pyromellitic dianhydride, chlorobenzene, aluminum chloride, sodium bicarbonate, etc. as raw materials. Mix 20 g of pyromellitic dianhydride, 200 g of chlorobenzene and 50 g of aluminum chloride evenly in a round-bottom flask, and heat it to 65 °C for reaction for 5 hours. Cool it to room temperature and stir for 6 hours. Pour the mixture in the flask into a pre-cooled 36% hydrochloric acid solution for quenching, filter the solid and dissolve it in a sodium bicarbonate solution, and then filter to collect the filtrate. Wash the filtrate three times with dichloromethane, and then acidify it with concentrated hydrochloric acid to obtain the white precipitate 2,5-bis(4-chlorobenzoyl) terephthalic acid.
[0075] S3. Prepare 2,9-dichloroperylene-5,7,12,14-tetrone using the product 2,5-bis(4-chlorobenzoyl) terephthalic acid from S2, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as raw materials. Add 140 mL of trifluoromethanesulfonic acid and 0.5 mL of trifluoromethanesulfonic anhydride to 14 g of 2,5-bis(4-chlorobenzoyl) terephthalic acid, and heat the mixture to 150 °C in argon and keep it for 12 hours. Wait for the mixture to cool to room temperature, collect the solid and wash it with deionized water until the pH value of the filtrate is 5.0. Finally, dry the solid in a vacuum oven at 100 °C for 12 hours to obtain 2,9-dichloroperylene-5,7,12,14-tetrone.
[0076] S4. Prepare polyperylene tetrone thioether intercalated / coated molybdenum ditelluride (PPTS@MoTe2) using the product molybdenum ditelluride from S1, the product 2,9-dichloroperylene-5,7,12,14-tetrone from S3, sodium sulfide nonahydrate, etc. as raw materials. Disperse 0.042 g of molybdenum ditelluride in 5 mL of N-methylpyrrolidone and ultrasonically disperse it for 30 minutes. Then add 0.204 g of 2,9-dichloroperylene-5,7,12,14-tetrone and 0.132 g of sodium sulfide nonahydrate, ultrasonically disperse it until it is completely dispersed, and then stir the mixture at 200 °C for 12 hours. After the reaction ends and cools to room temperature, filter to collect the product, wash the product with NMP, hot water, deionized water, ethanol, acetone for many times, and after drying the product, the obtained brownish-black powder is PPTS@MoTe2.
[0077] When the obtained PPTS@MoTe2 material is used as the anode of a sodium-ion battery, it can maintain a reversible specific capacity of about 281.5 mAh / g after 100 cycles at a current density of 100 mA / g.
[0078] Comparative Example 1
[0079] This comparative example relates to a molybdenum ditelluride anode material for a sodium-ion battery, and its preparation method includes the following steps:
[0080] S1. Prepare molybdenum ditelluride (MoTe2) using tellurium powder and molybdenum powder as raw materials. Weigh 0.656 g of molybdenum powder and 1.276 g of tellurium powder and place them in a mortar and grind them evenly. Then put the mixed powder into a quartz test tube. Subsequently, perform vacuum sealing treatment. While evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination treatment. Heat it to 800 °C at a heating rate of 5 °C per minute and hold for 24 hours. Wait for the reactants to complete the alloying reaction completely. After the muffle furnace cools to room temperature, obtain gray powder MoTe2.
[0081] When the obtained MoTe2 material is used as the anode of a sodium-ion battery, its cycling performance is as Figure 5 shown. MoTe2 can only maintain a reversible specific capacity of about 66.1 mAh / g after 100 cycles at a current density of 100 mA / g.
[0082] Comparative Example 2
[0083] This comparative example relates to a pentacene tetrone thioether / molybdenum ditelluride composite material for the anode of a sodium-ion battery, and its in-situ polymerization preparation method includes the following steps:
[0084] S1. Prepare molybdenum ditelluride (MoTe2) using tellurium powder and molybdenum powder as raw materials. Weigh 0.656 g of molybdenum powder and 1.276 g of tellurium powder and place them in a mortar and grind them evenly. Then put the mixed powder into a quartz test tube. Subsequently, perform vacuum sealing treatment. While evacuating the test tube, use a hydrogen-oxygen flame to seal it to ensure that the inside of the sealed test tube is a strictly vacuum environment. Then place the sealed test tube in a muffle furnace for high-temperature calcination treatment. Heat it to 800 °C at a heating rate of 5 °C per minute and hold for 24 hours. Wait for the reactants to complete the alloying reaction completely. After the muffle furnace cools to room temperature, obtain gray powder MoTe2.
[0085] S2. Prepare 2,5-bis(4-chlorobenzoyl)terephthalic acid using pyromellitic dianhydride, chlorobenzene, aluminum chloride, sodium bicarbonate, etc. as raw materials. Mix 20 g of pyromellitic dianhydride, 200 g of chlorobenzene, and 50 g of aluminum chloride evenly in a round-bottom flask, heat the mixture to 65 °C and react for 4 hours, then cool it to room temperature and stir for 6 hours. Pour the mixture in the flask into a pre-cooled 36% hydrochloric acid solution for quenching, filter the solid and dissolve it in a sodium bicarbonate solution, and then filter to collect the filtrate. Wash the filtrate three times with dichloromethane, and then acidify it with concentrated hydrochloric acid to obtain the white precipitate 2,5-bis(4-chlorobenzoyl)terephthalic acid.
[0086] S3. Prepare 2,9-dichloroperylene-5,7,12,14-tetrone using the product 2,5-bis(4-chlorobenzoyl)terephthalic acid from S2, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, etc. as raw materials. Add 140 mL of trifluoromethanesulfonic acid and 0.5 mL of trifluoromethanesulfonic anhydride to 14 g of 2,5-bis(4-chlorobenzoyl)terephthalic acid, and heat the mixture to 150 °C in argon and keep it for 12 hours. After the mixture cools to room temperature, collect the solid and wash it with deionized water until the pH value of the filtrate is 5.0. Finally, dry the solid in a vacuum oven at 100 °C for 12 hours to obtain 2,9-dichloroperylene-5,7,12,14-tetrone.
[0087] S4. Prepare molybdenum ditelluride intercalated / coated with poly(perylene tetrone thioether) (PPTS@MoTe2) using the product molybdenum ditelluride from S1, the product 2,9-dichloroperylene-5,7,12,14-tetrone from S3, sodium sulfide nonahydrate, etc. as raw materials. Disperse 0.084 g of molybdenum ditelluride in 5 mL of N-methylpyrrolidone and ultrasonically disperse it for 30 minutes. Then add 0.204 g of 2,9-dichloroperylene-5,7,12,14-tetrone and 0.132 g of sodium sulfide nonahydrate, ultrasonically disperse it until it is completely dispersed, and then stir the mixture at 200 °C for 12 hours. After the reaction ends and cools to room temperature, filter to collect the product, wash the product with NMP, hot water, deionized water, ethanol, and acetone multiple times, and after drying the product, the obtained brownish-black powder is PPTS@MoTe2, and its SEM micro-morphology is as Figure 6 shown. Although its surface is covered with the polymer PPTS, it can be seen that the coverage is not complete, and the outline of MoTe2 can be clearly seen.
[0088] When the obtained PPTS@MoTe2 material is used as the negative electrode of a sodium-ion battery, its cycling performance is as Figure 7 shown. PPTS@MoTe2 can maintain a reversible specific capacity of about 208.3 mAh / g after cycling 100 weeks at a current density of 100 mA / g.
[0089] The cycle performance comparison of the products prepared in the above Examples 1 to 6 and Comparative Examples 1 to 2 as the anode materials for sodium-ion batteries is as follows Figure 8 As shown: It can be seen that in Comparative Example 1, the specific capacity of the single MoTe2 material without PPTS coating after 100 cycles is only 66.1 mAh / g, which is due to the volume expansion of MoTe2 after multiple sodium ion insertion / extraction. In Comparative Example 2, part of MoTe2 in PPTS@MoTe2 is coated with PPTS, and the specific capacity after 100 cycles can reach 208.3 mAh / g, higher than that in Comparative Example 1, indicating that the flexible chain segments of PPTS can absorb mechanical stress and inhibit the volume expansion of the active material. The specific capacity of PPTS@MoTe2 in Examples 1 to 6 after 100 cycles is between 278.6 and 283.5 mAh / g, much higher than that of the single MoTe2 in Comparative Example 1 and the MoTe2 partially coated with PPTS in Comparative Example 2, highlighting the following advantages of PPTS@MoTe2: 1. As a conductive polymer, PPTS can form a continuous conductive network on the surface and between the layers of MoTe2, thus improving the cycle stability; 2. The flexible chain segments of PPTS in the PPTS@MoTe2 composite can absorb mechanical stress and inhibit the volume expansion of the active material; 3. MoTe2 provides the capacity for sodium ion insertion / extraction reactions, while PPTS can provide pseudocapacitance capacity through redox reactions, forming a synergistic energy storage mechanism.
[0090] The above embodiments are only specific embodiments of the present invention, and the description thereof is relatively specific and detailed, but it should not be construed as a limitation on the scope of the patent of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can be made, and these obvious replacement forms all belong to the protection scope of the present invention.
Claims
1. A preparation method of a sodium-ion battery anode pentacene tetrone thioether / molybdenum disulfide composite material, characterized in that It includes the following steps: Dispersing molybdenum disulfide in N-methylpyrrolidone, then adding 2,9-dichloroperylene-5,7,12,14-tetrone and sodium sulfide nonahydrate. After uniform dispersion, the mixture is stirred at high temperature until the reaction ends and cooled to room temperature. The product is collected by filtration, and after purification treatment and drying, PPTS@MoTe2 is obtained. The feeding ratio of molybdenum disulfide, 2,9-dichloroperylene-5,7,12,14-tetrone, sodium sulfide nonahydrate and N-methylpyrrolidone is (0.042 - 0.084 g):(0.204 - 0.408 g):(0.132 - 0.264 g):(5 - 10 mL).
2. The preparation method of the composite material of peropyrene tetrone thioether / molybdenum disulfide as the anode of a sodium ion battery according to claim 1, characterized in that: The preparation method of 2,9-dichloroperylene-5,7,12,14-tetrone is as follows: Add 2,5-bis(4-chlorobenzoyl)terephthalic acid into a mixed solution of trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride, and control the temperature of the mixture during the reaction in a protective atmosphere. After the mixture is cooled to room temperature, the solid is collected, washed and dried to obtain 2,9-dichloroperylene-5,7,12,14-tetrone. Among them, the feeding ratio of 2,5-bis(4-chlorobenzoyl)terephthalic acid, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride is (14 - 28 g):(140 - 280 g):(0.5 - 1.0 g).
3. The preparation method of the sodium ion battery anode pentacene tetrone thioether / molybdenum ditelluride composite material according to claim 2, characterized in that: The preparation method of 2,5-bis(4-chlorobenzoyl)terephthalic acid is as follows: Mix pyromellitic dianhydride, chlorobenzene, and aluminum chloride evenly, control the temperature during the reaction and then cool to room temperature. Take out the reactant and quench it in a pre-cooled 36% hydrochloric acid solution. Filter the solid and dissolve it in sodium bicarbonate solution, then filter to collect the filtrate, wash and acidify to obtain the precipitate 2,5-bis(4-chlorobenzoyl)terephthalic acid. Among them, the feeding ratio of pyromellitic dianhydride, chlorobenzene, and aluminum chloride is (20 - 40 g):(200 - 400 g):(50 - 100 g).
4. The preparation method of the composite material of pentacene tetrone thioether / molybdenum ditelluride as the anode of the sodium ion battery according to claim 3, characterized in that: The preparation method of molybdenum disulfide is as follows: Mix molybdenum powder and tellurium powder evenly by grinding, put them into a quartz test tube and seal it under vacuum, and carry out alloying reaction by high-temperature calcination. After cooling, MoTe2 powder is obtained. Among them, the feeding ratio of molybdenum powder and tellurium powder is (0.656 - 1.912 g):(1.276 - 2.552 g).
5. The preparation method of the sodium-ion battery anode pentacene tetrone thioether / molybdenum ditelluride composite material according to claim 4, characterized in that: In the preparation method of molybdenum disulfide, the conditions for high-temperature calcination are: heating rate 3 - 6 °C / minute, calcination temperature 750 - 850 °C, and holding time 24 - 48 hours.
6. The preparation method of the composite material of pentacene tetrone thioether / molybdenum ditelluride as the anode of the sodium ion battery according to claim 5, wherein: In the preparation method of 2,5-bis(4-chlorobenzoyl)terephthalic acid, the conditions for temperature-controlled reaction are: reaction temperature 65 - 70 °C, and reaction time 4 - 6 hours.
7. The preparation method of the sodium ion battery anode pentacene tetrone thioether / molybdenum ditelluride composite material according to claim 6, characterized in that: In the preparation method of 2,9-dichloroperylene-5,7,12,14-tetrone, the conditions for temperature-controlled reaction are: heating temperature 140 - 160 °C, and holding time 12 hours.
8. The preparation method of the sodium ion battery anode pentacene tetrone thioether / molybdenum disulfide composite according to claim 7, characterized in that: In the preparation method of MoTe2@PPTS, the conditions for high-temperature stirring reaction of the mixture are: reaction temperature 160 - 240 °C, and stirring time 10 - 14 hours.