Preparation method of a composite carbonaceous energy storage material

Abstract

A preparation method of a composite carbonaceous energy storage material, in which the carbon co-produced by natural gas thermal cracking, coal, and the co-liquefaction pitch of heavy oil are used as carbon precursors for co-carbonization. After the co-carbonization product is washed with inorganic acid or organic acid, potassium hydroxide and potassium carbonate are used as activators for activation to obtain activated carbon. The activated carbon is added to a reaction kettle filled with deionized water, and inorganic salts or organic salts are added to form a suspension. Air is evenly introduced into the suspension from the bottom of the reaction kettle. After the reaction, the suspension is repeatedly filtered and washed with water to obtain Fe-Ni-M supported carbon. The Fe-Ni-M supported carbon is placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain the energy storage material. The present invention uses the carbon co-produced by natural gas thermal cracking, coal, and the co-liquefaction pitch of heavy oil or the by-product pitch of coal tar slurry bed hydrogenation for co-carbonization, and couples metal sulfide with porous carbon to prepare an energy storage material, which has the characteristics of low processing cost and excellent comprehensive performance.

Description

Technical Field

[0001] The present invention relates to the technical field of resource utilization of by - product asphalt from coal - tar slurry - bed hydrogenation, coal - heavy oil co - liquefaction asphalt, and carbon black associated with acetylene production from natural gas pyrolysis, and particularly relates to a preparation method of a composite carbonaceous energy storage material. Background Art

[0002] The carbon black associated with acetylene production from natural gas pyrolysis is characterized by high water content, small particle size, large output, and poor quality. At present, there is no effective utilization technology, and it is often landfilled or used as fuel. With the increasing emphasis on environmental protection and resource recycling, the high - value utilization of carbon black associated with acetylene production from natural gas pyrolysis has become an industry pain point that urgently needs to be solved.

[0003] The carbon precursors of carbonaceous energy storage materials for supercapacitors mainly come from coal - based raw materials such as coal and coal tar, petroleum - based raw materials such as petroleum coke and petroleum asphalt, bio - based raw materials such as fruit shells, coconut shells, plant stems and leaves, and polymer materials such as starch and phenolic resin. There are generally defects such as insufficient technical and economic competitiveness due to high raw material costs, long processing processes, and low yields of preparing energy storage materials. Moreover, the quality of coal - based and petroleum - based raw materials is generally poor. There is no precedent for preparing carbonaceous energy storage materials for supercapacitors from natural gas - based raw materials.

[0004] Patent CN201620349559 provides a system for preparing activated carbon using carbon black, which uses carbon dioxide as an activator to physically activate carbon black to increase the specific surface area to prepare conventional activated carbon. However, the ability of physical activation to increase the specific surface area is limited, and the value - added of the prepared activated carbon is low.

[0005] The article doi:10.1016 / S1872 - 5813(21)60006 - 3 (Zhu Junsheng, Ding Xiaobo, Cao Jingpei, Zhang Shuangquan, Yue Xiaoming, Hu Guangzhou. Preparation and Capacitance Characteristics of Lignite - based Porous Carbon / CoNi2S4 Composites) discloses that using lignite as a carbon precursor, after extraction and activation with KOH solution, coal - based porous carbon is prepared, and the coal - based porous carbon is combined with CoNi2S4 by a simple hydrothermal method to prepare a carbonaceous energy storage material for supercapacitors. The mass specific capacitance reaches 1318.2 F / g at a current density of 4 A / g, but the capacitance retention rate is only 80.9% after 4000 charge - discharge cycles.

[0006] At present, the utilization of carbon black associated with acetylene production from natural gas pyrolysis has problems such as low added value and poor product performance, and the carbonaceous energy storage materials for supercapacitors generally have problems such as poor raw material quality, long processing processes, low proportion of mesoporous specific surface area, low yield of preparing energy storage materials, or high costs.

[0007] The carbon black with less ash content, smaller particle size and higher carbon content produced by the thermal cracking of natural gas to produce acetylene can be used to prepare a carbonaceous energy storage material for supercapacitors, so as to solve the above problems existing in the prior art. Summary of the Invention

[0008] In order to overcome the deficiencies of the above prior art, the purpose of the present invention is to provide a preparation method of a composite carbonaceous energy storage material, which makes full use of the respective unique advantages of carbon black and the by-product asphalt from the slurry bed hydrogenation of coal tar or the co-liquefaction asphalt of coal and heavy oil, gives full play to the synergistic pore-forming ability of different potassium source activators, and gives full play to the comprehensive performance advantages of the composite of metal sulfides and carbonaceous porous materials, and prepares carbon black into a carbonaceous energy storage material for supercapacitors with cost advantages and performance advantages, so as to realize the high-value utilization of carbon black. This method has the characteristics of low processing cost and excellent comprehensive performance.

[0009] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0010] A preparation method of a composite carbonaceous energy storage material, comprising the following steps:

[0011] (1) The carbon co-produced by the thermal cracking of natural gas and the co-liquefaction asphalt of coal and heavy oil are used as carbon precursors for co-carbonization. After the co-carbonization product is washed with inorganic acid or organic acid, it is activated with potassium hydroxide and potassium carbonate as activators to obtain activated carbon;

[0012] (2) Add the activated carbon to a reaction kettle filled with deionized water, and add inorganic salts or organic salts to form a suspension. Uniformly introduce air into the suspension from the bottom of the reaction kettle. After the reaction, the suspension is repeatedly filtered and washed with water until the pH of the filtrate remains unchanged, and then the filter cake is dried to obtain Fe-Ni-M supported carbon;

[0013] (3) Place the Fe-Ni-M supported carbon in a tube furnace and sulfide it in a hydrogen / hydrogen sulfide atmosphere to obtain an energy storage material, and the energy storage material is Fe-Ni-M sulfide composite carbon.

[0014] Preferably, in the step (1), the mass ratio of the carbon co-produced by the thermal cracking of natural gas to the co-liquefaction asphalt of coal and heavy oil is 6:4 - 8:2; the mass ratio of potassium hydroxide to potassium carbonate is 6:4 - 7:3.

[0015] Preferably, in the step (1), when carrying out co-carbonization, the carbonization temperature is 805 - 835 °C, when carrying out activation, the mass ratio of the activator to the carbon precursor is 3.2:1 - 3.4:1, the activation temperature is 810 - 830 °C, and the heating rate of both the carbonization temperature and the activation temperature is 8 °C / min.

[0016] Preferably, in the step (1), the co-carbonization time is 1.6 - 1.8 hours, and the co-activation time is 1.6 - 1.8 hours.

[0017] Preferably, in the step (1), the carbon co-produced by natural gas pyrolysis can also be used as a carbon precursor together with coal tar pitch in a mass ratio of 6:4 - 8:2 to prepare the composite carbonaceous energy storage material.

[0018] Preferably, in the step (2), the inorganic salt or organic salt is nickel salt, ferrous salt or metal M salt. Control the temperature in the reaction kettle to 42 °C, start stirring, and uniformly introduce air into the suspension from the bottom of the reaction kettle, and react for 2.5 hours.

[0019] Preferably, in the step (2), the nickel salt is one or more of nickel sulfate hexahydrate or nickel dodecylbenzenesulfonate;

[0020] The ferrous salt is one or more of ferrous sulfate heptahydrate or ferrous dodecylbenzenesulfonate;

[0021] The metal M is one or more of cobalt sulfate heptahydrate or cobalt dodecylbenzenesulfonate.

[0022] The mass ratio of the activated carbon to deionized water is 1:6 - 1:8, the mass ratio of metal nickel and metal iron in the nickel salt and ferrous salt is 6.5:3.5 - 7.5:2.5, and the total mass of metal nickel, metal iron and metal M contained in the organic salt or inorganic salt accounts for 0.003% - 0.8% of the mass of the activated carbon.

[0023] Advantages of the present invention:

[0024] The present invention utilizes the respective composition characteristics of the carbon co-produced by natural gas pyrolysis and heavy oil co-liquefied asphalt, and the complex polymerization or cross-linking reactions occurring during the carbonization and activation processes, and utilizes the advantage that the appropriate amount of ash contained can act as a template by occupying positions and is also convenient for pickling and removal; the carbon content of the carbon co-produced by natural gas pyrolysis and kerosene co-liquefied asphalt is high, and the gradient synergistic pore formation is realized by making full use of the different sensitive temperature ranges of the reactions of potassium carbonate and potassium hydroxide, so as to form a porous carbon with a high mesopore rate, and improve the storage and transport capacity of electrolyte ions; the composite of highly dispersed polymetallic sulfides and porous carbon not only improves the rate performance of the energy storage material, but also ensures the cycle performance of the energy storage material, and has more industrial application prospects.

[0025] The natural gas pyrolysis co-produced carbon-based energy storage material prepared by the present invention has a high specific surface area, and the specific surface area reaches more than 2700 m 2 / g.

[0026] The natural gas thermal cracking associated carbon-based energy storage material prepared by the present invention has a high mesopore specific surface area ratio, strong storage and transportation capacity of ions in the electrolyte, and good cycle performance.

[0027] The natural gas thermal cracking associated carbon-based energy storage material prepared by the present invention maintains good mass specific capacitance stability under high current density.

[0028] The inexpensive and readily available carbon associated with the pyrolysis of natural gas is used as the main carbon precursor. Through the compounding of the above-mentioned carbon precursors, the compounding of activators, and the compounding of metal sulfides and porous carbon, the comprehensive improvement of the performance of energy storage materials for supercapacitors prepared from carbon associated with the pyrolysis of natural gas and the overall reduction of costs are achieved. At the same time, the preparation process of existing porous carbon energy storage materials is improved, providing a high value-added method for utilizing carbon associated with the pyrolysis of natural gas. DETAILED DESCRIPTION

[0029] The present invention is further described in detail below in conjunction with embodiments.

[0030] Example 1

[0031] 6 g of natural gas thermal cracking associated carbon and 4 g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 805°C at a rate of 8°C / min in a tubular furnace for carbonization for 1.6 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material; a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6:4 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.2:1. The carbonized material was heated to 810°C in a tubular furnace at a rate of 8°C / min for 1.6 h to obtain activated carbon; the activated carbon was loaded into a 6-fold container. In a beaker of deionized water of its own mass, the temperature of the mixed liquid in the beaker is controlled to be 42°C, the stirring rate is set to 150r / min, and the mass ratio of metallic nickel and metallic iron in nickel sulfate hexahydrate and ferrous sulfate heptahydrate is 6.5:3.5, and the two metals account for 0.003% of the mass of activated carbon. They are weighed and added into the beaker, and air is blown in at 100ml / min. The reaction is carried out for 2.5h, and the loaded carbon is repeatedly washed with water until the pH value no longer changes to obtain the loaded carbon; the loaded carbon is placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon A.

[0032] Example 2

[0033] 8 g of natural gas thermal cracking associated carbon and 2 g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 835°C in a tubular furnace at a rate of 8°C / min for carbonization for 1.8 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material; a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 7:3 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.4:1. The carbonized material was heated to 830°C in a tubular furnace at a rate of 8°C / min for 1.8 h to obtain activated carbon; the activated carbon was loaded into a container containing 8 In a beaker filled with deionized water twice its own mass, the temperature of the mixed liquid in the beaker is controlled to be 42°C, the stirring rate is set to 150r / min, and the mass ratio of metallic nickel and metallic iron in nickel sulfate hexahydrate and ferrous sulfate heptahydrate is 7.5:2.5, and the two metals account for 0.8% of the mass of activated carbon. They are weighed and added into the beaker, and air is blown in at 100ml / min. The reaction is carried out for 2.5h, and the loaded carbon is repeatedly washed with water until the pH value no longer changes to obtain the loaded carbon; the loaded carbon is placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon B.

[0034] Example 3

[0035] 6 g of natural gas thermal cracking associated carbon and 4 g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 805°C in a tubular furnace at a rate of 8°C / min for carbonization for 1.6 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material; a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6:4 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.2:1. The carbonized material was activated at a temperature of 8°C / min to 810°C in a tubular furnace for 1.6 h to obtain activated carbon; the activated carbon was placed in a beaker filled with deionized water 6 times its own mass, and the activated carbon was controlled to The temperature of the mixed liquid in the beaker is 42°C, the stirring rate is set to 150r / min, the mass ratio of metallic nickel and metallic iron in nickel sulfate hexahydrate and ferrous sulfate heptahydrate is 6.5:3.5 and the two metals account for 0.003% of the mass of the activated carbon, and cobalt sulfate heptahydrate is weighed according to the metal cobalt accounting for 0.001% of the mass of the activated carbon, and then all are added into the beaker, and air is blown in at 100ml / min. The reaction is carried out for 2.5h, and the loaded carbon is repeatedly washed with water until the pH no longer changes to obtain the loaded carbon; the loaded carbon is placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon C.

[0036] Example 4

[0037] 7 g of natural gas thermal cracking associated carbon and 3 g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 815°C in a tubular furnace at a rate of 8°C / min for carbonization for 1.7 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material; a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6.5:3.5 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.3:1. The carbonized material was heated to 820°C in a tubular furnace at a rate of 8°C / min for 1.7 h to obtain activated carbon; the activated carbon was loaded into In a beaker filled with deionized water 6 times its own mass, the temperature of the mixed liquid in the beaker is controlled to be 42°C, the stirring rate is set to 150r / min, and the mass ratio of metallic nickel and metallic iron in nickel sulfate hexahydrate and ferrous sulfate heptahydrate is 7:3 and the two metals account for 0.008% of the mass of activated carbon. They are weighed and added into the beaker, and air is blown in at 100ml / min. The reaction is carried out for 2.5h, and the loaded carbon is repeatedly washed with water until the pH no longer changes to obtain the loaded carbon; the loaded carbon is placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon D.

[0038] Example 5

[0039] 7 g of natural gas thermal cracking associated carbon and 3 g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 815°C in a tubular furnace at a rate of 8°C / min for carbonization for 1.7 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material; a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6.5:3.5 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.3:1. The carbonized material was heated to 820°C in a tubular furnace at a rate of 8°C / min for 1.7 h to obtain activated carbon; the activated carbon was loaded into a container containing In a beaker filled with deionized water that is 6 times its own mass, the temperature of the mixed liquid in the beaker is controlled to be 42°C, the stirring rate is set to 150r / min, and the mass ratio of metallic nickel and metallic iron in nickel dodecylbenzenesulfonate and ferrous dodecylbenzenesulfonate is 7:3 and the two metals account for 0.008% of the mass of activated carbon. They are weighed and added into the beaker, and air is blown in at 100ml / min. The reaction is carried out for 2.5h, and the loaded carbon is repeatedly washed with water until the pH value no longer changes to obtain the loaded carbon; the loaded carbon is placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon E.

[0040] Example 6

[0041] 7g of natural gas thermal cracking associated carbon and 3g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 815℃ in a tubular furnace at a rate of 8℃ / min for carbonization for 1.7h. The carbonized product was washed three times with 1mol / L acetic acid to obtain a carbonized material; a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6.5:3.5 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.3:1. The carbonized material was heated to 820℃ in a tubular furnace at a rate of 8℃ / min for 1.7h to obtain activated carbon; the activated carbon was loaded into a container In a beaker containing deionized water 6 times its own mass, the temperature of the mixed liquid in the beaker is controlled to be 42°C, the stirring rate is set to 150r / min, nickel sulfate hexahydrate and metallic nickel and metallic iron in ferrous dodecylbenzenesulfonate are weighed and added into the beaker according to the mass ratio of 7:3 and the two metals accounting for 0.008% of the mass of activated carbon, and air is blown in at 100ml / min. The reaction is carried out for 2.5h, and the loaded carbon is repeatedly washed with water until the pH value no longer changes to obtain the loaded carbon; the loaded carbon is placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon F.

[0042] Example 7

[0043] 7g of natural gas thermal cracking associated carbon and 3g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 815℃ in a tubular furnace at a rate of 8℃ / min for carbonization for 1.7h. The carbonized product was washed three times with 1mol / L acetic acid to obtain a carbonized material; a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6.5:3.5 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.3:1. The carbonized material was heated to 820℃ in a tubular furnace at a rate of 8℃ / min for 1.7h to obtain activated carbon; the activated carbon was The carbon was loaded into a beaker containing deionized water six times its own mass, the temperature of the mixed liquid in the beaker was controlled at 42°C, the stirring rate was set at 150r / min, and the metal nickel and metal iron in nickel dodecylbenzenesulfonate were weighed and added into the beaker according to a mass ratio of 7:3 and two metals accounting for 0.008% of the mass of the activated carbon. Air was blown in at 100ml / min, and the reaction was carried out for 2.5h. The loaded carbon was repeatedly washed with water until the pH value no longer changed to obtain the loaded carbon. The loaded carbon was placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon G.

[0044] Example 8

[0045] Weigh 7 g of carbon produced by thermal cracking of natural gas and 3 g of pitch by-product from coal tar slurry bed hydrogenation, and mix and soak them thoroughly. In a tube furnace, heat at a rate of 8 °C / min to 815 °C and carbonize for 1.7 h. Wash the carbonized product 3 times with 1 mol / L acetic acid to obtain carbonized material; use a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6.5:3.5 as the activator, and the mass ratio of the activator to the carbonized material is 3.3:1. Activate the carbonized material in a tube furnace at a heating rate of 8 °C / min to 820 °C for 1.7 h to obtain activated carbon; put the activated carbon into a beaker containing 6 times its own mass of deionized water, control the temperature of the mixed solution in the beaker to be 42 °C, set the stirring rate to 150 r / min, weigh and add to the beaker according to the mass ratio of nickel and iron in dodecylbenzenesulfonic acid nickel being 7:3 and the total mass of the two metals accounting for 0.008% of the mass of the activated carbon, and blow in air at 100 ml / min and react for 2.5 h. Wash repeatedly with water until the pH no longer changes to obtain loaded carbon; place the loaded carbon in a tube furnace and sulfide it in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon H.

[0046] Comparative Example 1

[0047] According to the method disclosed in the reference article DOI: 10.13900 / j.cnki.jbc.2020.05.004 (Liu Muxin, Zhao Jianjun, Lu Hubiao, etc. Research on the preparation of activated carbon from carbon black [J]. Journal of Bengbu University, 2020, 9(05): 14 - 17), activated carbon A was obtained with an alkali-carbon ratio of 3:1.

[0048] Comparative Example 2

[0049] According to the method disclosed in the reference article DOI: 10.13900 / j.cnki.jbc.2020.05.004 (Liu Muxin, Zhao Jianjun, Lu Hubiao, etc. Research on the preparation of activated carbon from carbon black [J]. Journal of Bengbu University, 2020, 9(05): 14 - 17), activated carbon B was obtained with an alkali-carbon ratio of 4:1.

[0050] Comparative Example 3

[0051] According to the method disclosed in the reference article DOI: 10.13900 / j.cnki.jbc.2020.05.004 (Liu Muxin, Zhao Jianjun, Lu Hubiao, etc. Research on the preparation of activated carbon from carbon black [J]. Journal of Bengbu University, 2020, 9(05): 14 - 17), activated carbon C was obtained with an alkali-carbon ratio of 5:1.

[0052] Comparative Example 4

[0053] Composite carbon H was prepared according to Example 4 of the reference patent "A Suspension Bed Hydrotreating Multicomponent Composite Iron-based Catalyst and Its Preparation Method" (Application No. 201810445039.2).

[0054] Comparative Example 5

[0055] According to the method provided in the reference article doi:10.1016 / S1872-5813(21)60006-3 (Jun-sheng Zhu, Xiao-bo Ding, Jing-pei Cao, Shuang-quan Zhang, Xiao-ming Yue, Guang-zhou Hu. Preparation and Capacitance Properties of Lignite-based Porous Carbon / CoNi2S4 Composites), composite carbon I was prepared using natural gas pyrolysis by-product carbon as the carbon precursor.

[0056] Comparative Example 6

[0057] Weigh 10 g of natural gas pyrolysis by-product carbon, heat it in a tubular furnace at a heating rate of 8 °C / min to 805 °C and carbonize for 1.6 h. Wash the carbonized product 3 times with 1 mol / L sulfuric acid to obtain a carbonized material. Use a mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6:4 as the activator, and the mass ratio of the activator to the carbonized material is 3.2:1. Activate the carbonized material in a tubular furnace at a heating rate of 8 °C / min to 810 °C for 1.6 h to obtain activated carbon. Put the activated carbon into a beaker containing 6 times its own mass of deionized water, control the temperature of the mixed solution in the beaker to 42 °C, set the stirring rate to 150 r / min, weigh and add to the beaker according to the mass ratio of nickel and iron in nickel sulfate hexahydrate and ferrous sulfate heptahydrate being 6.5:3.5 and the total mass of the two metals accounting for 0.003% of the mass of the activated carbon. Bubble in air at 100 ml / min and react for 2.5 h. Wash repeatedly with water until the pH no longer changes to obtain the loaded carbon. Place the loaded carbon in a tubular furnace and sulfide it in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon J.

[0058] Comparative Example 7

[0059] 10 g of coal and heavy oil co-liquefied asphalt was weighed, and the temperature was raised to 805°C in a tubular furnace at a rate of 8°C / min for carbonization for 1.6 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material. A mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6:4 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.2:1. The carbonized material was heated to 810°C in a tubular furnace at a rate of 8°C / min for 1.6 h to obtain activated carbon. The activated carbon was placed in a deionized water container containing 6 times its own mass. The mixture was placed in a beaker of water, the temperature of the mixed liquid in the beaker was controlled to be 42°C, the stirring rate was set to 150r / min, the mass ratio of metallic nickel to metallic iron in nickel sulfate hexahydrate and ferrous sulfate heptahydrate was 6.5:3.5 and the two metals accounted for 0.003% of the mass of activated carbon, and were weighed and added into the beaker, 100ml / min of air was introduced, the reaction was carried out for 2.5h, and the loaded carbon was obtained after repeated water washing until the pH value no longer changed; the loaded carbon was placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain composite carbon K.

[0060] Comparative Example 8

[0061] 6 g of natural gas thermal cracking associated carbon and 4 g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 805°C in a tubular furnace at a rate of 8°C / min for carbonization for 1.6 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material; potassium hydroxide was used as an activator, and the mass ratio of the activator to the carbonized material was 3.2:1. The carbonized material was heated to 810°C in a tubular furnace at a rate of 8°C / min for 1.6 h to obtain activated carbon; the activated carbon was placed in a deionized water container containing 6 times its own mass. The mixture was placed in a beaker of water, the temperature of the mixed liquid in the beaker was controlled to be 42°C, the stirring rate was set to 150r / min, and the mass ratio of metallic nickel and metallic iron in nickel sulfate hexahydrate and ferrous sulfate heptahydrate was 6.5:3.5, and the two metals accounted for 0.003% of the mass of activated carbon, and were weighed and added into the beaker. Air was blown in at 100ml / min, and the reaction was carried out for 2.5h. The loaded carbon was repeatedly washed with water until the pH value no longer changed to obtain the loaded carbon; the loaded carbon was placed in a tubular furnace and sulfided in a hydrogen / hydrogen sulfide atmosphere to obtain the composite carbon L.

[0062] Comparative Example 9

[0063] 6 g of natural gas thermal cracking associated carbon and 4 g of coal and heavy oil co-liquefaction asphalt were weighed and fully mixed and infiltrated, and the temperature was raised to 805 °C in a tubular furnace at a rate of 8 °C / min for carbonization for 1.6 h. The carbonized product was washed three times with 1 mol / L sulfuric acid to obtain a carbonized material. A mixture of potassium hydroxide and potassium carbonate with a mass ratio of 6:4 was used as an activator, and the mass ratio of the activator to the carbonized material was 3.2:1. The carbonized material was activated at a temperature of 8 °C / min in a tubular furnace at 810 °C for 1.6 h to obtain composite carbon M.

[0064] The surface physical structure and chemical properties of the composite carbon AI and activated carbon AC obtained in Examples 1-7 and Comparative Examples 1-8 were measured respectively. The results are shown in Table 3.

[0065] Table 1 Properties of carbon associated with natural gas pyrolysis

[0066]

[0067]

[0068] Table 2 Properties of coal and heavy oil co-liquefaction asphalt

[0069]

[0070] Table 3 Industrial analysis of by-product asphalt from coal tar suspension bed hydrogenation

[0071]

[0072]

[0073] Table 4 Surface physical structure and electrochemical properties

[0074]

[0075]

[0076] It can be seen from Table 1, Table 2 and Table 3 that the energy storage material prepared by the technical solution of the present invention has a higher specific surface area, a larger proportion of mesoporous specific surface area, and has more comprehensive advantages in mass specific capacitance, cycle performance and rate performance.

[0077] The present invention makes full use of the advantages of co-carbonization of carbon associated with thermal cracking of natural gas and asphalt co-liquefied from coal and heavy oil or asphalt by-product of coal tar slurry bed hydrogenation, and couples the advantages of metal sulfide and porous carbon composite to prepare high-quality energy storage materials for supercapacitors, thereby solving the problems of resource utilization and low added value of carbon associated with acetylene produced from natural gas, and at the same time solves the problems of low yield, high cost, low mass specific capacitance and insufficient rate performance of current capacitor carbon production.

[0078] The above are only individual embodiments of the present invention and cannot be used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the general concept of the present invention are within the protection scope of the present invention.

Claims

1. A preparation method of a composite carbonaceous energy storage material, characterized in that, It includes the following steps: (1) The carbon co-produced by natural gas thermal cracking, coal, and the co-liquefaction pitch of heavy oil are used as carbon precursors for co-carbonization. After washing the co-carbonization product with inorganic acid or organic acid, it is activated with potassium hydroxide and potassium carbonate as activators to obtain activated carbon. (2) Add the activated carbon into a reaction kettle filled with deionized water, and add inorganic salt or organic salt to form a suspension. Uniformly introduce air into the suspension from the bottom of the reaction kettle. After the reaction, the suspension is repeatedly filtered and washed with water until the pH of the filtrate remains unchanged, and then the filter cake is dried to obtain Fe-Ni-M supported carbon. (3) Place the Fe-Ni-M supported carbon in a tube furnace and sulfide it in a hydrogen / hydrogen sulfide atmosphere to obtain an energy storage material, and the energy storage material is Fe-Ni-M sulfide composite carbon. In step (2), the inorganic salt or organic salt is nickel salt, ferrous salt, and metal M salt. In step (1), the mass ratio of the carbon co-produced by natural gas thermal cracking, coal, and the co-liquefaction pitch of heavy oil is 6:4 - 8:2; the mass ratio of potassium hydroxide and potassium carbonate is 6:4 - 7:

3.

2. The preparation method of a composite carbonaceous energy storage material according to claim 1, characterized in that, In step (1), during co-carbonization, the carbonization temperature is 805 - 835 °C, during activation, the mass ratio of the activator to the carbon precursor is 3.2:1 - 3.4:1, the activation temperature is 810 - 830 °C, and the heating rate to the carbonization temperature and the activation temperature is 8 °C / min.

3. The preparation method of a composite carbonaceous energy storage material according to claim 2, characterized in that, In step (1), the carbonization time is 1.6 - 1.8 hours, and the activation time is 1.6 - 1.8 hours.

4. The preparation method of a composite carbonaceous energy storage material according to claim 1, characterized in that, In step (1), coal tar pitch is used to replace the co-liquefaction pitch of coal and heavy oil.

5. The preparation method of a composite carbonaceous energy storage material according to claim 1, characterized in that, In step (2), control the temperature in the reaction kettle to 42 °C, start stirring, and uniformly introduce air into the suspension from the bottom of the reaction kettle for 2.5 hours.

6. The preparation method of a composite carbonaceous energy storage material according to claim 5, characterized in that, In step (2), the nickel salt is one or more of nickel sulfate hexahydrate or nickel dodecylbenzenesulfonate. The ferrous salt is one or more of ferrous sulfate heptahydrate or ferrous dodecylbenzenesulfonate. The metal M is one or more of cobalt sulfate heptahydrate or cobalt dodecylbenzenesulfonate.

7. The preparation method of a composite carbonaceous energy storage material according to claim 5, characterized in that, The mass ratio of the activated carbon to deionized water is 1:6 - 1:8, the mass ratio of metal nickel and metal iron in the nickel salt and ferrous salt is 6.5:3.5 - 7.5:2.5, and the total mass of metal nickel, metal iron, and metal M contained in the organic salt or inorganic salt accounts for 0.003% - 0.8% of the mass of the activated carbon.

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