Application of carbon material taking soot as carbon source in energy storage device
By using soot as a carbon source, nanoparticle carbon materials with amorphous carbon structures were prepared, solving the problems of complex and costly carbon material acquisition processes in the past, and achieving stable supply and efficient energy storage performance.
Patent Information
- Application Number
- CN202511020641.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-24
- Publication Date
- 2025-10-28
AI Technical Summary
The existing carbon material production process is complex, costly, and unstable, which hinders its large-scale application in energy storage devices.
Using carbon soot as a carbon source, nanoparticle carbon materials with amorphous carbon structure and graphite crystal domains are prepared through simple cleaning and one-step activation carbonization treatment, and applied to supercapacitor electrodes, lithium-ion battery anodes and conductive agents.
It achieves a stable supply of carbon materials, simplifies the production process, reduces energy consumption and costs, and provides high conductivity and good energy storage performance.
Smart Images
Figure CN120841518A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of carbon materials technology, specifically relating to the application of carbon materials with soot as a carbon source in energy storage devices. Background Technology
[0002] Supercapacitors and lithium-ion batteries are common green energy storage devices, especially due to their high power density, high energy density, and long service life, which have wide applications in vehicle power systems and energy storage.
[0003] Carbon materials are commonly used electrode materials in the aforementioned energy storage devices, possessing excellent conductivity, chemical stability, and advantages such as low volume change rate, low potential, structural stability, and low cost. Currently, commonly used carbon materials for electrodes mainly originate from biomass-derived carbon, fossil fuel-derived carbon, novel polymer-derived carbon, and other novel carbon materials. However, obtaining carbon materials from these sources often involves energy-intensive processes (pre-oxidation, high-temperature carbonization), high costs (raw materials such as polymer-derived carbon and graphene, as well as the cost of large amounts of activators), complex synthesis routes (pre-oxidation, activation, carbonization, etc.), and unstable sources (biomass, especially plant-based materials, is seasonal and geographically dependent), thus hindering their large-scale application. How to obtain carbon materials more efficiently, energy-savingly, and stably to achieve a continuous supply of carbon material anodes for energy storage is a current challenge. Summary of the Invention
[0004] This invention provides an application of carbon materials using soot as a carbon source in energy storage devices.
[0005] The technical solution of the present invention is as follows:
[0006] This invention provides an application of carbon materials using soot as a carbon source in energy storage devices. The carbon materials are obtained by using soot as raw material and undergoing simple cleaning and one-step activation and carbonization treatment. The carbon materials are nanoparticles with an amorphous carbon structure and locally have graphite crystal domains. The nanoparticles have slit or crack-like gap pores with a pore size distribution range of 10-50 nm, and are used in energy storage devices.
[0007] Furthermore, the carbon material is used in supercapacitor electrodes, lithium-ion battery anodes, and conductive agents.
[0008] This invention also provides a method for preparing carbon materials using soot as a carbon source, comprising:
[0009] The simple cleaning process is as follows: disperse the carbon soot in anhydrous ethanol, centrifuge at high speed, and then vacuum dry.
[0010] The activation carbonization process is as follows: the cleaned and dried carbon fumes are mixed with potassium hydroxide particles, dispersed in water, treated in a water bath, dried, and the dried mixture is activated carbonized. The aqueous solution of the carbonization product is neutralized with hydrochloric acid, washed, and dried to obtain the final product.
[0011] Furthermore, the dried carbon soot is mixed with potassium hydroxide particles at a mass ratio of 1:2.
[0012] Furthermore, the carbonization is carried out in a tube furnace filled with N2 at a temperature of 700-900°C for 2 hours.
[0013] Beneficial effects
[0014] The present invention proposes a method for preparing regenerated carbon materials from diesel engine emission particulate matter. For the first time, it proposes to use particulate matter from diesel engines as a source of conductive porous carbon materials. The raw material source is stable and has almost zero cost, which can support future large-scale utilization. Since diesel particulate matter itself is a carbonization product (carbon content >80%), it eliminates the need for separate activation or pre-carbonization steps required to prepare carbon materials from biomass or polymer precursors, which can simplify the production process and reduce energy consumption.
[0015] The present invention provides a method for treating particulate matter emitted by diesel engines, which involves simple cleaning and a one-step activation carbonization process. The carbon material obtained after the treatment has good conductivity and can be used as an electrode material for supercapacitors, a negative electrode material for lithium-ion batteries, a conductive agent, or other conductive carbon materials.
[0016] Compared with existing DPF regeneration methods, the process of this application does not require excessive consumption of fossil energy, has relatively lower costs, and does not cause secondary pollution to the environment. At the same time, it effectively treats particulate matter emissions in a green manner, realizes the regeneration and recycling of carbon particulate matter, and deeply integrates environmental governance with green energy technology. It provides innovative ideas and development directions for future joint research in multiple fields such as resource recycling, air emission control and high-performance energy storage, and greatly contributes to the realization of energy conservation, emission reduction and dual-carbon strategic goals. Attached Figure Description
[0017] Figure 1 This is a schematic diagram of the preparation method in Example 1.
[0018] Figure 2 This is an X-ray diffraction pattern.
[0019] Figure 3 This is a scanning electron microscope image.
[0020] Figure 4 This is a transmission electron microscope image.
[0021] Figure 5 These are the results of elemental analysis.
[0022] Figure 6 These are the results of nitrogen adsorption-desorption tests.
[0023] Figure 7 The results are from a four-probe conductivity test.
[0024] Figure 8 The performance of the carbon material PM-C obtained by the method of this application as an electrode material for supercapacitors is shown in (a) cyclic voltammetry curves at different scan rates; (b) charge-discharge curves at different current densities; (c) cyclic performance curves of the carbon material at a current density of 1.0 A / g; and (d) impedance test results before and after 2000 charge-discharge cycles.
[0025] Figure 9 The charge-discharge curves of PM-C carbon material obtained by the method of this application as a negative electrode material for lithium-ion batteries at a rate of 0.1C are shown.
[0026] Figure 10 The graphs show the cycle performance and rate performance curves of the carbon material PM-C obtained by the method of this application as a negative electrode material for lithium-ion batteries, where (a) is the cycle curve at different rates; and (b) is the rate characteristic curve.
[0027] Figure 11 This is a schematic diagram of the production line for collecting and processing carbon soot particles. Detailed Implementation
[0028] The following examples are intended to illustrate the present invention, and not to further limit the invention.
[0029] Example 1
[0030] This invention provides an application of carbon materials using soot as a carbon source in energy storage devices. Carbon materials are obtained by using soot as raw material and undergoing simple cleaning and one-step activation and carbonization treatment. The carbon materials are nanoparticles with an amorphous carbon structure and local graphite crystal domains. The nanoparticles have slit or crack-like gap pores with a pore size distribution range of 10-50 nm, and are used in energy storage devices.
[0031] The present invention provides an application of carbon materials with soot as a carbon source in energy storage devices, specifically, the application of carbon materials with soot as a carbon source in supercapacitor electrodes, lithium-ion battery negative electrodes, and conductive agents.
[0032] Example 2
[0033] This invention provides a method for preparing carbon materials using soot as a carbon source, comprising:
[0034] The simple cleaning process is as follows: disperse the carbon soot in anhydrous ethanol, centrifuge at high speed, and then vacuum dry.
[0035] The activation carbonization process is as follows: the cleaned and dried carbon fumes are mixed with potassium hydroxide particles, dispersed in water, treated in a water bath, dried, and the dried mixture is activated carbonized. The aqueous solution of the carbonization product is neutralized with hydrochloric acid, washed, and dried to obtain the final product.
[0036] The activation carbonization is carried out under a nitrogen atmosphere, with a heating rate of 2-5℃ / min and a calcination temperature of 700-900℃, for a calcination time of 2-8h.
[0037] The specific preparation method is as follows:
[0038] Slowly pour 5g of carbon soot particles (DES) into a beaker containing 100mL of anhydrous ethanol, and stir with a glass rod until a homogeneous mixture is formed. Centrifuge the ethanol and carbon soot mixture at high speed (6500-8000r / min, 8min). This cleaning step is mainly used to remove oily substances and other dust impurities from the carbon soot. Repeat the above cleaning process three times. (The amount of liquid and the specific number of times mentioned here "three times" depends on the centrifugation effect, but it can ensure complete removal of impurity ions.) Pour off the supernatant and place the deposited carbon soot in a vacuum oven to dry for 10-12 hours. Take the completely dried carbon soot and mix it with solid KOH at a mass ratio of 1:2. Then add 60mL of deionized water to the carbon soot and KOH mixture, and stir for 3 hours under an 80℃ water bath until a homogeneous mixed solution is formed. Place the beaker containing the mixed solution in a forced-air drying oven to dry until completely dry. The dried mixture was initially ground into a uniform fine powder using a mortar and pestle, then placed in a porcelain boat and activated carbonized for 2 hours in a tube furnace filled with N2 at a temperature of 700-900℃, with a heating rate of 2-5℃ / min, until the tube furnace cooled to room temperature. The carbonized sample was then collected for later use. The carbonized sample was poured into a beaker containing 50mL of deionized water and stirred thoroughly with a magnetic stirrer. Simultaneously, a 1mol / L HCl solution was prepared using 38% hydrochloric acid. The aqueous solution of the carbonized sample was adjusted to neutral using the prepared hydrochloric acid, and then the mixture was washed by high-speed centrifugation, repeated three times (the last two times using deionized water). The washed precipitate was then vacuum dried (100℃, 12h).
[0039] Preferably, because the initial carbon content of the soot is high, the amount of activator (such as KOH) used is reduced to 1 / 3 to 1 / 2 of the conventional amount, which can further reduce the cost of chemical reagents; the dried soot is mixed with potassium hydroxide particles at a mass ratio of 1:2.
[0040] The present invention proposes a method for preparing regenerated carbon materials from diesel engine emission particulate matter. For the first time, it proposes to use particulate matter from diesel engines as a source of conductive porous carbon materials. The raw material source is stable and has almost zero cost, which can support future large-scale utilization. Since diesel particulate matter itself is a carbonization product (carbon content >80%), it eliminates the need for separate activation or pre-carbonization steps required to prepare carbon materials from biomass or polymer precursors, which can simplify the production process and reduce energy consumption.
[0041] The method for treating particulate matter emitted by diesel engines in this application is a simple cleaning and one-step activation carbonization process. The carbon material obtained after the treatment has good conductivity and can be used as a supercapacitor electrode material, a lithium-ion battery anode material, a conductive agent or other conductive carbon material.
[0042] Compared with existing DPF regeneration methods, the process of this application does not require excessive consumption of fossil energy, has relatively lower costs, and does not cause secondary pollution to the environment. At the same time, it effectively treats particulate matter emissions in a green manner, realizes the regeneration and recycling of carbon particulate matter, and deeply integrates environmental governance with green energy technology. It provides innovative ideas and development directions for future joint research in multiple fields such as resource recycling, air emission control and high-performance energy storage, and greatly contributes to the realization of energy conservation, emission reduction and dual-carbon strategic goals.
[0043] It should be noted that the soot particles in this invention can be from a single source, including commercial vehicles, ships, generator sets, construction machinery, or agricultural machinery. Different pretreatment methods can be implemented depending on the source. Alternatively, the soot particles can be from multiple sources. Multi-source soot particle collection is our industrialized, large-scale solution, and its collection and processing methods are as follows: Figure 11 As shown, a processing line is established that includes raw material transportation, rapid carbon content detection, diversion, grading, mixing, cleaning, and activation processes. Raw carbon soot from commercial vehicles, ships, generator sets, construction machinery, and agricultural machinery is sent from the raw material warehouse to the rapid carbon content detection process. The carbon content is rapidly detected using LIBS detection technology. The soot is then diverted through a diversion valve. The diverted low-carbon soot undergoes at least desulfurization in a desulfurization tower, while the diverted high-carbon soot undergoes at least centrifugal separation and supercritical extraction. The qualified carbon soot particles are mixed in a mixer (this step can be done by adding a feeding channel and mixing in high-carbon biochar as an auxiliary regulator) and then undergo subsequent cleaning and activation carbonization. In the above processing line, the standards for low-carbon and high-carbon diversion are based on the actual indicators set in production, for example, fluctuating around 80%.
[0044] Example 3
[0045] Based on Examples 1 and 2, such as Figure 1Slowly pour 5g of carbon soot particles (DES) into a beaker containing 100mL of anhydrous ethanol, and stir with a glass rod until a homogeneous mixture (dispersion A) is formed. Centrifuge the ethanol and carbon soot mixture at high speed (8000r / min, 8min). This washing step is mainly used to remove oily substances and other dust impurities from the carbon soot. Repeat the above washing process three times. Pour off the supernatant and place the deposited carbon soot (remaining part B) in a vacuum oven to dry for 12h. Take the completely dried carbon soot (PM-1) and mix it with solid KOH at a mass ratio of 1:2. Then add 60mL of deionized water to the carbon soot and KOH mixture (PM-2) and stir for 3h in an 80℃ water bath until a homogeneous mixed solution is formed. Place the beaker containing the mixed solution in a forced-air drying oven to dry until completely dry. The dried mixture was initially ground into a uniform fine powder using a mortar and pestle, then placed in a porcelain boat and activated carbonized in a tube furnace filled with N2 at 700℃ for 2 hours, with a heating rate of 2℃ / min, until the tube furnace cooled to room temperature. The carbonized sample (PM-3) was then collected for later use. The carbonized sample was poured into a beaker containing 50 mL of deionized water and stirred thoroughly with a magnetic force. Simultaneously, a 1 mol / L HCl solution was prepared using 38% hydrochloric acid. The aqueous solution of the carbonized sample was adjusted to neutral using the prepared hydrochloric acid, and then the mixture was centrifuged at high speed to obtain product PM-4. This was washed twice more with deionized water to obtain product PM-5. The washed precipitate was vacuum dried (100℃, 12 hours), and the resulting PM-6 was ball-milled to obtain PM-C.
[0046] Experimental results
[0047] The carbon material obtained in Example 3 was subjected to the following experiments.
[0048] 1. Phase characterization
[0049] Figure 2 The image shows an X-ray diffraction (XRD) pattern, where DES-C represents the carbon material (PM-C) obtained using the method described in this application, specifically Example 3, and DES represents the raw soot collected from the diesel engine's DPF. It can be seen that after treatment using the method described in this application, the soot is effectively purified, and the resulting product is mainly amorphous carbon material with localized graphite domains.
[0050] 2. Morphological characteristics
[0051] Depend on Figure 3 Scanning electron microscope (SEM) images show that PM-C consists of nanoscale particles.
[0052] Depend on Figure 4Transmission electron microscopy (TEM) images show that PM-C has an amorphous carbon structure with localized graphite domains.
[0053] 3. Elemental Analysis
[0054] Elemental analysis was performed on the carbon material (PM-C) obtained using the method described in this application. Figure 5 As can be seen from the elemental analysis, the carbon content is 93.9%, with an additional 4.4% oxygen. The Cu content is due to the influence of the copper mesh used in the test, and the content of other impurities does not exceed 0.2%.
[0055] 4. Nitrogen adsorption-desorption test
[0056] Depend on Figure 6 The nitrogen adsorption-desorption test results show that the carbon material (PM-C) obtained by the method of this application has porosity characteristics, with a pore size distribution range of 10-50 nm, mainly consisting of mesopores and macropores, and a specific surface area of 181 m². 2 / g.
[0057] 5. Conductivity test
[0058] Figure 7 The four-probe conductivity test results for carbon materials show that the product obtained after treatment by the method of this application has obvious conductive properties, with a conductivity of about 1.4 S / cm, which belongs to activated carbon materials with good conductivity.
[0059] 6. Energy storage characteristics
[0060] Figure 8 The performance of PM-C carbon material obtained by the method of this application as an electrode material for supercapacitors is shown. Among them, (a) is the cyclic voltammetry curve at different scan rates, showing the obvious double-layer capacitance characteristics of carbon material; (b) is the charge-discharge curve at different current densities, showing good capacitance characteristics; (c) is the cycling performance curve of carbon material at a current density of 1.0 A / g, showing good cycling stability; (d) is the impedance test curve before and after 2000 charge-discharge cycles, showing good impedance characteristics.
[0061] This application also tested the electrochemical performance of PM-C carbon material obtained by the method of this application as a negative electrode for lithium batteries. Figure 9 The charge-discharge curves at a 0.1C rate clearly show the typical lithium intercalation potential of the carbon material. Furthermore, the initial discharge specific capacity is as high as 720 mAh / g, and the second discharge specific capacity still reaches approximately 380 mAh / g. Figure 10 The figures show the cycle performance and rate performance curves, where (a) is the cycle curve at different rates, showing good cycle stability; and (b) is the rate performance curve, showing excellent rate performance.
Claims
1. An application of carbon materials using soot as a carbon source in energy storage devices, characterized in that, Carbon materials are obtained by using carbon soot as raw material and through simple cleaning and one-step activation carbonization treatment. The carbon materials are nanoparticles with an amorphous carbon structure and local graphite crystal domains. The nanoparticles have slit or crack-like gap pores with a pore size distribution range of 10-50 nm and are used in energy storage devices.
2. A method for preparing carbon materials using soot as a carbon source, characterized in that, include: The simple cleaning process is as follows: disperse the carbon soot in anhydrous ethanol, centrifuge at high speed, and then vacuum dry. The activation carbonization process is as follows: the cleaned and dried carbon fumes are mixed with potassium hydroxide particles, dispersed in water, treated in a water bath, dried, and the dried mixture is activated carbonized. The aqueous solution of the carbonization product is neutralized with hydrochloric acid, washed, and dried to obtain the final product.
3. The method for preparing carbon materials using soot as a carbon source according to claim 2, characterized in that, The dried carbon soot is mixed with potassium hydroxide particles at a mass ratio of 1:
2.
4. The method for preparing carbon materials using soot as a carbon source according to claim 2, characterized in that, The carbonization process involves carbonizing for 2 hours in a tubular furnace filled with N2 at a temperature of 700-900°C.
5. The application of carbon materials using soot as a carbon source in energy storage devices according to claim 1, characterized in that, Applications of the carbon material in supercapacitor electrodes, lithium-ion battery anodes, and conductive agents.