AU2021105930A4 - A Preparation Method for Self-supporting Heteroatom Doping Sludge Carbon Electrode Material - Google Patents
A Preparation Method for Self-supporting Heteroatom Doping Sludge Carbon Electrode Material Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 178
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000007772 electrode material Substances 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims description 45
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 42
- 229920001568 phenolic resin Polymers 0.000 claims description 42
- 239000005011 phenolic resin Substances 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 30
- 238000003763 carbonization Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000009656 pre-carbonization Methods 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 37
- 239000001257 hydrogen Substances 0.000 abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 36
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002019 doping agent Substances 0.000 abstract description 5
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- 239000000126 substance Substances 0.000 abstract description 4
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- 238000011068 loading method Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 8
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- 239000000463 material Substances 0.000 description 5
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- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 229920005596 polymer binder Polymers 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
of Descriptions
The invention provides a preparation method for self-supporting heteroatom doping sludge
carbon electrode material. Compared with the existing technology, the self-supporting heteroatom
doping sludge carbon electrode material prepared by the invention can simultaneously meet the
requirements of hydrogen production catalyst and working electrode, and "Combine the Two into
One", which not only effectively avoids the problems of traditional powder catalysts, but also
effectively increases the active sites of hydrogen evolution reaction due to the unique porous
self-supporting structure, and solves the problem of high consumption and low efficiency of the
current electrochemical hydrogen evolution technology. In addition, the preparation method
provided by the invention is simple and quick, does not need the loading steps, and does not need
to add a variety of chemical additives such as dopants, modifiers and pore-forming agents, which
reduces the preparation cost, reflects the role of waste reuse and high added-value, and also
provides a new electrode material for hydrogen evolution technology of electrolytic water.
Description
Descriptions A Preparation Method for Self-supporting Heteroatom Doping Sludge Carbon Electrode Material
Technical Field
[0001] The invention relates to the technical field of electrocatalysis, in particular to a preparation method for self-supporting heteroatom doping sludge carbon electrode material.
Background Technology
[0002] Hydrogen energy is recognized as a clean, high combustion heat value and environmentally friendly energy. Hydrogen energy can also be used as a medium for storage, transportation and conversion of other clean energy resources (solar energy, wind energy and biological energy, etc.). Electrolytic water is an important hydrogen preparation method. Most of the catalysts for the hydrogen evolution reaction (HER) of electrolytic water are precious metal-based (such as Pt) materials with scarce reserves and high cost. In contrast, the development of low-cost and high-activity non-precious metal catalysts is an important challenge in the field of hydrogen production.
[0003] Carbon materials have gradually entered people's visual field due to their low cost, abundant resources and good stability. Traditional hydrogen evolution catalytic materials need to be doped by complex chemical methods to improve the hydrogen evolution performance of catalysts. However, in the synthesis process of doping carbon catalytic materials, chemical agents need to be added as dopants, sometimes doping carbon precursors, pore-forming agents and templates also need to be added to improve the content of doping atoms in carbon materials, the catalytic activity of catalytic materials and the active sites of reactions. Due to the complex reactions involved, the cost of preparing catalytic materials is increased and by-products are easy to be produced.
[0004] Currently, the form of hydrogen evolution catalysts for electrolytic water is mostly powder. When preparing the working electrode, it is necessary to add polymer binders and conductive additives to load the catalysts on the electrode, but there are the following problems:
[0005] (1) The morphology and structure of the catalysts cannot be effectively controlled, which leads to a large amount of dead volume on the catalysts, and a reduction of electrochemical active sites, forms an obstacle interface detrimental to the reactions on the surface of the electrode, and limits the electron conduction between the electrode and the electrolyte in the electrochemical process and the mass transfer of reactants/products in the heterogeneous reaction process.
[0006] (2) Due to the continuous escape of the gas precipitated on the electrode surface during the electrocatalytic hydrogen evolution reactions, the catalysts coated on the electrode are easy to separate, which damages the activity and service life of the catalysts.
[0007] In view of this, it is necessary to provide a technical solution to solve the above problems.
Summary of the Invention
[0008] The purpose of the invention is to provide a preparation method for self-supporting heteroatom doping sludge carbon electrode material to solve the problem of high consumption and low efficiency of traditional electrochemical hydrogen evolution technology; the electrode material has low production cost, and does not need to add chemical agents as dopants, modifiers and pore-forming agents in the preparation process, which fully reflects the role of waste reuse to produce high added-value.
[0009] In order to achieve the above purpose, the invention adopts the following technical solutions:
[0010] A preparation method for self-supporting heteroatom doping sludge carbon electrode material, which comprises the following steps:
[0011] 1) Place the dry sludge powder in an atmosphere furnace, intake inert gas, heat and pre-carbonize to obtain the first sludge carbon powder, wash and dry the first sludge carbon powder to obtain the second sludge carbon powder;
[0012] 2) Place the phenolic resin in a container, add deionized water for the first ultrasonic dispersion, and then add the second sludge carbon powder for the second ultrasonic dispersion to obtain a uniform mixture; transfer the mixture to an evaporator, and heat and dry in a vacuum state to obtain a slurry mixture of sludge self-doping phenolic resin;
[0013] 3) Press and form the slurry mixture of sludge self-doping phenolic resin, and cure it to obtain the flake mixture of sludge self-doping phenolic resin; then, place the flake mixture of sludge self-doping phenolic resin in an atmosphere furnace, intake inert gas, and keep it heating up and carbonizing under anaerobic conditions, until the flake mixture of sludge self-doping phenolic resin has porous self-supporting structure; after carbonization, wash it to neutral and dry to obtain a self-supporting heteroatom doping sludge carbon electrode material.
[0014] The self-supporting heteroatom doping sludge carbon electrode material prepared by the invention has an independent supporting structure, can be directly applied to the working electrode of electrochemical reactions, does not need to coat the catalyst on the electrode, nor does it need the coating of organic binders and conductive additives, and makes full use of the characteristics of heteroatom doping contained in sludge to enhance the performance of electrocatalytic hydrogen evolution. The preparation method ensures the integrity and mechanical strength of the self-supporting electrode catalyst, and is conducive to the electron transfer and gas conduction between the electrode and the electrolyte; and the preparation process is simple, the raw materials are easy to obtain, and the electrode itself has good activity and stability, so it has a wide application value. In addition, compared with powder catalysts, the self-supporting sludge carbon electrode material has rich pore structure. On the one hand, it is conducive to the infiltration of electrolyte, the diffusion of ions and reaction products, and the improvement of electrocatalytic reaction kinetics in the electrochemical process; on the other hand, it increases its active surface area and electrochemical active sites.
[0015] Of which, the phenolic resin used in the invention is the earliest synthetic resin, which has the advantages of mature production process, low price, high carbonization yield, single component, low impurity content, easy activation and pore formation, and has broad application prospects as electrode materials. Sludge has the characteristics of heteroatom self-doping, and these heteroatoms can not only improve the catalytic performance of carbon materials, but also enhance the stability of carbon materials. It ultrasonicly disperses and mixes the sludge and phenolic resin, and carbonizes them at high temperature under anaerobic conditions to obtain a new electrode material with self-supporting structure, which gives full play to the characteristics of sludge heteroatom self-doping. On the one hand, it realizes the resource disposal of sludge, and on the other hand, combined with the application in the field of electrocatalytic hydrogen production, it provides a new practical application mode for sludge resource utilization technology, and has good innovation and research value.
[0016] Preferably, the preparation process of the dry sludge powder is as follows: First dry the sludge to obtain the block dry sludge, the block dry sludge is crushed and mesh sieved to obtain the fine sludge powder, clean the fine sludge powder by magnetic mixing, and dry to obtain the dry sludge powder. The weighed sludge preferably uses the pre-treated sludge to avoid excessive impurities in the sludge. It can select the sludge in the digestion tank, the sludge in the digestion tank undergoes anaerobic biological treatment, most of the impurities have been removed, and the organic matter in the sludge is also degraded by bacteria into methane-based organic matter under anaerobic conditions. In this way, in the subsequent pre-carbonization and carbonization process, the organic matter will be decomposed more quickly and easily, which is conducive to the uniform and continuous formation of holes.
[0017] Preferably, the drying temperature of the sludge is 80-105°C; the sieve pore of the mesh sieve is 60-80 mesh; the magnetic mixing time of the fine sludge powder is 0.5-1h, and the drying temperature of the fine sludge powder is 60-80°C.
[0018] Preferably, in Step 1), place the dry sludge powder in an atmosphere furnace, intake inert gas, heat and pre-carbonize to obtain the first sludge carbon powder; wash the first sludge carbon powder with deionized water and absolute ethyl alcohol under the condition of magnetic mixing, and dry to obtain the second sludge carbon powder. The contact area of sludge carbon powder with small particles is large, and the mixing reaction with phenolic resin will be more uniform. Due to the small particles as a whole, the mixture formed by the two will be more uniform and consistent in the subsequent pressing and forming and the construction of self-supporting structure and other process; in addition, due to the small force between small particles, the gas generated by the decomposition of organic matter is easier to be discharged.
[0019] Preferably, in Step 1), the pre-carbonization temperature is 400~- 500°C, the pre-carbonization time is 1-2h, and the intake flow of the inert gas is 200-300mL/min; the magnetic mixing time of the first sludge carbon powder is 1-2h; the drying temperature of the first sludge carbon powder is 60-80°C. Keep it at the temperature of 400~500°C for pre-carbonization, first decompose a part of matter in the sludge and discharge the produced gas to form some holes in advance, so as to provide a basis for subsequent mixing with phenolic resin and carbonization at high temperature. It can not only mix more uniformly, but also form a certain supporting structure, which is more conducive to the formation of subsequent self-supporting structure, so as to obtain a self-supporting heteroatom doping sludge carbon electrode material.
[0020] Preferably, in Step 2), the weight ratio of the phenolic resin to the second sludge carbon powder is 1:2-1:4. The deionized water can be mixed with phenolic resin according to the ratio of (80 ~ 100): (1 ~ 2). Mixing according to the above ratio can ensure the uniform and consistent mixing of the phenolic resin and the second sludge carbon powder. The higher the ratio of the second sludge carbon powder, the higher the heteroatoms of the sludge, the more holes formed inside and on the surface of the obtained sludge carbon electrode material, the more active sites for the corresponding electrocatalytic hydrogen evolution reaction, and the higher the stability of the electrode material. However, if the ratio of the second sludge carbon powder is too high and the ratio of phenolic resin is insufficient, it will cause low carbonization rate, which will affect the formation of holes of the second sludge carbon powder and the effect of hydrogen evolution of the electrode material. In this way, it is better to keep the weight ratio of phenolic resin to the second sludge carbon powder at 1:2 ~ 1:4. Specifically, the weight of phenolic resin can be 5 ~ g, the amount of deionized water can be 400 ~ 500ml, and the weight of the second sludge carbon powder can be 15 ~ 20g.
[0021] Preferably, in Step 2), the time of the first ultrasonic dispersion and the second ultrasonic dispersion is 1-2h; the drying temperature of the mixture is 60-80°C, and the drying time of the mixture is 6-8h. The specific ultrasonic time can be changed with the addition of phenolic resin and the carbonization content of the second sludge, so as to ensure that the two can finally reach the state of uniform mixing.
[0022] Preferably, in Step 3), the pressed and formed pressing force for the slurry mixture of sludge self-doping phenolic resin is 20-30Mpa; the curing is constant temperature curing at a temperature of 180-220°C; the curing time is 5-6h. Keep it curing at a constant temperature can ensure that all sides of the mixture are uniformly cured. The interior and surface of the mixture should not affect its properties due to temperature differences. Curing at 180-220°C can also play a preheating effect, and lay a solid foundation for subsequent high-temperature carbonization. Preferably, the constant temperature curing temperature is 200°C.
[0023] Preferably, in Step 3), the intake flow of the inert gas is 200-400mL/min; the heating rate of the carbonization is 5-10C/min, and the carbonization temperature is 800-1000°C; the carbonization time is 2-2.5h. The uniform heating rate helps to fully stimulate the early reaction of organic components in the sludge, and provides a basis for the rapid decomposition of organic components under the condition of high-temperature anaerobic carbonization. The decomposed gas can be discharged continuously, so that abundant holes are formed inside and on the surface of the sludge carbon electrode, and the porous self-supporting structure can also be formed uniformly under the condition.
[0024] Preferably, in Step 3), after carbonization, first acid wash, and then water wash to neutral, and dry to obtain a self-supporting heteroatom doping sludge carbon electrode material; of which, the acid concentration of the acid washing is 0.1-0.2M, and the drying temperature is -80°C. The acid used for acid washing can be at least one of HN03, HCl and H2SO4.
[0025] The beneficial effects of the invention are as follows:
[0026] 1) Compared with the prior art, the self-supporting heteroatom doping sludge carbon electrode material prepared by the invention can simultaneously meet the requirements of hydrogen production catalyst and working electrode, and "Combine the Two into One", which not only effectively avoids the problems of traditional powder catalysts, but also effectively increases the active sites of hydrogen evolution reaction due to the unique porous self-supporting structure, and solves the problem of high consumption and low efficiency of the current electrochemical hydrogen evolution technology. In addition, the preparation method provided by the invention is simple and quick, does not need the loading steps, and does not need to add a variety of chemical additives such as dopants, modifiers and pore-forming agents, which reduces the preparation cost, reflects the role of waste reuse and high added-value, and also provides a new electrode material for hydrogen evolution technology of electrolytic water.
[0027] 2) The preparation method of the invention first ultrasonicly disperses and mixes the sludge and phenolic resin, presses and forms them, and then carbonizes them under high temperature anaerobic conditions to finally convert them into an electrode material. The self-supporting heteroatom doping sludge carbon electrode material obtained by the preparation method, on the one hand, realizes the resource disposal of sludge, and on the other hand, combined with the application in the field of electrocatalytic hydrogen production, provides a new practical application mode for sludge resource utilization technology.
[0028] 3) Under high-temperature anaerobic carbonization conditions, rapidly decompose the organic components of sludge and discharge the produced gas. Due to the continuous discharge of gas, abundant holes are formed inside and on the surface of the sludge carbon electrode material, which increases its active surface area, and then increases the active sites of sludge carbon electrode material for electrocatalytic hydrogen evolution reaction. It is conducive to the progress of hydrogen production reaction and the precipitation of hydrogen, prevents the blockage and deactivation of sludge carbon electrode material, and improves the stability of sludge carbon electrode material.
[0029] 4) The sludge itself contains heteroatom catalytic components such as Fe, S and P, which has the advantage of heteroatom self-doping. The doping heteroatom is conducive to the process of catalytic hydrogen evolution reaction, and further improves the electrocatalytic hydrogen evolution effect of sludge carbon electrode material. If it is regarded as a catalyst, it is equivalent to prolonging the activity and service life of the catalyst.
Brief Description of Drawings
[0030] Figure 1 is a flow chart of the preparation method of the invention.
[0031] Figure 2 is the first SEM diagram of the electrode material of Embodiment 3.
[0032] Figure 3 is the second SEM diagram of the electrode material of Embodiment 3.
[0033] Figure 4 is an element analysis diagram of the electrode material of Embodiment 3.
[0034] Figure 5 is the linear current-voltage curves of hydrogen evolution of electrode materials in Embodiments 1, 2 and 3 made at different temperatures.
[0035] Figure 6 is a current-time curve of the electrode material of Embodiment 3 at 1000 °C.
Detailed Description of the Presently Preferred Embodiments
[0036] In order to make the technical solutions and advantages of the invention more clear, the invention and its beneficial effects will be further described in detail below in combination with the specific embodiments and the drawings of descriptions, but the embodiments of the invention are not limited to this.
[0037] Embodiment 1
[0038] As shown in Figure 1, a preparation method for self-supporting heteroatom doping sludge carbon electrode material, which comprises the following steps:
[0039] 1) Dry the sludge in the digestion tank naturally under outdoor conditions, and then put it in a drying oven to dry the sludge to obtain a block dry sludge, and the drying temperature is 105°C; take the block dry sludge out and put it in a pulverizer to pulverize and polish, then pass through a 60-mesh mesh sieve to obtain a fine sludge powder; then place thefine sludge powder in a container, add deionized water for magnetic mixing and cleaning for lh, after filtering with a 0.45tm of filter membrane, and then place it in a drying oven to dry at 60°C for 6h to obtain a dry sludge powder.
[0040] 2) Place the dry sludge powder in a tubular atmosphere furnace with an intake flow of 250mL/min of inert gas N2, pre-carbonize at 450°C for lh to obtain the first sludge carbon powder, mix it for lh and wash the first sludge carbon powder with deionized water and absolute ethyl alcohol under the condition of magnetic mixing, and dry to obtain the second sludge carbon powder, and the drying temperature is 60°C.
[0041] 3) Take 1Og of phenolic resin in a container, add 500mL of deionized water for the first ultrasonic dispersion, and the dispersion time is 2h; then add 20g of the second sludge carbon powder for the second ultrasonic dispersion, and the dispersion time is 2h; to obtain a uniform mixture; transfer the mixture to a rotary evaporator, and heat up to 70°C and dry for 6h in a vacuum state to obtain a slurry mixture of sludge self-doping phenolic resin;
[0042] 4) Use a 20 - 20 - 3mm cylindrical mold to shape the slurry mixture of sludge self-doping phenolic resin for 30min, and then press it with a tablet press at 30Mpa to form a plate with a diameter of 20 - 20mm and a thickness of 3mm, and cure it in a vacuum constant temperature drying oven at a temperature of 200°C for 6h to obtain a flake mixture of sludge self-doping phenolic resin; then, place the flake mixture of sludge self-doping phenolic resin in a tubular atmosphere furnace, heat and carbonize it under the protection of 3OOmL/min of nitrogen atmosphere, heat to 800°C at the heating rate of 5°C/min, after carbonizing at high temperature for 2h, cool it to room temperature and then take it out to complete the carbonization; then, acid wash it with 0.1M of HN03 for 6h, and then water wash it to neutral, and dry it in a drying oven at 60°C to obtain a self-supporting heteroatom doping sludge carbon electrode material.
[0043] Embodiment 2
[0044] As shown in Figure 1, a preparation method for self-supporting heteroatom doping sludge carbon electrode material, which comprises the following steps:
[0045] 1) Dry the sludge in the digestion tank naturally under outdoor conditions, and then put it in a drying oven to dry the sludge to obtain a block dry sludge, and the drying temperature is °C; take the block dry sludge out and put it in a pulverizer to pulverize and polish, then pass through a 60-mesh mesh sieve to obtain a fine sludge powder; then place thefine sludge powder in a container, add deionized water for magnetic mixing and cleaning for lh, after filtering with a 0.45tm of filter membrane, and then place it in a drying oven to dry at 80°C for 5.5h to obtain a dry sludge powder.
[0046] 2) Place the dry sludge powder in a tubular atmosphere furnace with an intake flow of 300mL/min of inert gas N2, pre-carbonize at 500°C for lh to obtain the first sludge carbon powder, mix it for 1.5h and wash the first sludge carbon powder with deionized water and absolute ethyl alcohol under the condition of magnetic mixing, and dry to obtain the second sludge carbon powder, and the drying temperature is 70°C.
[0047] 3) Take 7.5g of phenolic resin in a container, add 450mL of deionized water for the first ultrasonic dispersion, and the dispersion time is 1.5h; then add 17.5g of the second sludge carbon powder for the second ultrasonic dispersion, and the dispersion time is 1.5h; to obtain a uniform mixture; transfer the mixture to a rotary evaporator, and heat up to 70°C and dry for 6h in a vacuum state to obtain a slurry mixture of sludge self-doping phenolic resin;
[0048] 4) Use a 20 - 20 - 3mm cylindrical mold to shape the slurry mixture of sludge self-doping phenolic resin for 30min, and then press it with a tablet press at 30Mpa to form a plate with a diameter of 20 - 20mm and a thickness of 3mm, and cure it in a vacuum constant temperature drying oven at a temperature of 200°C for 5h to obtain a flake mixture of sludge self-doping phenolic resin; then, place the flake mixture of sludge self-doping phenolic resin in a tubular atmosphere furnace, heat and carbonize it under the protection of 300mL/min of nitrogen atmosphere, heat to 900°C at the heating rate of 7.5°C/min, after carbonizing at high temperature for 2h, cool it to room temperature and then take it out to complete the carbonization; then, acid wash it with 0.1M of HNO3 for 6h, and then water wash it to neutral, and dry it in a drying oven at 60°C to obtain a self-supporting heteroatom doping sludge carbon electrode material.
[0049] Embodiment 3
[0050] As shown in Figure 1, a preparation method for self-supporting heteroatom doping sludge carbon electrode material, which comprises the following steps:
[0051] 1) Dry the sludge in the digestion tank naturally under outdoor conditions, and then put it in a drying oven to dry the sludge to obtain a block dry sludge, and the drying temperature is 105°C; take the block dry sludge out and put it in a pulverizer to pulverize and polish, then pass through a 60-mesh mesh sieve to obtain a fine sludge powder; then place thefine sludge powder in a container, add deionized water for magnetic mixing and cleaning for lh, after filtering with a 0.45tm of filter membrane, and then place it in a drying oven to dry at 60°C for 6h to obtain a dry sludge powder.
[0052] 2) Place the dry sludge powder in a tubular atmosphere furnace with an intake flow of 200mL/min of inert gas N2, pre-carbonize at 400°C for 2h to obtain the first sludge carbon powder. Mix it for 2h and wash thefirst sludge carbon powder with deionized water and absolute ethyl alcohol under the condition of magnetic mixing, and dry to obtain the second sludge carbon powder, and the drying temperature is 80°C.
[0053] 3) Take 5g of phenolic resin in a container, add 400mL of deionized water for the first ultrasonic dispersion, and the dispersion time is lh; then add 15g of the second sludge carbon powder for the second ultrasonic dispersion, and the dispersion time is 1.5h; to obtain a uniform mixture; transfer the mixture to a rotary evaporator, and heat up to 60°C and dry for 6h in a vacuum state to obtain a slurry mixture of sludge self-doping phenolic resin;
[0054] 4) Use a 20 - 20 - 3mm cylindrical mold to shape the slurry mixture of sludge self-doping phenolic resin for 30min, and then press it with a tablet press at 30Mpa to form a plate with a diameter of 20 - 20mm and a thickness of 3mm, and cure it in a vacuum constant temperature drying oven at a temperature of 180°C for 6h to obtain a flake mixture of sludge self-doping phenolic resin; then, place the flake mixture of sludge self-doping phenolic resin in a tubular atmosphere furnace, heat and carbonize it under the protection of 200mL/min nitrogen atmosphere, heat to 1000°C at the heating rate of 10°C/min, after carbonizing at high temperature for 2h, cool it to room temperature and then take it out to complete the carbonization; then, acid wash it with 0.1M of HNO3 for 6h, and then water wash it to neutral, and dry it in a drying oven at 60°C to obtain a self-supporting heteroatom doping sludge carbon electrode material.
[0055] Characterize the self-supporting heteroatom doping sludge carbon electrode material obtained in Embodiment 3 and directly apply it to the electrochemical experiment of hydrogen evolution as a working electrode, and the characterization and experimental results are shown in Figures 2 ~ 6.
[0056] It can be seen from Figures 2-4 that the electrode material is a porous structure and contains heteroatoms such as S, P and Fe, which has the characteristics of heteroatom self-doping, and the carbon material doped with these heteroatoms is conducive to the hydrogen evolution reaction.
[0057] In the electrochemical experiment of hydrogen evolution, the three-electrode electrochemical reaction is conducted for the experiment, of which, the working electrode is the self-supporting heteroatom doping sludge carbon electrode of the invention, the counter electrode is a graphite rod, the reference electrode is a saturated calomel electrode, and the electrolyte is 0.5M of H2SO4. It can be seen from Figure 5 that the overpotential of sludge carbon electrode materials at different temperatures when the hydrogen evolution reaction reaches 10mA is -173mV, -314mV, -385mV, and the hydrogen evolution current efficiency of sludge carbon electrode materials is better than that of conventional carbon-based electrode materials such as graphite plate and graphite felt. It can be seen from Figure 6 that after a long-term analysis of current stability, it can be concluded that the prepared self-supporting heteroatom doping sludge carbon electrode material has excellent stability. It indicates that the self-supporting heteroatom doping sludge carbon electrode material can be used as an independent working electrode for hydrogen evolution experiment, and it is a new electrocatalytic carbon electrode material.
[0058] To sum up the data results, it can be seen that the self-supporting heteroatom doping sludge carbon electrode material of the invention can simultaneously meet the requirements of hydrogen production catalyst and working electrode, and "Combine the Two into One", which not only omits the load settings of catalysts, but also omits the addition of various chemical additives such as dopants, modifiers and pore-forming agents, and not only reduces the production cost, but also improves the efficiency of electrochemical hydrogen evolution technology.
[0059] According to the disclosure and teaching of the above descriptions, those technical personnel in the field of the invention can also change and modify the above embodiments. Therefore, the invention is not limited to the above specific embodiments. Any obvious improvements, replacements or modifications made by those technical personnel in the field on the basis of the invention shall fall within to the protection scope of the invention. In addition, although some specific terms are used in the descriptions, these terms are only for the convenience of descriptions and do not constitute any limitation to the invention.
Claims (10)
1. A preparation method for self-supporting heteroatom doping sludge carbon electrode material, which is characterized in that, it comprises the following steps: 1) Place the dry sludge powder in an atmosphere furnace, intake inert gas, heat and pre-carbonize to obtain the first sludge carbon powder, wash and dry the first sludge carbon powder to obtain the second sludge carbon powder; 2) Place the phenolic resin in a container, add deionized water for the first ultrasonic dispersion, and then add the second sludge carbon powder for the second ultrasonic dispersion to obtain a uniform mixture; transfer the mixture to an evaporator, and heat and dry in a vacuum state to obtain a slurry mixture of sludge self-doping phenolic resin; 3) Press and form the slurry mixture of sludge self-doping phenolic resin, and cure it to obtain the flake mixture of sludge self-doping phenolic resin; then, place the flake mixture of sludge self-doping phenolic resin in an atmosphere furnace, intake inert gas, and keep it heating up and carbonizing under anaerobic conditions, until the flake mixture of sludge self-doping phenolic resin has porous self-supporting structure; after carbonization, wash it to neutral and dry to obtain a self-supporting heteroatom doping sludge carbon electrode material.
2. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in claim 1, which is characterized in that, the preparation process of the dry sludge powder is as follows: first dry the sludge to obtain the block dry sludge, the block dry sludge is crushed and mesh sieved to obtain the fine sludge powder, clean the fine sludge powder by magnetic mixing, and dry to obtain the dry sludge powder.
3. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in claim 2, which is characterized in that, the drying temperature of the sludge is 80 105°C; the sieve pore of the mesh sieve is 60-80 mesh; the magnetic mixing time of the fine sludge powder is 0.5~-h, and the drying temperature of the fine sludge powder is 60-80°C.
4. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in claim 1, which is characterized in that, in Step 1), place the dry sludge powder in an atmosphere furnace, intake inert gas, heat and pre-carbonize to obtain the first sludge carbon powder; wash the first sludge carbon powder with deionized water and absolute ethyl alcohol under the condition of magnetic mixing, and dry to obtain the second sludge carbon powder.
5. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in claim 4, which is characterized in that, in Step 1), the pre-carbonization temperature is 400-500°C, the pre-carbonization time is 1-2h, and the intake flow of the inert gas is 200 300mL/min; the magnetic mixing time of the first sludge carbon powder is 1 2h; the drying temperature of the first sludge carbon powder is 60-80°C.
6. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in claim 1, which is characterized in that, in Step 2), the weight ratio of the phenolic resin to the second sludge carbon powder is 1:2-1:4.
7. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in Claim 1, which is characterized in that, in Step 2), the time of the first ultrasonic dispersion and the second ultrasonic dispersion is 1~2h; the drying temperature of the mixture is 60 80°C, and the drying time of the mixture is 6-8h.
8. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in claim 1, which is characterized in that, in Step 3), the pressed and formed pressing force for the slurry mixture of sludge self-doping phenolic resin is 20-3OMpa; the curing is constant temperature curing at a temperature of 180-22 0 °C; the curing time is 5-6h.
9. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in claim 1, which is characterized in that, in Step 3), the intake flow of the inert gas is 200-4OOmL/min; the heating rate of the carbonization is 5-1OC/min, and the carbonization temperature is 800-1000°C; the carbonization time is 2-2.5h.
10. The preparation method for self-supporting heteroatom doping sludge carbon electrode material as described in Claim 1, which is characterized in that, in Step 3), after carbonization, first acid wash, and then water wash to neutral, and dry to obtain a self-supporting heteroatom doping sludge carbon electrode material; of which, the acid concentration of the acid washing is 0.1-0.2M, and the drying temperature is 60 0C.
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