CN210325550U - Preparation system of straw microwave hydrothermal-based supercapacitor active carbon electrode material - Google Patents
Preparation system of straw microwave hydrothermal-based supercapacitor active carbon electrode material Download PDFInfo
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Abstract
The utility model discloses a straw microwave hydrothermal base supercapacitor active carbon electrode material preparation system, its microwave low temperature acid hydrothermal device include straw feed bin, rubbing crusher, phosphoric acid liquid storage pot, microwave hydrothermal reation kettle, filter, liquid product jar, hydrothermal carbon storage tank, high temperature basicity activation device includes potassium hydroxide storage tank, first mixer, nitrogen cylinder, tubular pyrolysis oven, gaseous purifier, gas holder, hydrochloric acid pond, clean water basin, active carbon storage tank, electrode material preparation facilities includes acetylene black storage tank, NMP storage tank, PVDF storage tank, second mixer, foam nickel storage tank, coating machine, vacuum drying machine, tablet press; the system improves the production process of the biomass-based supercapacitor, not only can realize the clean energy utilization of the whole components of the straws, but also can realize the development and utilization of the high-performance supercapacitor.
Description
Technical Field
The utility model relates to a supercapacitor electrode material prepares technical field, specifically indicates a straw microwave hydrothermal base supercapacitor active carbon electrode material preparation system.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a battery, has the advantages of high power density of the traditional capacitor and high energy density of a secondary battery, and has the advantages of high charging speed, long cycle life and no pollution to the environment. In view of a plurality of performance advantages, the super capacitor can be widely applied to a plurality of fields such as automobile industry, aerospace, national defense science and technology, information technology, electronic industry and the like, and belongs to a standard full-series low-carbon economic core product. Energy density and power density are main indexes for measuring the performance of the super capacitor, and the properties of the electrode material are key factors for determining the electrochemical performance of the capacitor, such as energy density, power density and the like. The activated carbon is an artificial carbon material product with a highly developed pore structure and a very large specific surface area, and has the advantages of large specific surface area, high chemical stability, good conductivity, simple preparation, low price and the like, so the activated carbon is always the preferred material for manufacturing the electrode of the supercapacitor.
At present, most of precursors for preparing the porous activated carbon are carbon-containing petrochemical products and some high polymer materials, and with the shortage of fossil resources, biomass with low price and wide sources becomes an important raw material for preparing the porous carbon material. The straw resources in China are rich, the amount of the straw collectable resources is 8.42 hundred million tons every year, and the straw has the characteristics of environmental protection, low price and the like, the content of cellulose, hemicellulose and lignin in the straw is rich, and the content of C element is about 40-50%, so that the straw is an important raw material for preparing carbon-based materials. The agricultural waste straw is used as a precursor for preparing the porous activated carbon, so that the production cost can be reduced, and the environmental problem caused by biological waste can be relieved.
The prior preparation methods of the porous activated carbon mainly comprise a chemical activation method and a hydrothermal carbonization method. The chemical activation method comprises mixing the required materials with activating agent, activating at 600-3、H3PO4The active carbon prepared by the method has large specific surface area and high porosity, but the surface of the active carbon has less oxygen-containing functional groups which can be extractedThe wettability between the surface of the high-activity carbon and electrolyte ions enables the ion migration to be smoother, and the high-activity carbon and the electrolyte ions can generate reversible Faraday redox reaction, so that the electric capacity is improved. The hydrothermal carbonization method is a carbonization process performed in a closed pressure vessel at a certain temperature (high temperature: 300 ℃; low temperature: about 200 ℃) by using water as a solvent, and the surface of the carbon material prepared by the method has rich oxygen-containing functional groups, which is beneficial to generation of pseudo capacitance and improvement of the performance of an electrode material, but the specific surface area of the carbon material is limited, and the internal pore structure is not developed.
The two preparation methods are combined and optimized, agricultural waste straws are used as raw materials, hydrothermal carbonization is firstly carried out, a microwave field is introduced in the hydrothermal process, the straws are subjected to low-temperature microwave hydrothermal reaction at a relatively high hydrolysis rate at a relatively low hydrothermal temperature, a phosphoric acid catalyst is added to ensure that the straws are fully converted, straw hydrothermal carbon rich in oxygen-containing functional groups can be obtained, the straw hydrothermal carbon is subjected to chemical activation at a high temperature, KOH is used as an activating agent, straw microwave hydrothermal activated carbon which is large in specific surface area, developed in pores, high in chemical stability and rich in oxygen-containing functional groups can be prepared, and the prepared activated carbon electrode material is large in specific capacitance, high in energy density and good in conductivity.
Disclosure of Invention
The utility model aims at providing a straw microwave hydrothermal base ultracapacitor system active carbon electrode material preparation system, this system uses the straw as the raw materials, through microwave hydrothermal and high temperature activation two-step method, preparation straw hydrothermal base ultracapacitor system active carbon electrode material to accomplish ultracapacitor system's equipment, this system has improved living beings base ultracapacitor system's production technology, not only can realize the clean energy utilization of the full component of straw, can realize high performance ultracapacitor system's development and utilization simultaneously.
In order to realize the purpose, the utility model relates to a straw microwave hydrothermal base ultracapacitor system active carbon electrode material preparation system which characterized in that: the device comprises a microwave low-temperature acid hydrothermal device, a high-temperature alkaline activation device and an electrode material preparation device, wherein the microwave low-temperature acid hydrothermal device comprises a straw bin, a pulverizer, a phosphoric acid liquid storage tank, a microwave hydrothermal reaction kettle, a filter, a liquid product tank and a hydrothermal carbon storage tank, the high-temperature alkaline activation device comprises a potassium hydroxide storage tank, a first stirrer, a nitrogen bottle, a tubular pyrolysis furnace, a gas purification device, a gas storage tank, a hydrochloric acid tank, a clear water tank and an active carbon storage tank, and the electrode material preparation device comprises an acetylene black storage tank, an NMP (N-methyl pyrrolidone) storage tank, a PVDF (polyvinylidene fluoride) storage tank, a second stirrer, a foamed nickel storage tank, a coating machine, a vacuum drying machine and a tablet press;
the straw discharge port of the straw bin is connected with the straw feed port of the pulverizer, the straw discharge port of the pulverizer, the phosphoric acid discharge port of the phosphoric acid liquid storage tank and the straw feed port of the microwave hydrothermal reaction kettle are connected through a three-way pipe, a solid-liquid mixture outlet of the microwave hydrothermal reaction kettle is connected with a solid-liquid mixture inlet of the filter, a liquid recovery device is further arranged inside the microwave hydrothermal reaction kettle, a liquid backflow outlet of the microwave hydrothermal reaction kettle is connected with a liquid backflow inlet of the phosphoric acid liquid storage tank, a liquid outlet of the filter is connected with a liquid feed port of the liquid product tank, and a solid outlet of the filter is connected with a solid feed port of the;
a hydrothermal carbon outlet of the hydrothermal carbon storage tank and a potassium hydroxide outlet of the potassium hydroxide storage tank are connected with a mixture feed inlet of a first stirrer through a three-way pipe, the mixture outlet of the first stirrer is connected with a solid feed inlet of a tubular pyrolysis furnace, a nitrogen outlet of a nitrogen bottle is connected with a gas feed inlet of the tubular pyrolysis furnace, a gas product outlet of the tubular pyrolysis furnace is connected with an input port of a gas purification device, the solid product outlet of the tubular pyrolysis furnace is connected with a feed inlet of a hydrochloric acid pool, the gas outlet of the gas purification device is connected with a gas inlet of a gas storage tank, a discharge port of the hydrochloric acid pool is connected with a feed inlet of a clean water pool, and a discharge port of the clean water pool is connected with an active;
the utility model discloses a coating machine, including active carbon storage tank, NMP storage tank, PVDF storage tank, vacuum drying machine, the input of vacuum drying machine is connected to the output of coating machine, the output of vacuum drying machine inserts the tablet press.
Compared with the prior art, the utility model has the advantages that:
the utility model discloses following beneficial effect has:
1. the system can utilize straws with any moisture content, does not need to be dried, directly carries out hydrothermal reaction on the straws under the catalysis of microwave water bath, and can reduce the drying energy consumption of the system.
2. The microwave hydrothermal reaction kettle is internally provided with a liquid recovery device, so that microwave hydrothermal liquid products can be recycled, the quality of the liquid products can be improved, nutrient components and carbon microspheres in the liquid products can be increased, and the water resource consumption can be reduced.
3. The system realizes the full component utilization of the straws, a liquid-phase product in the microwave hydrothermal reaction process can be used as a nutrient solution or a sterilizing agent, a solid-phase product hydrothermal carbon can be used as a precursor for producing hydrothermal-based activated carbon, and a gas-phase product in the high-temperature activation process is rich in H2CO, etc. can be used as high-quality fuel gas after purification treatment.
4. The system provides a method combining microwave low-temperature acidic hydrothermal and high-temperature alkaline activation, which can ensure higher hydrolysis rate of straws, prepare hydrothermal carbon rich in carbon microspheres and oxygen-containing functional groups, and meanwhile, the straw hydrothermal activated carbon has high specific surface area, porous structure and high conductivity, shows excellent electrochemical performance, has environmental protection and advancement in the process of preparing the supercapacitor, and is beneficial to promoting the industrial production of the hydrothermal activated carbon.
Drawings
Fig. 1 is a schematic structural diagram of a system for preparing the straw microwave hydrothermal base supercapacitor active carbon electrode material of the present invention.
FIG. 2 is a scanning electron microscope SEM image of 260 ℃ rice straw hydrothermal carbon.
FIG. 3 is a scanning electron microscope SEM image of the rice straw hydrothermal-based activated carbon at 900 ℃.
FIG. 4 is a graph of cyclic voltammetry CV of the 900 ℃ rice straw hydrothermal-based activated carbon at different scanning rates.
FIG. 5 is a GCD curve of constant current charge and discharge performance of the rice straw hydrothermal-based activated carbon at 900 ℃ under different current densities.
In FIG. 2, 10.0kV is the working voltage of the scanning electron microscope, 12.7mm is the working distance, 100k is the magnification, and 500nm is the length scale;
in FIG. 3, 10.0kV is the working voltage of the scanning electron microscope, 12.7mm is the working distance, 100k is the magnification, and the length scale is 5.00 um.
The device comprises a straw bin 1, a straw bin 2, a pulverizer 3, a phosphoric acid liquid storage tank 4, a microwave hydrothermal reaction kettle 5, a filter 6, a liquid product tank 7, a hydrothermal carbon storage tank 8, a potassium hydroxide storage tank 9, a first stirrer 9, a nitrogen bottle 10, a tubular pyrolysis furnace 11, a gas purification device 12, a gas storage tank 13, a hydrochloric acid tank 14, a clear water tank 15, an activated carbon storage tank 16, an acetylene black storage tank 17, an NMP storage tank 18, a PVDF storage tank 19, a second stirrer 20, a nickel foam storage tank 21, a coating machine 22, a vacuum drying machine 23, a tablet press 24 and a supercapacitor 25.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the system for preparing the straw microwave hydrothermal-based supercapacitor activated carbon electrode material comprises a microwave low-temperature acidic hydrothermal device, a high-temperature alkaline activation device and an electrode material preparation device, wherein the microwave low-temperature acidic hydrothermal device comprises a straw bin 1, a pulverizer 2, a phosphoric acid liquid storage tank 3, a microwave hydrothermal reaction kettle 4, a filter 5, a liquid product tank 6 and a hydrothermal carbon storage tank 7, the high-temperature alkaline activation device comprises a potassium hydroxide storage tank 8, a first stirrer 9, a nitrogen cylinder 10, a tubular pyrolysis furnace 11, a gas purification device 12, a gas storage tank 13, a hydrochloric acid tank 14, a clear water tank 15 and an activated carbon storage tank 16, the electrode material preparation device comprises an acetylene black storage tank 17, an NMP storage tank 18, a PVDF storage tank 19, a second stirrer 20, a foamed nickel storage tank 21, a coating machine 22, a vacuum drying machine 23, a vacuum drying machine 16, and a cathode material preparation method, A tablet press 24;
the straw discharge port of the straw bin 1 is connected with the straw feed port of the pulverizer 2, the straw discharge port of the pulverizer 2, the phosphoric acid discharge port of the phosphoric acid liquid storage tank 3 and the straw feed port of the microwave hydrothermal reaction kettle 4 are connected through a three-way pipe, the solid-liquid mixture outlet of the microwave hydrothermal reaction kettle 4 is connected with the solid-liquid mixture inlet of the filter 5, the liquid recovery device is further arranged inside the microwave hydrothermal reaction kettle 4, the liquid backflow outlet of the microwave hydrothermal reaction kettle 4 is connected with the liquid backflow inlet of the phosphoric acid liquid storage tank 3, the liquid outlet of the filter 5 is connected with the liquid feed port of the liquid product tank 6, and the solid outlet of the filter 5 is connected with the solid feed port of the hydrothermal carbon storage;
a hydrothermal carbon outlet of the hydrothermal carbon storage tank 7 and a potassium hydroxide outlet of the potassium hydroxide storage tank 8 are connected with a mixture feed inlet of a first stirrer 9 through a three-way pipe, the mixture outlet of the first stirrer 9 is connected with a solid feed inlet of a tubular pyrolysis furnace 11, a nitrogen outlet of a nitrogen bottle 10 is connected with a gas feed inlet of the tubular pyrolysis furnace 11, a gas product outlet of the tubular pyrolysis furnace 11 is connected with an input port of a gas purification device 12, the solid product outlet of the tubular pyrolysis furnace 11 is connected with a feed inlet of a hydrochloric acid tank 14, the gas outlet of the gas purification device 12 is connected with a gas inlet of a gas storage tank 13, a discharge port of the hydrochloric acid tank 14 is connected with a feed inlet of a clean water tank 15, and a discharge port of the clean water tank 15 is connected with an active;
activated carbon discharge gate, acetylene black discharge gate, NMP storage tank 18's NMP discharge gate, PVDF storage tank 19's PVDF discharge gate and second stir the mixture feed inlet of material machine 20 and pass through the five-way pipe and link to each other, the second stirs the mixture feed inlet of the mixture exit linkage coating machine 22 of material machine 20, the input of coating machine 22 is connected to the discharge gate of foam nickel storage tank 21, the input of vacuum drying machine 23 is connected to the output of coating machine 22, the output of vacuum drying machine 23 inserts tablet press 24.
Among the above-mentioned technical scheme, microwave hydrothermal reation kettle 4 is through setting up liquid recovery unit and sensor in the reation kettle bottom, can make the liquid product by recycle, liquid reflux outlet is connected to liquid recovery unit bottom, then be equipped with the filter screen all around and only allow liquid to get into recovery unit, the portable baffle of filter screen outside cover, liquid volume in the reation kettle is monitored through the sensor, after 30 ~ 50% entering filter screen of liquid product, the portable baffle covers the filter screen, after the microwave hydrothermal reaction finishes next time, remove the baffle once more and expose the filter screen and carry out liquid recovery.
The bottom of the hydrochloric acid pool 14 is provided with a filter screen and a movable baffle, and after the hydrothermal-based activated carbon containing potassium hydroxide fully reacts with hydrochloric acid, the movable baffle exposes the filter screen to enable all liquid to enter the waste liquid treatment system, so that the residual hydrothermal-based activated carbon is sent into the clean water pool 15.
The bottom of the clean water tank 15 is also provided with a filter screen and a movable baffle, ventilation pipelines are arranged around the clean water tank, and after the clean water is drained through the filter screen, the ventilation pipelines are opened to accelerate the airing of the hydrothermal-based activated carbon.
In the technical scheme, a phosphoric acid concentration sensor is arranged in the phosphoric acid liquid storage tank 3, and the phosphoric acid concentration is detected by the phosphoric acid concentration sensor, so that the concentration of phosphoric acid in the tank is controlled.
In the above technical scheme, the hydrochloric acid tank 14 and the clean water tank 15 can control the inflow and outflow of liquid, and the clean water tank 15 can be used as a place for naturally drying the activated carbon.
In the technical scheme, the three-way pipe is a rounded corner converging three-way pipe. The five-way pipe is a round-angle confluence five-way pipe.
In the electrode material manufacturing system, the coating machine 22, the vacuum drying machine 23, and the tablet press machine 24 may be connected to each other by a robot arm to transport the product.
A preparation method of the straw microwave hydrothermal base super capacitor activated carbon electrode material by using the system comprises the following steps:
step 1: straws with any moisture content are sent into a crusher 2 for crushing through a straw discharge port of a straw bin 1;
step 2: the crushed straws and phosphoric acid in a phosphoric acid liquid storage tank 3 are sent into a microwave hydrothermal reaction kettle 4 through a three-way pipe, so that the mixture of the straws and the phosphoric acid is subjected to microwave hydrothermal reaction;
and step 3: enabling 30-50% of a liquid product after hydrothermal reaction to enter a phosphoric acid liquid storage tank 3 through a liquid backflow outlet of a microwave hydrothermal reaction kettle 4 through a liquid recovery device in the microwave hydrothermal reaction kettle 4, meanwhile, detecting the concentration of phosphoric acid through a sensor in the phosphoric acid liquid storage tank 3, controlling the concentration of phosphoric acid in the tank to be 5-20%, then sending a solid-liquid mixture left in the microwave hydrothermal reaction kettle 4 into a filter 5 through a solid-liquid mixture outlet for solid-liquid separation, enabling the liquid product after solid-liquid separation to enter a liquid product tank 6 through a liquid outlet, and enabling the solid product after solid-liquid separation to enter a hydrothermal carbon storage tank 7 through a solid outlet;
and 4, step 4: feeding the hydrothermal carbon output by the hydrothermal carbon storage tank 7 and the potassium hydroxide output by the potassium hydroxide storage tank 8 into a first stirrer 9 through a three-way pipe, and uniformly mixing the mixture in the first stirrer 9;
and 5: sending the uniformly mixed mixture into a tubular pyrolysis furnace 11 through a mixture outlet of a first stirrer 9, simultaneously opening a nitrogen bottle 10 to enable nitrogen to enter the tubular pyrolysis furnace 11 from a gas feed inlet of the tubular pyrolysis furnace 11, and enabling the mixture to be subjected to high-temperature activation for 0.5-2 hours at a nitrogen flow rate of 0.5-2L/min and a temperature of 600-900 ℃;
step 6: gaseous products (CO, CH) at the reaction of step 54、H2、CnHm、CO2) Through the outlet of the tubular pyrolysis furnace 11 into a gas purification device 12 for purification (removal of CO)2) The purified gas product is conveyed to a gas storage tank 13 through a gas outlet of a gas purification device 12 for storage;
and 7: feeding the solid product (hydrothermal activated carbon containing potassium hydroxide) reacted in the step 5 into a hydrochloric acid tank 14 through a solid product outlet of a tubular pyrolysis furnace 11 for neutralization and cleaning, feeding the cleaned solid product into a clean water tank 15 through a feed inlet of the clean water tank 15 for cleaning, draining water after cleaning, airing the activated carbon, and feeding the activated carbon into an activated carbon storage tank 16 through a discharge outlet of the clean water tank 15 for storage;
and 8: the activated carbon in the activated carbon storage tank 16, the acetylene black in the acetylene black storage tank 17, the NMP in the NMP storage tank 18 and the PVDF in the PVDF storage tank 19 are sent into a second stirrer 20 through a five-way pipe, so that the four substances are uniformly mixed, the NMP is a dispersing agent and is used for dissolving the PVDF as a binder, and the NMP is added according to the using amount of the PVDF so that the PVDF can be completely dissolved;
and step 9: sending the uniformly mixed material obtained in the step 8 into a coater 22 through a mixture outlet of a second stirrer 20 from a mixture feed port of the coater 22, and then sending the nickel foam in a storage tank 21 of the nickel foam to the coater 22, so that the mixture of the second stirrer 20 is uniformly coated on the nickel foam;
step 10: feeding the foamed nickel coated in the step 9 into a vacuum drier for drying through a mechanical arm;
step 11: feeding the vacuum-dried coated foamed nickel into a tablet press 24 to prepare an electrode slice;
step 12: and (5) assembling the super capacitor by the electrode plates obtained in the step (11).
In the technical scheme, the mixture of the straw and the phosphoric acid is subjected to microwave hydrothermal reaction in a microwave hydrothermal reaction kettle 4 at 180-260 ℃ for 1-3 h. The microwave hydrothermal reaction is carried out under the parameters, the hydrothermal carbon rich in a nano carbon microsphere structure and a large amount of surface oxygen-containing functional groups can be obtained, and the hydrothermal carbon can be easily combined with other molecules, ions and functional groups to form a novel functional carbon material and can be used as a precursor for preparing porous materials and novel carbon-based nano materials.
In step 4 of the above technical scheme, the mass ratio of hydrothermal carbon to potassium hydroxide is controlled to be 3: 1-1: 3; by adopting the parameter, the carbon microsphere structure in the hydrothermal carbon basically disappears, the surface of the obtained hydrothermal-based activated carbon is smoother, and a multi-layer pore structure with rich pore size can be observed in the hydrothermal-based activated carbon;
and 7, controlling the mass ratio of the active carbon to the acetylene black to the PVDF to be about 8:1:1, uniformly mixing the four substances; by adopting the parameters, the prepared electrode material has better cyclic voltammetry performance, constant current charge-discharge performance, electrochemical impedance spectrum performance and electrode cyclic performance;
and 10, sending the foamed nickel coated in the step 9 into a vacuum drying machine at the temperature of 110-120 ℃ for drying for 12-24 hours.
And 11, feeding the vacuum-dried coated foamed nickel into a tablet press 24, maintaining the pressure for 3-5 min at 10-12 MPa to prepare an electrode plate, and detecting the electrochemical performance.
In the technical scheme, the liquid recovery device in the microwave hydrothermal reaction kettle 4 in the step 3 enables a hydrothermal liquid product to be repeatedly utilized, so that the quality of the liquid product can be improved, the nutrient content and carbon microspheres in the liquid product are increased, and the water resource consumption can be reduced.
In the technical scheme, the liquid product obtained in the step 3 can be used as a nutrient solution or a sterilizing agent.
In the above technical scheme, the gas product obtained in step 6 is rich in H2CO, etc., can be used as high-quality fuel gas.
In the above technical scheme, the phosphoric acid liquid storage tank 3, the microwave hydrothermal reaction kettle 4, the filter 5, the liquid product tank 6 and the hydrochloric acid tank 14 are made of acid-resistant materials, the potassium hydroxide storage tank 8, the first stirrer 9 and the tubular pyrolysis furnace 11 are made of alkali-resistant materials, and the nitrogen cylinder 10, the gas purification device 12 and the gas storage tank 13 are made of high-pressure-resistant materials.
A method for preparing a super capacitor by using the electrode material comprises the following steps:
step 101: cleaning the button battery case with ethanol, soaking for 10-20 min, wiping with degreased cotton, and drying in a dryer for 18-24 h for later use;
step 102: weighing 2 groups of the electrode plates for later use;
step 103: opening the positive electrode shell upwards, horizontally placing the positive electrode shell on the panel, and dropping electrolyte at the center of the positive electrode shell;
step 104: placing the positive plate into a positive shell, and dropwise adding electrolyte to the electrode plate to ensure that the electrode plate is completely and uniformly wetted;
step 105: covering the positive plate with a diaphragm, and dropwise adding electrolyte to completely and uniformly wet the diaphragm;
step 106: clamping the other electrode plate in the center of the diaphragm, covering the gasket and the spring piece, and adding electrolyte to completely wet the gasket and the spring piece and the electrode plate covered with the gasket and the spring piece;
step 107: covering a negative electrode shell, and pressing for 1-2 min by using a button cell hydraulic press to obtain the button type super capacitor 25.
The utility model discloses a preparation system of straw microwave hydrothermal base ultracapacitor system active carbon electrode material, through send into straw after smashing and the dilute solution of phosphoric acid and react 1 ~ 3h in the microwave hydrothermal reation kettle of 180 ~ 260 ℃, filter the hydrothermal result again and obtain liquid product and the hydrothermal carbon that is rich in the carbosphere to obtain the precursor of preparation active carbon. And then mixing hydrothermal carbon and an activating agent KOH according to the mass ratio of 3: 1-1: 3, mixing, feeding into a tubular pyrolysis furnace, carrying out carbonization and activation for 0.5-2 h at 600-900 ℃ in a nitrogen atmosphere, wherein the obtained gas product can be used as fuel gas, and the solid product is neutralized and cleaned by HCl and dried to obtain the hydrothermal-based activated carbon. And then mixing the hydrothermal-based activated carbon, the acetylene black and the PVDF according to the mass ratio of 8:1:1, adding a proper amount of NMP solvent, uniformly mixing, uniformly coating on the foamed nickel, drying and pressing to obtain the electrode material, and inspecting the electrochemical performance of the electrode material. And adding an electrode diaphragm between the two qualified electrode materials, and assembling to prepare the super capacitor. The utility model discloses improved living beings base ultracapacitor system's production technology, not only can realize the clean energy utilization of the full component of straw, can realize high performance ultracapacitor system's development and utilization simultaneously.
Example 1
Step 1: rice straws with any moisture content are sent into a crusher 2 for crushing through a straw discharge port of a straw bin 1;
step 2: feeding the crushed rice straws and 10% phosphoric acid into a microwave hydrothermal reaction kettle 4 through a fillet confluence three-way pipe, and carrying out microwave hydrothermal reaction on the mixture of the rice straws and the 10% phosphoric acid at 260 ℃ for 60 min;
and step 3: after the reaction in the step 2 is finished, enabling part of liquid to enter a phosphoric acid liquid storage tank 3 through a liquid backflow outlet of a microwave hydrothermal reaction kettle 4 through a liquid recovery device in the microwave hydrothermal reaction kettle 4, simultaneously detecting the concentration of phosphoric acid through a sensor in the phosphoric acid liquid storage tank 3, controlling the concentration of phosphoric acid in the tank to be 10%, sending the residual solid-liquid mixture in the microwave hydrothermal reaction kettle 4 into a filter 5 through a solid-liquid mixture outlet of the microwave hydrothermal reaction kettle 4 for filtering, enabling the filtered liquid product to enter a liquid product tank 6 through a liquid outlet, and enabling the filtered solid product to enter a hydrothermal carbon storage tank 7 through a solid outlet;
and 4, step 4: and (3) feeding the hydrothermal carbon and the potassium hydroxide obtained in the step (3) into a first stirrer 9 through a fillet confluence three-way pipe, and controlling the mass ratio of the hydrothermal carbon to the potassium hydroxide to be 1:1, uniformly mixing the mixture in a first stirrer 9;
and 5: feeding the uniformly mixed mixture into a tubular pyrolysis furnace 11 from a solid feeding hole of the tubular pyrolysis furnace 11 through a mixture outlet of a first stirrer 9, simultaneously opening a nitrogen bottle 10 to enable nitrogen to enter the tubular pyrolysis furnace 11 from a gas feeding hole of the tubular pyrolysis furnace 11, and enabling the mixture to be subjected to high-temperature activation at 900 ℃ for 60min at a nitrogen flow rate of 1L/min;
step 6: gas products generated in the reaction in the step 5 enter a gas purification device 12 through a gas product outlet of a tubular pyrolysis furnace 11 for purification, and the purified gas products are sent into a gas storage tank 13 through a gas outlet of the gas purification device 12 for storage;
and 7: feeding the solid product reacted in the step 5 into a hydrochloric acid tank 14 through a solid product outlet of a tubular pyrolysis furnace 11 for neutralization and cleaning, feeding the cleaned solid product into a clean water tank 15 through a feed inlet of the clean water tank 15 for cleaning, draining water after cleaning to dry the activated carbon, and feeding the activated carbon into an activated carbon storage tank 16 through a discharge outlet of the clean water tank 15 for storage;
and 8: and (2) sending the activated carbon, the acetylene black, the PVDF and a small amount of NMP into a second stirrer 20 through a fillet confluence five-way pipe, and controlling the mass ratio of the activated carbon, the acetylene black and the PVDF to be about 8:1:1, uniformly mixing the four substances;
and step 9: the uniformly mixed substances in the step 8 enter a coating machine 22 from a mixture feed inlet of the coating machine 22 through a mixture outlet of a second stirrer 20, and the foamed nickel in a foamed nickel storage tank 21 is sent to the coating machine 22, so that the mixture is uniformly coated on the foamed nickel;
step 10: feeding the foamed nickel coated in the step 9 into a vacuum dryer 23 at 120 ℃ by a manipulator for drying for 24 hours;
step 11: feeding the coated nickel foam subjected to vacuum drying into a tablet press 24 through a manipulator, maintaining the pressure for 3min at 10MPa to prepare an electrode plate, and detecting the electrochemical performance;
step 12: and (5) assembling the super capacitor 25 by the electrode plates obtained in the step (11).
With the rise of the hydrothermal temperature, the hydrothermal reaction is intensified, the yield of the hydrothermal carbon of the rice straw is reduced, the yield of the liquid phase is increased, and after the microwave hydrothermal reaction is carried out on the rice straw at the temperature of 260 ℃, the yield of the hydrothermal carbon is about 40%, and the yield of the liquid phase is about 60%.
Table 1 shows the yield of the product of the high-temperature activated carbon activated at 900 ℃ and the composition of the gas product of the microwave hydrothermal carbon of rice straws at 260 ℃;
as can be seen from Table 1, the yield of the microwave hydrothermal-based activated carbon of the rice straw at 900 ℃ is 10.96%, and the yield of the gas generated by high-temperature activation is 20.63%, wherein the activated carbon is rich in CO and CH4、CnHm、H2Equal combustible gas, and with H2The content is the maximum, which indicates that the gas product obtained in the step 6 can be used as high-quality fuel gas.
From the figure 2, the rice straw hydrothermal carbon with the temperature of 260 ℃ has more nano carbon microsphere structures on the surface and inside and rich pore structures, and can be used as a precursor for preparing porous materials and novel carbon-based nano materials.
As can be seen from fig. 3, after KOH activation, the carbon microsphere structure in the rice straw hydrothermal carbon basically disappears, the surface of the rice straw microwave hydrothermal-based activated carbon is smoother, and a multi-level pore structure with rich pore size can be observed therein.
Table 2 shows the specific surface area and pore size distribution of 260 ℃ rice straw hydrothermal carbon and 900 ℃ hydrothermal-based activated carbon.
As can be seen from Table 2, the specific surface area of the 260 ℃ rice straw hydrothermal carbon is relatively small, mesopores are taken as main parts in the pore structure, the rice straw hydrothermal carbon can be used as a precursor for preparing activated carbon through certain modification, and when the activation temperature is 900 ℃, the specific surface area of the rice straw hydrothermal activated carbon can reach 1569.6044m2Per g, total pore volume can reach 1.1421cm3/g。
FIG. 4 is a graph of cyclic voltammetry CV of the 900 ℃ rice straw hydrothermal-based activated carbon at different scanning rates. The potential window of the cyclic voltammetry test is from 0V to 1.0V, and the scan rate is 5, 10, 20, 50, 100mv/s respectively. Under a low scanning rate, the cyclic voltammetry curve of the rice straw microwave hydrothermal-based activated carbon presents a symmetrical rectangular shape, which shows that the rice straw hydrothermal-based activated carbon has typical double electric layer capacitance characteristics. The larger the integral area of the cyclic voltammetry CV curve is, the higher the specific capacitance is, and the graph shows that the 900 ℃ rice straw microwave hydrothermal-based activated carbon has higher specific capacitance.
FIG. 5 is a GCD curve of constant current charge and discharge performance of the rice straw hydrothermal-based activated carbon at 900 ℃ under different current densities. The constant current charge-discharge curve of the 900 ℃ rice straw microwave hydrothermal based activated carbon presents an ideal isosceles triangle for the supercapacitor, and the result shows that the 900 ℃ rice straw microwave hydrothermal based activated carbon has good electrochemical reversibility and capacitance characteristics. When the current density is 1A g-1The specific capacitance of the rice straw microwave hydrothermal-based activated carbon at 900 ℃ is 150.12F g-1。
In conclusion, the rice straw microwave hydrothermal carbon has rich nano carbon microsphere structures and oxygen-containing functional groups, and the activated carbon prepared from the rice straw microwave hydrothermal carbon has rich macroporous, mesoporous and microporous network structures, has good electrochemical performance, and is a good electrode material for preparing a supercapacitor.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
Claims (5)
1. A straw microwave hydrothermal base super capacitor active carbon electrode material preparation system is characterized in that: it includes microwave low temperature acid hydrothermal device, high temperature basicity activation device, electrode material preparation facilities, wherein, microwave low temperature acid hydrothermal device includes straw feed bin (1), rubbing crusher (2), phosphoric acid liquid storage pot (3), microwave hydrothermal reation kettle (4), filter (5), liquid product jar (6), hydrothermal carbon storage tank (7), high temperature basicity activation device includes potassium hydroxide storage tank (8), first stirring machine (9), nitrogen cylinder (10), tubular pyrolysis oven (11), gaseous purifier (12), gas holder (13), hydrochloric acid pond (14), clean water pond (15), active carbon storage tank (16), electrode material preparation facilities includes acetylene black storage tank (17), NMP storage tank (18), PVDF storage tank (19), second stirring machine (20), foam nickel storage tank (21), coating machine (22), A vacuum drier (23) and a tablet press (24);
the straw discharge port of the straw bin (1) is connected with the straw feed port of the pulverizer (2), the straw discharge port of the pulverizer (2), the phosphoric acid discharge port of the phosphoric acid liquid storage tank (3) and the straw feed port of the microwave hydrothermal reaction kettle (4) are connected through a three-way pipe, the solid-liquid mixture outlet of the microwave hydrothermal reaction kettle (4) is connected with the solid-liquid mixture inlet of the filter (5), the liquid reflux outlet of the microwave hydrothermal reaction kettle (4) is connected with the liquid reflux inlet of the phosphoric acid liquid storage tank (3), the liquid outlet of the filter (5) is connected with the liquid feed port of the liquid product tank (6), and the solid outlet of the filter (5) is connected with the solid feed port of the hydrothermal carbon storage tank (7);
a hydrothermal carbon outlet of the hydrothermal carbon storage tank (7) and a potassium hydroxide outlet of the potassium hydroxide storage tank (8) are connected with a mixture feed inlet of the first stirrer (9) through a three-way pipe, a mixture outlet of the first stirrer (9) is connected with a solid feed inlet of the tubular pyrolysis furnace (11), a nitrogen outlet of the nitrogen bottle (10) is connected with a gas feed inlet of the tubular pyrolysis furnace (11), a gas product outlet of the tubular pyrolysis furnace (11) is connected with an input port of the gas purification device (12), a solid product outlet of the tubular pyrolysis furnace (11) is connected with a feed inlet of the hydrochloric acid tank (14), a gas outlet of the gas purification device (12) is connected with a gas inlet of the gas storage tank (13), a discharge port of the hydrochloric acid tank (14) is connected with a feed inlet of the clean water tank (15), and a discharge port of the clean water tank (15) is connected with an active carbon feed inlet of the active carbon storage tank (16);
the active carbon discharge gate of active carbon storage tank (16), the acetylene black discharge gate of acetylene black storage tank (17), the NMP discharge gate of NMP storage tank (18), the PVDF discharge gate of PVDF storage tank (19) and the mixture feed inlet that the second stirred material machine (20) link to each other through the five-way pipe, the mixture feed inlet of mixture exit linkage coating machine (22) of second stirred material machine (20), the input of coating machine (22) is connected to the discharge gate of foam nickel storage tank (21), the input of vacuum drying machine (23) is connected to the output of coating machine (22), the output of vacuum drying machine (23) inserts tablet press (24).
2. The system for preparing the straw microwave hydrothermal base supercapacitor active carbon electrode material according to claim 1, characterized in that: and a phosphoric acid concentration sensor is arranged in the phosphoric acid liquid storage tank (3), and the phosphoric acid concentration is detected by the phosphoric acid concentration sensor, so that the concentration of phosphoric acid in the tank is controlled.
3. The system for preparing the straw microwave hydrothermal base supercapacitor active carbon electrode material according to claim 1, characterized in that: the hydrochloric acid pool (14) and the clean water pool (15) can control the inflow and outflow of liquid, and the clean water pool (15) can be used as a field for drying the activated carbon.
4. The system for preparing the straw microwave hydrothermal base supercapacitor active carbon electrode material according to claim 1, characterized in that: the three-way pipe is a rounded corner converging three-way pipe.
5. The system for preparing the straw microwave hydrothermal base supercapacitor active carbon electrode material according to claim 1, characterized in that: the five-way pipe is a round-angle confluence five-way pipe.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110556250A (en) * | 2019-09-02 | 2019-12-10 | 华中农业大学 | System and method for preparing straw microwave hydrothermal-based supercapacitor active carbon electrode material |
| CN112138699A (en) * | 2020-09-25 | 2020-12-29 | 拉萨波玛拉生物科技有限公司 | Preparation method of N-rich hydrothermal carbon material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110556250A (en) * | 2019-09-02 | 2019-12-10 | 华中农业大学 | System and method for preparing straw microwave hydrothermal-based supercapacitor active carbon electrode material |
| CN112138699A (en) * | 2020-09-25 | 2020-12-29 | 拉萨波玛拉生物科技有限公司 | Preparation method of N-rich hydrothermal carbon material |
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