CN108033447B - Preparation method of porous biomass carbon, porous biomass carbon and application - Google Patents
Preparation method of porous biomass carbon, porous biomass carbon and application Download PDFInfo
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Abstract
The invention relates to a preparation method of porous biomass carbon, the porous biomass carbon and application. A preparation method of porous biomass carbon comprises the following steps: mixing straws with a calcium chloride solution, and standing for 12-24 hours to obtain a mixture, wherein the mass ratio of the straws to the calcium chloride in the calcium chloride solution is 1: 1.5-1: 3; drying the mixture, and then carbonizing the mixture at the low temperature of 300-350 ℃ for 2-3 hours to obtain low-temperature carbide; heating the low-temperature carbide to 500-700 ℃ to carry out high-temperature activation treatment for 1-3 hours to obtain a pre-product; and soaking the pre-product in strong inorganic acid for 12-24 hours, and washing the pre-product with water at 70-80 ℃ to be neutral to obtain the porous biomass carbon. The porous biomass carbon prepared by the preparation method of the porous biomass carbon can improve the charge-discharge specific capacity and the cycling stability of the lithium ion battery.
Description
Technical Field
The invention relates to a preparation method of porous biomass carbon, the porous biomass carbon and application.
Background
With the rapid development of social economy and the dramatic increase of population, people have greater and greater energy demand, but due to the non-regenerability of fossil energy such as petroleum, coal, natural gas and the like, the demand of economic and social development can not be met gradually after long-time exploitation. In addition, a large amount of greenhouse gases and toxic gases generated after the fossil energy is combusted are harmful to the living environment of people. In recent years, with the improvement of environmental awareness of people, people have more and more high call for clean energy, and the development of new clean, efficient and energy-saving energy sources to replace fossil energy becomes a focus of attention of researchers.
Lithium ion has been widely paid attention since the world as a clean and efficient green power source, and compared with the conventional battery, the lithium ion battery has the advantages of high working voltage, wide working temperature range, high energy density, no memory effect and the like. In recent years, with the popularization of intelligent electronic devices, lithium ion batteries have been widely used in mobile phones, digital cameras, smart watches, and the like. In addition, active research and application are carried out at home and abroad for the application in the fields of electric vehicles, new energy vehicles, aerospace, military equipment and the like. Therefore, lithium ion batteries are a great research trend at present, and the improvement of the specific capacity, the cycle rate and the cycle stability of the batteries becomes a main focus of lithium ion battery research.
The negative electrode material is one of the key materials of the lithium ion battery, and the carbon material is still widely concerned as the negative electrode material of the lithium battery which is researched and applied at the earliest. The crop straws serving as agricultural wastes are easy to cause fire when being burnt, and simultaneously release a large amount of carbon dioxide to intensify the carbon dioxide effect, so that the research on obtaining the activated carbon by carbonizing the straws is carried out to a certain extent. However, when the activated carbon obtained by the existing preparation method is used as a lithium ion battery negative electrode material, the charge-discharge capacity and the cycle stability of the lithium ion battery are poor.
Disclosure of Invention
Therefore, a preparation method of the porous biomass carbon capable of improving the charge-discharge specific capacity and the cycling stability of the lithium ion battery, the porous biomass carbon and the application are needed to be provided.
A preparation method of porous biomass carbon comprises the following steps:
mixing straws with a calcium chloride solution, and standing for 12-24 hours to obtain a mixture, wherein the mass ratio of the straws to the calcium chloride in the calcium chloride solution is 1: 1.5-1: 3;
drying the mixture, and then carbonizing the mixture at the low temperature of 300-350 ℃ for 2-3 hours to obtain low-temperature carbide;
heating the low-temperature carbide to 500-700 ℃ to carry out high-temperature activation treatment for 1-3 hours to obtain a pre-product; and
and soaking the pre-product by using inorganic strong acid for 12-24 hours, and washing the pre-product by using water at the temperature of 70-80 ℃ until the pre-product is neutral to obtain the porous biomass carbon.
The preparation method of the porous biomass carbon has the following advantages:
(1) the straw is used as a carbon source, so that the cost is low, the resource reutilization is realized, and the environmental pollution is reduced;
(2) the calcium chloride which can be recycled is used as the activating agent, so that the price is low, and the production cost is reduced;
(3) the pore size of the prepared porous biomass carbon can be conveniently controlled by adjusting the concentration and the dosage of the calcium chloride solution;
(4) the calcium chloride has good flame retardant effect, can effectively prevent the oxidation of the incandescent carbon in the straw carbonization and activation treatment processes, and can improve the yield of the activated carbon;
(5) the prepared porous biomass carbon is used as a negative electrode material of the lithium ion battery, and can improve the discharge specific capacity and the cycling stability of the lithium ion battery.
In one embodiment, the straw is corn stover; and/or
The straw is in powder form.
In one embodiment, the strong inorganic acid is at least one selected from hydrochloric acid, sulfuric acid, and nitric acid.
In one embodiment, the concentration of the strong inorganic acid is 2 mol/L-6 mol/L.
In one embodiment, the solid-to-liquid ratio of the pre-product to the inorganic strong acid is 1g:10 mL-1 g:20 mL.
In one embodiment, in the step of carbonizing the mixture at a low temperature of 300-350 ℃ for 2-3 hours after drying the mixture to obtain the low-temperature carbide, the mixture is dried at a temperature of 60-70 ℃ to be dried.
In one embodiment, before the step of soaking the pre-product with strong inorganic acid for 12 to 24 hours, the method further comprises the following steps: washing the pre-product with water to obtain a recovered calcium chloride solution.
In one embodiment, the method further comprises the following steps: and drying the porous biomass carbon and then grinding.
The porous biomass carbon obtained by the preparation method of the porous biomass carbon.
The application of the porous biomass carbon in the battery.
Drawings
FIG. 1 is a scanning electron micrograph of porous biomass carbon prepared in example 1 at 80000 Xmagnification;
FIG. 2 is a transmission electron micrograph of porous biomass carbon prepared in example 1 at 30000 Xmagnification;
fig. 3 is a discharge graph at 0.2C current density for a lithium ion battery using the porous biomass carbon of example 1;
fig. 4 is a charge profile at 0.2C current density for a lithium ion battery using the porous biomass carbon of example 1;
fig. 5 is a discharge curve at 0.2C current density for a lithium ion battery using the porous biomass carbon of comparative example 1;
fig. 6 is a charge profile at current density of 0.2C for a lithium ion battery using the porous biomass carbon of comparative example 1;
fig. 7 is a discharge curve at 0.2C current density for a lithium ion battery using the porous biomass carbon of comparative example 2;
fig. 8 is a charge profile at current density of 0.2C for a lithium ion battery using the porous biomass carbon of comparative example 2.
Detailed Description
The method for producing the porous biomass carbon, and the use thereof will be described in further detail below with reference to specific embodiments.
The method for preparing porous biomass carbon according to the embodiment includes the steps of:
and S110, mixing the straws with a calcium chloride solution, and standing for 12-24 hours to obtain a mixture, wherein the mass ratio of the straws to the calcium chloride in the calcium chloride solution is 1: 1.5-1: 3.
In one embodiment, the straw is corn stover. Of course, in other embodiments, the straw may also be the remainder of the wheat, rice, potatoes, oilseed rape, cotton, sugar cane or other coarse grain crop after harvesting the seed.
In one embodiment, the straw is crushed and the crushed straw is mixed with a calcium chloride solution.
In one embodiment, the straw is in powder form. Preferably, the particle size of the straw powder is 800 micrometers to 900 micrometers, preferably 850 micrometers.
In one embodiment, the concentration of the calcium chloride solution is 2mol/L to 4mol/L, and preferably 3 mol/L.
In one embodiment, the solid-to-liquid ratio of the straw to the calcium chloride solution is 10g:200 mL-30 g:200mL, preferably 20g:200 mL.
In one embodiment, the mixture is obtained by mixing the straws with the calcium chloride solution and then standing for 12-24 hours at room temperature, preferably 24 hours.
In one embodiment, the mass ratio of the straws to the calcium chloride in the calcium chloride solution is 1: 2.5.
And step S120, drying the mixture, and then carbonizing the mixture at the low temperature of 300-350 ℃ for 2-3 hours to obtain low-temperature carbide.
In one embodiment, the mixture is dried at 60-70 deg.C. Preferably, the drying is carried out at a constant temperature of 60 ℃.
In one embodiment, the mixture is placed in an oven for drying.
In one embodiment, the straws are heated to 300-350 ℃ at the heating rate of 8-10 ℃/min for carbonization treatment.
In one embodiment, the mixture is dried and then carbonized at a low temperature of 300 ℃.
In one embodiment, the mixture is dried and placed in a crucible with a cover, and low temperature carbonization is performed in a muffle furnace.
In one embodiment, the time for the low temperature carbonization treatment is 2 hours.
And S130, heating the low-temperature carbide to 500-700 ℃ to carry out high-temperature activation treatment for 1-3 hours to obtain a pre-product.
In one embodiment, the low temperature carbides are heated to 600 ℃ for high temperature activation.
In one embodiment, the time for the high temperature activation treatment is 2 hours.
In one embodiment, low temperature carbides are placed in a crucible with a lid and subjected to a high temperature activation process in a muffle furnace.
In one embodiment, the low-temperature carbide is heated to 500-700 ℃ at the heating rate of 8-10 ℃/min for carbonization treatment.
In one embodiment, the low-temperature carbide is heated to 500-700 ℃ to be subjected to high-temperature activation treatment for 1-3 hours, and is naturally cooled to room temperature to obtain a pre-product.
In one embodiment, the pre-product is washed with water to provide a recovered calcium chloride solution. Preferably, the washing is carried out with deionized water, and the ratio of the pre-product to the deionized water is 1g:10mL to 1g:20 mL. The recovered calcium chloride solution can be reused in step S110.
And S140, soaking the pre-product in strong inorganic acid for 12-24 hours, and washing the pre-product with water at 70-80 ℃ until the pre-product is neutral to obtain the porous biomass carbon.
In one embodiment, the inorganic strong acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid, and preferably hydrochloric acid.
In one embodiment, the concentration of the strong inorganic acid is 2mol/L to 6 mol/L.
In one embodiment, the solid-to-liquid ratio of the pre-product to the inorganic strong acid is 1g:10 mL-1 g:20 mL.
In one embodiment, the pre-product is soaked in strong inorganic acid and then is subjected to solid-liquid separation to obtain a solid, and the solid is washed by water at 70-80 ℃.
In one example, the pre-product is soaked with a strong inorganic acid for 24 hours.
And S150, drying the porous biomass carbon and then grinding.
In one embodiment, the porous biomass carbon is dried at 60-70 ℃ for drying treatment. Preferably, the drying is carried out at a constant temperature of 60 ℃.
In one embodiment, the porous biomass carbon is placed in an oven for drying.
In one example, the porous biomass carbon is ground using an agate mortar for 0.2 to 0.6 hours.
In one embodiment, the porous biomass carbon is ground until the particle size of the porous biomass carbon is between 800 microns and 900 microns.
The preparation method of the porous biomass carbon has the following advantages:
(1) the straw is used as the carbon source, so that the cost is low, the resource recycling is realized, the environmental pollution is reduced, the problem of environmental pollution caused by improper treatment of waste crops is solved, the maximum utilization of resources is realized, and the preparation cost of the porous biomass carbon is reduced;
(2) the calcium chloride which can be recycled is used as the activating agent, so that the price is low, and the production cost is reduced;
(3) the pore size of the prepared porous biomass carbon can be conveniently controlled by adjusting the concentration and the dosage of the calcium chloride solution;
(4) the calcium chloride has good flame retardant effect, can effectively prevent the oxidation of the incandescent carbon in the straw carbonization and activation treatment processes, and can improve the yield of the activated carbon;
(5) the prepared porous biomass carbon is used as a negative electrode material of the lithium ion battery, and can improve the discharge specific capacity and the cycling stability of the lithium ion battery.
The porous biomass carbon according to an embodiment is produced by the above-described method for producing a porous biomass carbon.
In one embodiment, the porous biomass carbon has a specific surface area of 237.2m2/g～370.6m2/g。
In one embodiment, the porous biomass carbon has a porosity of 61% to 70%.
In one embodiment, the porous biomass carbon has a pore size of 7.24% to 9.65%.
The porous biomass carbon is used as a negative electrode material of the lithium ion battery, so that the discharge specific capacity and the cycling stability of the lithium ion battery can be improved, and the discharge specific capacity can reach 646 milliampere per gram after 100 cycles and is far more than the theoretical capacity of graphite; the working voltage is 0-3V, the working temperature range is minus 25 ℃ to 60 ℃, the discharge specific capacity is high, and the self-discharge rate is low.
The application of the porous biomass carbon in the battery.
In one embodiment, the battery is a lithium ion battery.
In one embodiment, the porous biomass carbon is used as a negative electrode material of a lithium ion battery.
The porous biomass carbon is applied to the battery, and can improve the discharge specific capacity and the cycling stability of the battery, particularly a lithium ion battery.
The following description will be given with reference to specific examples.
Example 1
The preparation of the porous biomass carbon comprises the following steps:
crushing corn straws into powder, uniformly mixing 20g of corn straw powder with 200ml of 3mol/L calcium chloride solution, and standing for 24 hours at room temperature;
drying the mixture in an oven at a constant temperature of 60 ℃, placing the mixture in a crucible with a cover, heating the mixture to 300 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and carbonizing the mixture at a low temperature for 3 hours to obtain a low-temperature carbide;
and continuously heating the low-temperature carbide in a muffle furnace at the heating rate of 10 ℃/min to 600 ℃ for high-temperature activation for 2 hours, and naturally cooling to room temperature to obtain a pre-product. Putting the pre-product into a beaker, adding 100mL of deionized water, and washing to obtain a recovered calcium chloride solution;
and (3) soaking the pre-product in 100mL of 2mol/L hydrochloric acid solution for 24 hours, washing the pre-product with 70 ℃ deionized water to be neutral, drying the pre-product in an oven at a constant temperature of 60 ℃, and grinding the pre-product for 0.5 hour by using an agate mortar to obtain the porous biomass carbon.
Example 2
The preparation of the porous biomass carbon comprises the following steps:
crushing corn straws into powder, uniformly mixing 10g of corn straw powder with 200ml of 2mol/L calcium chloride solution, and standing for 24 hours at room temperature;
drying the mixture in an oven at a constant temperature of 60 ℃, placing the mixture in a crucible with a cover, heating the mixture to 300 ℃ in a muffle furnace at a heating rate of 9 ℃/min, and carbonizing the mixture at a low temperature for 3 hours to obtain low-temperature carbide;
and continuously heating the low-temperature carbide in a muffle furnace at the heating rate of 9 ℃/min to 500 ℃ for high-temperature activation for 1 hour, and naturally cooling to room temperature to obtain a pre-product. Putting the pre-product into a beaker, adding 100mL of deionized water, and washing to obtain a recovered calcium chloride solution;
and (3) soaking the pre-product in 100mL of 4mol/L hydrochloric acid solution for 24 hours, washing the pre-product with 80 ℃ deionized water to be neutral, drying the pre-product in an oven at a constant temperature of 60 ℃, and grinding the pre-product for 0.3 hour by using an agate mortar to obtain the porous biomass carbon.
Example 3
The preparation of the porous biomass carbon comprises the following steps:
crushing corn straws into powder, uniformly mixing 30g of corn straw powder with 200ml of 4mol/L calcium chloride solution, and standing for 12 hours at room temperature;
drying the mixture in an oven at a constant temperature of 65 ℃, placing the mixture in a crucible with a cover, heating the mixture to 350 ℃ in a muffle furnace at a heating rate of 8 ℃/min, and carbonizing the mixture at a low temperature for 2 hours to obtain low-temperature carbide;
and continuously heating the low-temperature carbide in a muffle furnace at the heating rate of 8 ℃/min to 700 ℃ for high-temperature activation for 3 hours, and naturally cooling to room temperature to obtain a pre-product. Putting the pre-product into a beaker, adding 100mL of deionized water, and washing to obtain a recovered calcium chloride solution;
and (3) soaking the pre-product in 100mL of 6mol/L hydrochloric acid solution for 12 hours, washing the pre-product with 70 ℃ deionized water to be neutral, drying the pre-product in an oven at a constant temperature of 70 ℃, and grinding the pre-product for 0.4 hour by using an agate mortar to obtain the porous biomass carbon.
Example 4
The preparation of the porous biomass carbon comprises the following steps:
crushing corn straws into powder, uniformly mixing 20g of corn straw powder with 200ml of 2mol/L calcium chloride solution, and standing for 16 hours at room temperature;
drying the mixture in an oven at a constant temperature of 60 ℃, placing the mixture in a crucible with a cover, heating the mixture to 330 ℃ in a muffle furnace at a heating rate of 9 ℃/min, and carbonizing the mixture at a low temperature for 2 hours to obtain low-temperature carbide;
and continuously heating the low-temperature carbide in a muffle furnace at the heating rate of 9 ℃/min to 700 ℃ for high-temperature activation for 2 hours, and naturally cooling to room temperature to obtain a pre-product. Putting the pre-product into a beaker, adding 100mL of deionized water, and washing to obtain a recovered calcium chloride solution;
and (3) soaking the pre-product in 100mL of 2mol/L hydrochloric acid solution for 16 hours, washing the pre-product with deionized water at 75 ℃ to be neutral, drying the pre-product in an oven at a constant temperature of 60 ℃, and grinding the pre-product for 0.6 hour by using an agate mortar to obtain the porous biomass carbon.
Example 5
The preparation of the porous biomass carbon comprises the following steps:
crushing corn straws into powder, uniformly mixing 20g of corn straw powder with 200ml of 4mol/L calcium chloride solution, and standing for 20 hours at room temperature;
drying the mixture in an oven at a constant temperature of 70 ℃, placing the mixture in a crucible with a cover, heating the mixture to 340 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and carrying out low-temperature carbonization for 2.5 hours to obtain low-temperature carbide;
and continuously heating the low-temperature carbide in a muffle furnace at the heating rate of 10 ℃/min to 600 ℃ for high-temperature activation for 3 hours, and naturally cooling to room temperature to obtain a pre-product. Putting the pre-product into a beaker, adding 100mL of deionized water, and washing to obtain a recovered calcium chloride solution;
and (3) soaking the pre-product in 100mL of 6mol/L hydrochloric acid solution for 20 hours, washing the pre-product with deionized water at 75 ℃ to be neutral, drying the pre-product in an oven at a constant temperature of 60 ℃, and grinding the pre-product for 0.2 hour by using an agate mortar to obtain the porous biomass carbon.
Comparative example 1
The preparation of the biomass carbon comprises the following steps:
crushing corn straws into powder, placing 20g of the corn straw powder into a crucible with a cover, heating the corn straw powder to 300 ℃ in a muffle furnace at the heating rate of 10 ℃/min, and carbonizing the corn straw powder for 3 hours at low temperature to obtain low-temperature carbide;
and continuously heating the low-temperature carbide in a muffle furnace at the heating rate of 10 ℃/min to 600 ℃, preserving the heat for 2 hours, and naturally cooling to room temperature to obtain a pre-product.
And (3) soaking the pre-product in 100mL of 2mol/L hydrochloric acid solution for 24 hours, washing the pre-product with 70 ℃ deionized water to be neutral, drying the pre-product in an oven at a constant temperature of 60 ℃, and grinding the pre-product for 0.5 hour by using an agate mortar to obtain the biomass carbon.
Comparative example 2
Crushing corn straws into powder, placing 20g of the corn straw powder into a crucible with a cover, heating the corn straw powder to 300 ℃ in a muffle furnace at the heating rate of 10 ℃/min, and carbonizing the corn straw powder for 3 hours at low temperature to obtain low-temperature carbide;
uniformly mixing the low-temperature carbide with 200ml of 3mol/L calcium chloride solution, and standing for 24 hours at room temperature;
and (3) drying the mixture in an oven at a constant temperature of 60 ℃, continuously heating to 600 ℃ in a muffle furnace at a heating rate of 10 ℃/min for high-temperature activation for 2 hours, and naturally cooling to room temperature to obtain a pre-product. Putting the pre-product into a beaker, adding 100mL of deionized water, and washing to obtain a recovered calcium chloride solution;
and (3) soaking the pre-product in 100mL of 2mol/L hydrochloric acid solution for 24 hours, washing the pre-product with 70 ℃ deionized water to be neutral, drying the pre-product in an oven at a constant temperature of 60 ℃, and grinding the pre-product for 0.5 hour by using an agate mortar to obtain the porous biomass carbon.
Referring to fig. 1 to 2 together, fig. 1 is a scanning electron microscope photograph of the porous biomass carbon prepared in example 1 at magnification of 80000 times, and fig. 2 is a transmission electron microscope photograph of the porous biomass carbon prepared in example 1 at magnification of 30000 times.
As can be seen from fig. 1 to 2, the prepared porous biomass carbon has a loose material structure and a rich pore structure.
The specific surface areas of the porous biomass carbons obtained in examples 1 to 5 and comparative examples 1 to 2 were measured by BET, and the porosities of the porous biomass carbons obtained in examples 1 to 5 and comparative examples 1 to 2 were measured by BJH, and the results are shown in table 1.
TABLE 1
| Order of item | Specific surface area (m)2/g) | Porosity of the material |
| Example 1 | 370.6 | 70％ |
| Example 2 | 365.4 | 68％ |
| Example 3 | 287.2 | 61％ |
| Example 4 | 273.8 | 65％ |
| Example 5 | 365.5 | 63％ |
| Comparative example 1 | 45 | 8％ |
| Comparative example 2 | 187.1 | 47.3％ |
The porous biomass carbon of example 1, comparative example 1, and comparative example 2 was applied to a lithium ion battery for charge and discharge tests.
During charging and discharging tests, the porous biomass carbon, acetylene black and PVDF are uniformly mixed according to the mass ratio of 8:1:1 to obtain a mixture, then NMP is dropwise added into the mixture and stirred for 6 hours to form uniformly mixed slurry, the slurry is uniformly coated on copper foil and dried for 12 hours in a vacuum drying oven at 120 ℃, and the copper foil is punched into small wafers with the diameter of 12 mm by using a punching machine after drying. The cathode of the lithium ion battery is prepared by the method and is applied to the lithium ion battery with the model number of CR 2025. Among them, the type CR2025 lithium ion battery uses a lithium sheet as a counter electrode, a diaphragm is PP, and an electrolyte is EC/DMC (1: 1). And carrying out charge and discharge tests on the lithium ion battery.
The test was carried out on a blue CT2001A multichannel battery test system at a current density of 0.2C, the end voltage range was 0.02-3.0V, the cycle performance of the lithium ion battery using the porous biomass carbon of example 1 is shown in FIGS. 3-4, the cycle performance of the lithium ion battery using the biomass carbon of comparative example 1 is shown in FIGS. 5-6, and the cycle performance of the lithium ion battery using the porous biomass carbon of comparative example 2 is shown in FIGS. 7-8.
As can be seen from fig. 3 and 4, when the porous biomass carbon of example 1 is used as the negative electrode material of the lithium ion battery, after 100 cycles of charge and discharge at a current density of 0.2C, the specific discharge capacity reaches 646 milliampere per gram, and the specific charge capacity reaches 632.6 milliampere per gram; the biomass carbon of the comparative example 1 is used as a negative electrode material of the lithium ion battery, and after 100 times of charge-discharge cycles under the current density of 0.2C, the discharge specific capacity is 146.1 milliampere per gram, and the charge specific capacity reaches 145.5 milliampere per gram; the porous biomass carbon of comparative example 2 is used as the negative electrode material of the lithium ion battery, and after 100 times of charge-discharge cycles at the current density of 0.2C, the specific discharge capacity reaches 225.2 milliampere per gram, and the specific charge capacity reaches 226.6 milliampere per gram.
It can be seen from fig. 3 to 8 that the porous biomass carbon of example 1 has a higher charge-discharge specific capacity than the biomass carbon of comparative example 1 and comparative example 2 as the negative electrode material of the lithium ion battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The application of the porous biomass carbon in the battery is characterized in that the porous biomass carbon is used as a negative electrode material of the lithium ion battery, and the preparation method of the porous biomass carbon comprises the following steps:
mixing straws with a calcium chloride solution, and standing for 12-24 hours to obtain a mixture, wherein the mass ratio of the straws to the calcium chloride in the calcium chloride solution is 1: 1.5-1: 3;
drying the mixture, and then carbonizing the mixture at the low temperature of 300-350 ℃ for 2-3 hours to obtain low-temperature carbide;
heating the low-temperature carbide to 500-700 ℃ to carry out high-temperature activation treatment for 1-3 hours to obtain a pre-product; and
soaking the pre-product for 12-24 hours by using inorganic strong acid, wherein the solid-to-liquid ratio of the pre-product to the inorganic strong acid is 1g:10 mL-1 g:20mL, and washing the pre-product to be neutral by using water at the temperature of 70-80 ℃ to obtain porous biomass carbon; the porosity of the porous biomass carbon is 61-70%, and the specific surface area of the porous biomass carbon is 237.2m2/g～370.6m2/g。
2. The use of the porous biomass carbon of claim 1 in a battery, wherein the straw is corn straw.
3. The use of the porous biomass carbon of claim 1 in a battery, wherein the straw is in powder form.
4. The use of the porous biomass carbon according to claim 1, wherein the strong inorganic acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid.
5. The use of the porous biomass carbon according to claim 1, wherein the concentration of the strong inorganic acid is 2mol/L to 6 mol/L.
6. The use of the porous biomass carbon in a battery according to claim 1, wherein the pre-product is soaked with strong inorganic acid for a period of 24 hours.
7. The use of the porous biomass carbon in the battery according to claim 1, wherein in the step of drying the mixture and then carbonizing the mixture at a low temperature of 300 ℃ to 350 ℃ for 2 hours to 3 hours to obtain a low-temperature carbide, the mixture is dried at a temperature of 60 ℃ to 70 ℃ and then dried.
8. The use of the porous biomass carbon in a battery according to claim 1, further comprising, before the step of soaking the pre-product with a strong inorganic acid for 12 to 24 hours, the steps of: washing the pre-product with water to obtain a recovered calcium chloride solution.
9. The use of the porous biomass carbon of claim 1 in a battery, further comprising the steps of: and drying the porous biomass carbon and then grinding.
10. The use of the porous biomass carbon according to claim 9 in a battery, wherein the porous biomass carbon is ground until the particle size of the porous biomass carbon is 800 to 900 microns.
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| CN108424303A (en) * | 2018-06-11 | 2018-08-21 | 孙永妮 | A method of preparing pest-resistant organic composite fertilizer using agriculture wastes |
| CN109734473B (en) * | 2019-03-11 | 2021-09-28 | 福州大学 | Porous ceramic and preparation method thereof |
| CN111864206B (en) * | 2019-04-30 | 2023-11-03 | 贝特瑞新材料集团股份有限公司 | Hard carbon negative electrode material, preparation method thereof, pole piece containing hard carbon negative electrode material and lithium ion battery |
| CN111408348A (en) * | 2020-04-28 | 2020-07-14 | 南阳师范学院 | Preparation method of straw-based porous biochar nanospheres |
| CN113381014B (en) * | 2021-06-08 | 2023-03-03 | 西安亚弘泰新能源科技有限公司 | Preparation method of ultralow-temperature lithium ion battery negative electrode material |
| CN113247985A (en) * | 2021-07-09 | 2021-08-13 | 生态环境部华南环境科学研究所 | TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method |
| CN113713771A (en) * | 2021-09-29 | 2021-11-30 | 长春工业大学 | Method for preparing adsorbing material and pentosan through biomass catalysis hydrothermal method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB125230A (en) * | 1918-04-16 | 1919-04-16 | Tai Koo Sugar Refining Company | Improved Process for the Production of Decolourizing Carbon. |
| CN1245776A (en) * | 1999-08-31 | 2000-03-01 | 林天安 | Method for preparing vehicular active carbon by using straw stalks and saw dust |
| CN103213982A (en) * | 2013-04-28 | 2013-07-24 | 广西大学 | Method for preparing activated carbon by carrying out microwave irradiation on banana straws |
| CN103539115A (en) * | 2013-10-31 | 2014-01-29 | 张京三 | Method for producing carbon fiber with castor seed shells and castor straws as raw materials |
| CN104071788A (en) * | 2014-07-02 | 2014-10-01 | 浙江大学 | Preparation method and application of improved straw active carbon based on CaCl2 |
| CN107151016A (en) * | 2017-06-28 | 2017-09-12 | 宿州市逢源生物科技有限公司 | A kind of preparation method that straw biomass charcoal is prepared under carbon dioxide atmosphere |
-
2017
- 2017-12-07 CN CN201711285423.2A patent/CN108033447B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB125230A (en) * | 1918-04-16 | 1919-04-16 | Tai Koo Sugar Refining Company | Improved Process for the Production of Decolourizing Carbon. |
| CN1245776A (en) * | 1999-08-31 | 2000-03-01 | 林天安 | Method for preparing vehicular active carbon by using straw stalks and saw dust |
| CN103213982A (en) * | 2013-04-28 | 2013-07-24 | 广西大学 | Method for preparing activated carbon by carrying out microwave irradiation on banana straws |
| CN103539115A (en) * | 2013-10-31 | 2014-01-29 | 张京三 | Method for producing carbon fiber with castor seed shells and castor straws as raw materials |
| CN104071788A (en) * | 2014-07-02 | 2014-10-01 | 浙江大学 | Preparation method and application of improved straw active carbon based on CaCl2 |
| CN107151016A (en) * | 2017-06-28 | 2017-09-12 | 宿州市逢源生物科技有限公司 | A kind of preparation method that straw biomass charcoal is prepared under carbon dioxide atmosphere |
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