CN110697717A - Biological morph-genetic structure SbC battery negative electrode material and preparation method thereof - Google Patents
Biological morph-genetic structure SbC battery negative electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN110697717A CN110697717A CN201910862744.7A CN201910862744A CN110697717A CN 110697717 A CN110697717 A CN 110697717A CN 201910862744 A CN201910862744 A CN 201910862744A CN 110697717 A CN110697717 A CN 110697717A
- Authority
- CN
- China
- Prior art keywords
- biological
- morph
- sbc
- negative electrode
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a SbC battery cathode material with a biological morph-genetic structure and a preparation method thereof, which comprises the steps of soaking diaphragma juglandis in acid liquor to obtain biological morph-genetic carbon with a retained raw material structure, and preparing a SbC composite material by a biological morph-genetic carbon composite method, wherein the invention has the following beneficial effects: 1. the electronic conductivity of Sb is improved by compounding with carbon; 2. the larger pore channels can provide a faster diffusion channel for the movement of K +, and the cellular thin-wall structure existing among different pore channels can shorten the transmission distance of K + in the SbC composite material, thereby improving the ionic conductivity of the composite material; 3. the specific surface area of the material can be improved by a plurality of micro-porous channels, and the specific capacity of the battery can be increased along with the improvement of the specific surface area; 4. the pore structure in the biological morph-genetic carbon can be controllably adjusted through KOH activation, so that the relation between different structures and performances can be further researched.
Description
Technical Field
The invention belongs to the field of energy materials, and particularly relates to a SbC battery cathode material with a biological genetic structure and a preparation method thereof.
Background
At present, since researchers are still in the beginning stage of research on potassium ion batteries and mainly focus on the research on positive electrode materials, and the types of materials studied have many similar directions to Li + batteries, and the research on negative electrode materials of potassium ion batteries is also necessary, metal negative electrode materials are adopted herein: sb and a core wood (carbon source) are doped through hydrothermal treatment, so that the obtained composite carbon has high specific capacity of a metal material and stable cycle performance of a carbon-based negative electrode.
As described above, antimony is a K + battery alloy cathode with great potential, but with respect to the problems of low antimony ion and electronic conductivity, and easy occurrence of volume expansion, the existing research is actually to perform nanocrystallization treatment on Sb, for example, Sb is prepared into structures such as nanoscale rods and nanoscale tubes, so that the ion transmission path is shortened, the specific surface area of the material is increased, and the ion conductivity is further improved. Meanwhile, Sb and carbon are combined into a composite material, such as SbC composite material and the like, so that the electronic conductivity and the electronic acceptance of the active material are improved. However, there are many deficiencies in the research so far:
① nanometer Sb particles are easy to agglomerate, so the agglomeration problem is reduced by using a carbon-coated composite method, ② has great difficulty and uncertainty due to the complex process for constructing a special structure, and a simple method needs to be found to construct a structure suitable for K + migration so as to realize controllable adjustment.
The biological morphgenetic material has a structure with multi-level distribution, the pore size distribution of the biological morphgenetic material is from nano-scale to micron-scale and is not the same, and the pore size of the biological morphgenetic material can be further increased by a KOH activation mode. The special hierarchical porous structure of the core-division wood is exactly in line with the ideal structure of the battery electrode material, and because the core-division wood has a plurality of pore passages with different sizes, different pore passages can provide different effects for the battery, electrolyte can be buffered in larger pores, the pore passages can also be used as the passages for the rapid transmission of ions, and a plurality of micro-pore passages can provide larger specific surface area for the carbon source.
① is compounded with carbon to improve the electronic conductivity of Sb, larger pore channels provide faster diffusion channels for the movement of K +, cellular thin-wall structures among different pore channels can shorten the transmission distance of K + in SbC composite material to improve the ionic conductivity, the specific surface area of the material can be improved by a plurality of micro pore channels, the specific capacity of a battery can be increased along with the improvement of the specific surface area, and the pore channel structure in the biological morphotropic carbon can be controllably adjusted through KOH activation, so that the relation among different structures and performances can be further researched.
Disclosure of Invention
Aiming at the technical defects, the invention provides a SbC battery cathode material with a biological morph-genetic structure and a preparation method thereof, the invention adopts a biological morph-genetic material such as diaphragma juglandis, is natural, environment-friendly, cheap and easy to obtain, and adopts the following technical scheme.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a biological morph-genetic structure SbC battery negative electrode material comprises the following steps:
s1, selecting a core wood and mechanically stripping;
s2, cleaning the surface of the split core wood mechanically stripped in the step S1 with deionized water to remove impurities;
s3, putting the diaphragma juglandis processed in the step S2 into a drying oven for drying for 24 hours, and selecting a certain mass of dried diaphragma juglandis to be soaked in a hydrochloric acid solution with a certain concentration for 24 hours after drying;
s4, adding the diaphragma juglandis subjected to soaking in the step S3 and KOH into a cylindrical nickel boat according to a certain mass ratio, adding a proper amount of deionized water until the diaphragma juglandis completely soaked for 24 hours, covering with a preservative film and pricking;
s5, pouring out the KOH solution in the nickel boat, putting the nickel boat in a drying box at 60 ℃, and drying the air components for 48 hours;
s6, after being fully dried, the diaphragma juglandis is put into a nickel boat and put into a tube furnace, a certain temperature rise gradient is set, and the diaphragma juglandis is fired in argon atmosphere;
s7, after the firing is finished, naturally cooling the material to be below 80 ℃, closing the tube furnace and the argon bottle, cooling for 12 hours, and taking out the material;
s8, grinding the material cooled in the step S7 by using a mortar and enabling the material to pass through a 300-mesh sieve to obtain biological morph-genetic carbon;
s9, introducing 1g of sodium hypophosphite, 0.5g of biological morphgenetic carbon, 0.20g of sodium hydroxide and antimony trichloride into a reaction kettle and dissolving in ethanol;
s10, the reaction kettle cover is stirred for 2 hours by using a film. Then the reaction kettle is put into a large kettle and placed in a homogeneous reactor, the temperature is set to be 180 ℃, the rotating speed is 11, and the hydrothermal treatment is carried out for 12 hours;
s11, opening the reaction kettle after the reaction kettle is fully cooled, taking out the mixed liquid, and carrying out solid-liquid separation by using a high-speed centrifuge;
s12, taking out the solid, adding a large amount of deionized water, performing suction filtration by using a suction filtration instrument, and washing off NaCl in the solid phase;
s13, taking out the cleaned solid phase, putting the solid phase into a glass culture dish, and putting the glass culture dish into a drying oven to dry for 12 hours at the temperature of 60 ℃;
s14, placing the pure Sb, the citric acid and the deionized water dried in the step S13 in a glass cup, placing the glass cup on a magnetic stirrer, stirring the glass cup for 30min, and then placing the glass cup in a drying oven to dry the glass cup for 48 h;
and S15, placing the dried solid mixture in a nickel boat and placing the nickel boat in a tube furnace, setting a certain temperature rise gradient, and firing the mixture in an argon atmosphere to obtain the biological morph-genetic structure SbC battery cathode material.
Preferably, the mass of the split core wood after the completion of the drying in the step S3 is 25 g.
Preferably, the concentration of hydrochloric acid in the step S3 is 1 mol/L.
Preferably, in step S4, the mass ratio of cedar to KOH is 1: 1.
preferably, the temperature rise gradient in the step S6 is 60min for 20-200 ℃, the temperature is slowly raised to 200-400 ℃ according to 2 ℃/min, 200min for 400-800 ℃, and the temperature is preserved for 120min at 800 ℃.
Preferably, the temperature rise gradient in the step S15 is 60min at 20-200 ℃, 90min at 200-650 ℃, and then the temperature is kept at 650 ℃ for 4 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the electronic conductivity of Sb is improved by compounding with carbon;
2. the larger pore channels can provide a faster diffusion channel for the movement of K +, and the cellular thin-wall structure existing among different pore channels can shorten the transmission distance of K + in the SbC composite material, thereby improving the ionic conductivity of the composite material;
3. the specific surface area of the material can be improved by the plurality of micro-pores, and the specific capacity of the battery can be increased along with the improvement of the specific surface area;
4. the pore structure in the biological morph-genetic carbon can be controllably adjusted through KOH activation, so that the relation between different structures and performances can be further researched.
Drawings
FIGS. 1-4 are SEM, XRD, rate performance curves and impedance performance curves of electrode materials prepared by the direct compounding method.
FIGS. 5-8 are SEM, XRD, rate performance curves and impedance performance curves of electrode materials prepared by KOH activation recombination.
FIGS. 9-12 are SEM, XRD, rate performance curves and impedance performance curves of electrode materials prepared by carbon coating.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a biological morph-genetic structure SbC battery negative electrode material comprises the following steps:
s1, selecting a core wood and mechanically stripping;
s2, cleaning the surface of the split core wood mechanically stripped in the step S1 with deionized water to remove impurities;
s3, placing 25g of diaphragma juglandis processed in the step S2 into a drying oven for drying for 24 hours, and selecting a certain mass of dried diaphragma juglandis to be soaked in a hydrochloric acid solution with the concentration of 1mol/L for 24 hours after drying;
s4, mixing the diaphragma juglandis after the soaking in the step S3 with KOH according to the mass ratio of 1: 1, adding the mixture into a cylindrical nickel boat, adding a proper amount of deionized water until the mixture is completely soaked for 24 hours, covering a preservative film on the cylindrical nickel boat, and pricking holes;
s5, pouring out the KOH solution in the nickel boat, putting the nickel boat in a drying box at 60 ℃, and drying the air components for 48 hours;
s6, after being fully dried, the diaphragma juglandis is put in a nickel boat and put in a tube furnace, protected firing is carried out under argon atmosphere, and a temperature rise gradient is set, namely 60min is needed at 20-200 ℃, the temperature is slowly raised at 200-400 ℃ according to 2 ℃/min, 200min is needed at 400-800 ℃, and the temperature is preserved for 120min at 800 ℃;
s7, after the firing is finished, naturally cooling the material to be below 80 ℃, closing the tube furnace and the argon bottle, cooling for 12 hours, and taking out the material;
s8, grinding the material cooled in the step S7 by using a mortar and enabling the material to pass through a 300-mesh sieve to obtain biological morph-genetic carbon;
s9, introducing 1g of sodium hypophosphite, 0.5g of biological morphgenetic carbon, 0.20g of sodium hydroxide and antimony trichloride into a reaction kettle and dissolving in ethanol;
s10, the reaction kettle cover is stirred for 2 hours by using a film. Then the reaction kettle is put into a large kettle and placed in a homogeneous reactor, the temperature is set to be 180 ℃, the rotating speed is 11, and the hydrothermal treatment is carried out for 12 hours;
s11, opening the reaction kettle after the reaction kettle is fully cooled, taking out the mixed liquid, and carrying out solid-liquid separation by using a high-speed centrifuge;
s12, taking out the solid, adding a large amount of deionized water, performing suction filtration by using a suction filtration instrument, and washing off NaCl in the solid phase;
s13, taking out the cleaned solid phase, putting the solid phase into a glass culture dish, and putting the glass culture dish into a drying oven to dry for 12 hours at the temperature of 60 ℃;
s14, placing the pure Sb, the citric acid and the deionized water dried in the step S13 in a glass cup, placing the glass cup on a magnetic stirrer, stirring the glass cup for 30min, and then placing the glass cup in a drying oven to dry the glass cup for 48 h;
s15, placing the dried solid mixture in a nickel boat and placing the nickel boat in a tube furnace, setting a certain temperature rise gradient, namely, 60min is needed at 20-200 ℃, 90min is needed at 200-650 ℃, then, heat preservation is carried out for 4h at 650 ℃, and protective firing is carried out under argon atmosphere to obtain the biological morph-genetic structure SbC battery cathode material;
this compounding method is the KOH activated compounding method (diaphragma + KOH + SbCl 3).
Example 2
A preparation method of a biological morph-genetic structure SbC battery negative electrode material comprises the following steps:
s1, selecting a core wood and mechanically stripping;
s2, cleaning the surface of the split core wood mechanically stripped in the step S1 with deionized water to remove impurities;
s3, diluting the diaphragma juglandis with deionized water until the PH value reaches 7;
s4, putting the diaphragma juglandis into the drying oven again, and drying for 48h at the temperature of 60 ℃. Fully drying the mixture;
s5, after being fully dried, the diaphragma juglandis is put in a nickel boat and put in a tube furnace, protected firing is carried out under argon atmosphere, and a temperature rise gradient is set, namely 60min is needed at 20-200 ℃, the temperature is slowly raised at 200-400 ℃ according to 2 ℃/min, 200min is needed at 400-800 ℃, and the temperature is preserved for 120min at 800 ℃;
s6, after the firing is finished, naturally cooling the material to be below 80 ℃, closing the tube furnace and the argon bottle, cooling for 12 hours, and taking out the material;
s7, grinding the material cooled in the step S7 by using a mortar and enabling the material to pass through a 300-mesh sieve to obtain biological morph-genetic carbon;
s8, introducing 1g of sodium hypophosphite, 0.5g of biological morphgenetic carbon, 0.20g of sodium hydroxide and antimony trichloride into a reaction kettle and dissolving in ethanol;
s9, the reaction kettle cover is stirred for 2 hours by using a film. Then the reaction kettle is put into a large kettle and placed in a homogeneous reactor, the temperature is set to be 180 ℃, the rotating speed is 11, and the hydrothermal treatment is carried out for 12 hours;
s10, opening the reaction kettle after the reaction kettle is fully cooled, taking out the mixed liquid, and carrying out solid-liquid separation by using a high-speed centrifuge;
s11, taking out the solid, adding a large amount of deionized water, performing suction filtration by using a suction filtration instrument, and washing off NaCl in the solid phase;
s12, taking out the cleaned solid phase, putting the solid phase into a glass culture dish, and putting the glass culture dish into a drying oven to dry for 12 hours at the temperature of 60 ℃;
s13, placing the pure Sb, the citric acid and the deionized water dried in the step S13 in a glass cup, placing the glass cup on a magnetic stirrer, stirring the glass cup for 30min, and then placing the glass cup in a drying oven to dry the glass cup for 48 h;
s14, placing the dried solid mixture in a nickel boat and placing the nickel boat in a tube furnace, setting a certain temperature rise gradient, namely, 60min is needed at 20-200 ℃, 90min is needed at 200-650 ℃, then, heat preservation is carried out for 4h at 650 ℃, and protective firing is carried out under argon atmosphere to obtain the biological morph-genetic structure SbC battery cathode material;
firstly, 10ml of ethanol is taken out by a 20ml measuring cylinder and placed in 4 glasses with the volume of 50ml and the glasses are marked as No. 1, No. 2, No. 3 and No. 4 respectively, and then 0.30g, 0.50g and 1g of SbCl3 are respectively weighed and added into the glasses with the volume of 2, No. 3 and No. 4, and the 4 glasses are marked as A group. Then, 4 parts of 15ml ethanol are respectively weighed by a 20ml measuring cylinder into 4 reaction kettles (which are marked as 1, 2, 3 and 4 and correspond to glass cups in the same way), 4 parts of 1g sodium hypophosphite (NaH2PO 2. H2O) and 0.2g sodium hydroxide (NaOH) are respectively weighed by a medicine spoon and are respectively added into 4 reaction kettles, and the 4 reaction kettles are marked as group B. And placing A, B groups of beakers and reaction kettles into an ultrasonic cleaning instrument for ultrasonic treatment for 15 min. And after ultrasonic treatment, placing the B group of reaction kettles on a magnetic stirrer, adding a rotor for stirring, and slowly dropwise adding the solution in the A group into the reaction kettle corresponding to the B group by using a disposable rubber-head dropper. The reaction vessel was then stirred on the lid with a film for 2 h. Then the reaction kettle is put into a large kettle and placed in a homogeneous reactor (180 ℃, the rotating speed is about 11) for hydrothermal treatment for 8 hours.
This preparation is a direct compounding process (diaphragma + SbCl 3).
Example 3
A preparation method of a biological morph-genetic structure SbC battery negative electrode material comprises the following steps:
s1, selecting a core wood and mechanically stripping;
s2, cleaning the surface of the split core wood mechanically stripped in the step S1 with deionized water to remove impurities;
s3, placing 25g of diaphragma juglandis processed in the step S2 into a drying oven for drying for 24 hours, and selecting a certain mass of dried diaphragma juglandis to be soaked in a hydrochloric acid solution with the concentration of 1mol/L for 24 hours after drying;
s4, mixing the diaphragma juglandis after the soaking in the step S3 with KOH according to the mass ratio of 1: 1, adding the mixture into a cylindrical nickel boat, adding a proper amount of deionized water until the mixture is completely soaked for 24 hours, covering a preservative film on the cylindrical nickel boat, and pricking holes;
s5, pouring out the KOH solution in the nickel boat, putting the nickel boat in a drying box at 60 ℃, and drying the air components for 48 hours;
s6, after being fully dried, the diaphragma juglandis is put in a nickel boat and put in a tube furnace, protected firing is carried out under argon atmosphere, and a temperature rise gradient is set, namely 60min is needed at 20-200 ℃, the temperature is slowly raised at 200-400 ℃ according to 2 ℃/min, 200min is needed at 400-800 ℃, and the temperature is preserved for 120min at 800 ℃;
s7, after the firing is finished, naturally cooling the material to be below 80 ℃, closing the tube furnace and the argon bottle, cooling for 12 hours, and taking out the material;
s8, grinding the material cooled in the step S7 by using a mortar and enabling the material to pass through a 300-mesh sieve to obtain biological morph-genetic carbon;
s9, obtaining the nano-grade pure antimony, which comprises the following steps:
a: weighing 10ml of ethanol in a 20ml volumetric flask, putting the ethanol in a 50ml glass cup, and weighing 4.56g of SbCl3 in a spoon;
b: 15ml of ethanol is weighed in a 20ml volumetric flask and placed in a reaction kettle, then 2.44g of sodium hypophosphite and 0.30g of sodium hydroxide are weighed in a medicine spoon, and a beaker and the reaction kettle are placed in an ultrasonic cleaning instrument and are subjected to ultrasonic treatment for 15 min. And after ultrasonic treatment, placing the B group of reaction kettles on a magnetic stirrer, adding a rotor for stirring, and slowly dropwise adding the solution in the A group into the reaction kettle corresponding to the B group by using a disposable rubber-head dropper. The reaction vessel was then stirred on the lid with a film for 2 h. Then the reaction kettle is put into a large kettle and placed in a homogeneous reactor (180 ℃, the rotating speed is about 11) for hydrothermal treatment for 12 hours.
C: and opening the reaction kettle after the reaction kettle is fully cooled, taking out the mixed liquid, performing solid-liquid separation by using a high-speed centrifuge, centrifuging the mixed liquid for about 5 times in three pipes by taking absolute ethyl alcohol as a solvent until the pH value is neutral (to prevent residual Sb3+ from reacting with water to generate Sb2O3), taking out the solid, adding a large amount of deionized water, and performing suction filtration by using a suction filtration instrument to wash off NaCl in the solid phase. Then, the washed solid phase was taken out and placed in a glass petri dish, and the dish was dried in a drying oven at 60 ℃ for 12 hours to obtain dry Sb.
This preparation is a carbon coating process (citric acid + SbCl 3).
Further, XRD test is carried out on the dried pure Sb to observe whether impurities are contained or not, and if the impurities are not contained, the molar mass ratio of the citric acid to the pure Sb is respectively 0: 1. 1: 2. 1: 1. 2: 1, (namely 0g, 0.96g, 1.92g and 3.84g of citric acid respectively) citric acid + deionized water + pure antimony, placing the mixture in a glass cup, placing the glass cup on a magnetic stirrer, stirring the mixture for 30min, and then placing the glass cup in a drying oven to dry the glass cup for 48 h. And placing the dried solid mixture in a nickel boat, placing the nickel boat in a tubular furnace, calcining the solid mixture at 650 ℃ under the protection of argon atmosphere, wherein 60min is needed when the temperature is increased from room temperature to 200 ℃, 90min is needed when the temperature is increased from 200 ℃ to 650 ℃, and then preserving the heat for 4h at 650 ℃, thereby obtaining the SbC material prepared by the carbon coating method.
The invention has the following beneficial effects:
compared with the prior art, the invention has the following beneficial effects:
1. the electronic conductivity of Sb is improved by compounding with carbon;
2. the larger pore channels can provide a faster diffusion channel for the movement of K +, and the cellular thin-wall structure existing among different pore channels can shorten the transmission distance of K + in the SbC composite material, thereby improving the ionic conductivity of the composite material;
3. the specific surface area of the material can be improved by the plurality of micro-pores, and the specific capacity of the battery can be increased along with the improvement of the specific surface area;
4. the pore structure in the biological morph-genetic carbon can be controllably adjusted through KOH activation, so that the relation between different structures and performances can be further researched.
Claims (7)
1. A preparation method of a biological morph-genetic structure SbC battery negative electrode material is characterized by comprising the following steps:
s1, selecting a core wood and mechanically stripping;
s2, cleaning the surface of the split core wood mechanically stripped in the step S1 with deionized water to remove impurities;
s3, putting the diaphragma juglandis processed in the step S2 into a drying oven for drying for 24 hours, and selecting a certain mass of dried diaphragma juglandis to be soaked in a hydrochloric acid solution with a certain concentration for 24 hours after drying;
s4, adding the diaphragma juglandis subjected to soaking in the step S3 and KOH into a cylindrical nickel boat according to a certain mass ratio, adding a proper amount of deionized water until the diaphragma juglandis completely soaked for 24 hours, covering with a preservative film and pricking;
s5, pouring out the KOH solution in the nickel boat, putting the nickel boat in a drying box at 60 ℃, and drying the air components for 48 hours;
s6, after being fully dried, the diaphragma juglandis is put into a nickel boat and put into a tube furnace, a certain temperature rise gradient is set, and the diaphragma juglandis is fired in argon atmosphere;
s7, after the firing is finished, naturally cooling the material to be below 80 ℃, closing the tube furnace and the argon bottle, cooling for 12 hours, and taking out the material;
s8, grinding the material cooled in the step S7 by using a mortar and enabling the material to pass through a 300-mesh sieve to obtain biological morph-genetic carbon;
s9, introducing 1g of sodium hypophosphite, 0.5g of biological morphgenetic carbon, 0.20g of sodium hydroxide and antimony trichloride into a reaction kettle and dissolving in ethanol;
s10, the reaction kettle cover is stirred for 2 hours by using a film. Then the reaction kettle is put into a large kettle and placed in a homogeneous reactor, the temperature is set to be 180 ℃, the rotating speed is 11, and the hydrothermal treatment is carried out for 12 hours;
s11, opening the reaction kettle after the reaction kettle is fully cooled, taking out the mixed liquid, and carrying out solid-liquid separation by using a high-speed centrifuge;
s12, taking out the solid, adding a large amount of deionized water, performing suction filtration by using a suction filtration instrument, and washing off NaCl in the solid phase;
s13, taking out the cleaned solid phase, putting the solid phase into a glass culture dish, and putting the glass culture dish into a drying oven to dry for 12 hours at the temperature of 60 ℃;
s14, placing the pure Sb, the citric acid and the deionized water dried in the step S13 in a glass cup, placing the glass cup on a magnetic stirrer, stirring the glass cup for 30min, and then placing the glass cup in a drying oven to dry the glass cup for 48 h;
and S15, placing the dried solid mixture in a nickel boat and placing the nickel boat in a tube furnace, setting a certain temperature rise gradient, and firing the mixture in an argon atmosphere to obtain the biological morph-genetic structure SbC battery cathode material.
2. The method for preparing the negative electrode material of the biological morph-genetic structure SbC battery according to claim 1, wherein the method comprises the following steps: the mass of the diaphragma juglandis is 25g after the drying in the step S3 is finished.
3. The method for preparing the negative electrode material of the biological morph-genetic structure SbC battery according to claim 1, wherein the method comprises the following steps: the concentration of the hydrochloric acid in the step S3 is 1 mol/L.
4. The method for preparing the negative electrode material of the biological morph-genetic structure SbC battery according to claim 1, wherein the method comprises the following steps: in the step S4, the mass ratio of the central wood to the KOH is 1: 1.
5. the method for preparing the negative electrode material of the biological morph-genetic structure SbC battery according to claim 1, wherein the method comprises the following steps: the temperature rise gradient in the step S6 is 60min for 20-200 ℃, the temperature is slowly raised at 200-400 ℃ according to 2 ℃/min, 200min for 400-800 ℃, and the temperature is preserved for 120min at 800 ℃.
6. The method for preparing the negative electrode material of the biological morph-genetic structure SbC battery according to claim 1, wherein the method comprises the following steps: the temperature rise gradient in the step S15 is 60min at 20-200 ℃, 90min at 200-650 ℃, and then the temperature is kept for 4h at 650 ℃.
7. A biological morph-genetic structure SbC battery negative electrode material is characterized in that: the biological morph-genetic structure SbC battery negative electrode material is prepared by the preparation method of the biological morph-genetic structure SbC battery negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910862744.7A CN110697717B (en) | 2019-09-12 | 2019-09-12 | Sb/C battery cathode material with biological morph-genetic structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910862744.7A CN110697717B (en) | 2019-09-12 | 2019-09-12 | Sb/C battery cathode material with biological morph-genetic structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110697717A true CN110697717A (en) | 2020-01-17 |
| CN110697717B CN110697717B (en) | 2021-09-21 |
Family
ID=69194818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910862744.7A Active CN110697717B (en) | 2019-09-12 | 2019-09-12 | Sb/C battery cathode material with biological morph-genetic structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110697717B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100258761A1 (en) * | 2005-10-17 | 2010-10-14 | Gue-Sung Kim | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN102324497A (en) * | 2011-09-21 | 2012-01-18 | 上海大学 | A kind of graphene-supported carbon coats the preparation method of the lithium cell cathode material of tin antimony |
| US20120045687A1 (en) * | 2010-08-19 | 2012-02-23 | Byd Company Limited | Negative active materials, lithium ion batteries, and methods thereof |
| CN103219502A (en) * | 2013-04-28 | 2013-07-24 | 华南师范大学 | Lithium ion battery negative electrode material Sn2Sb/C nuclear shell as well as preparation method and application thereof |
| CN107275618A (en) * | 2017-07-05 | 2017-10-20 | 中国矿业大学 | A kind of preparation method of carbon-coated antimony porous material for ion battery negative pole |
| CN110061215A (en) * | 2019-04-24 | 2019-07-26 | 华中科技大学 | A kind of composite construction and preparation method thereof for negative electrode of lithium ion battery |
-
2019
- 2019-09-12 CN CN201910862744.7A patent/CN110697717B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100258761A1 (en) * | 2005-10-17 | 2010-10-14 | Gue-Sung Kim | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| US20120045687A1 (en) * | 2010-08-19 | 2012-02-23 | Byd Company Limited | Negative active materials, lithium ion batteries, and methods thereof |
| CN102324497A (en) * | 2011-09-21 | 2012-01-18 | 上海大学 | A kind of graphene-supported carbon coats the preparation method of the lithium cell cathode material of tin antimony |
| CN103219502A (en) * | 2013-04-28 | 2013-07-24 | 华南师范大学 | Lithium ion battery negative electrode material Sn2Sb/C nuclear shell as well as preparation method and application thereof |
| CN107275618A (en) * | 2017-07-05 | 2017-10-20 | 中国矿业大学 | A kind of preparation method of carbon-coated antimony porous material for ion battery negative pole |
| CN110061215A (en) * | 2019-04-24 | 2019-07-26 | 华中科技大学 | A kind of composite construction and preparation method thereof for negative electrode of lithium ion battery |
Non-Patent Citations (4)
| Title |
|---|
| NANA WANG ET AL: "One-Dimensional Yolk−Shell Sb@Ti−O−P Nanostructures as a High-Capacity and High-Rate Anode Material for Sodium Ion Batteries", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| XUAN-MANH PHAM ET AL: "A self-encapsulated porous Sb–C nanocomposite anode with excellent Na-ion storage performance", 《NANOSCALE》 * |
| 孟伟嘉: "锑/生物质碳微球作为锂/钠离子电池负极材料的稳定性研究", 《中国优秀硕士学位论文全文数据库·工程科技Ⅰ辑》 * |
| 罗雯: "锑基及铋基纳米电极材料的设计制备和电化学性能研究", 《中国博士学位论文全文数据库·工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110697717B (en) | 2021-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110492081B (en) | Preparation method and application of cobalt selenide/zinc selenide @ nitrogen-doped porous carbon nanotube | |
| CN109216681B (en) | Based on TiO2Lithium metal cathode material of nanotube array/titanium foam and preparation method thereof | |
| CN105810929A (en) | Treatment method for reducing residual alkalis on surface of high nickel material | |
| CN109037552B (en) | Preparation method of diaphragm material for sodium-sulfur battery | |
| CN106711443B (en) | A kind of shuttle shape cobalt acid manganese material and its preparation and application | |
| CN108539263B (en) | Preparation method of solid electrolytes with sandwich structure | |
| CN108428882B (en) | Zinc silicate/carbon micro-nano hierarchical structure compound and preparation method thereof | |
| CN110697717B (en) | Sb/C battery cathode material with biological morph-genetic structure and preparation method thereof | |
| CN112786863A (en) | Zn2SiO4Preparation method of high-rate lithium ion battery cathode material | |
| CN112520709A (en) | Preparation and application method of ultrathin tungsten diselenide nanoflower | |
| CN109286018B (en) | Preparation method of ultrathin two-dimensional carbon sheet | |
| CN109133191B (en) | Three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material and preparation method thereof | |
| CN110518197A (en) | A kind of diatom complex material and preparation method thereof and the application in lithium ion battery | |
| CN107394151B (en) | A kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide | |
| CN110483219A (en) | Cubic structure Composite Energetic Materials and preparation method thereof | |
| CN114883748A (en) | Composite diaphragm for lithium ion battery and preparation method thereof | |
| CN114773617A (en) | Core-shell gradient ternary precursor and preparation method and application thereof | |
| CN110171814B (en) | Method for synthesizing carbon nanosheet by catalysis of water-soluble KCl and energy storage and sustained release application | |
| CN114039044A (en) | Three-dimensional electrode material composed of carbon-coated nanosheets and preparation method thereof | |
| CN113562716A (en) | Solvothermal preparation of Zn0.5Ti2（PO4）3Method for preparing/C nano-flake negative electrode material | |
| CN116632233B (en) | High-performance sodium ion battery doped hard carbon negative electrode material and preparation method thereof | |
| CN109256528B (en) | Lithium iron phosphate-bacterial cellulose-graphene composite material and preparation method and application thereof | |
| CN109301200A (en) | AZO modified 3 D copper/lithium an- ode material preparation method | |
| CN115911321B (en) | Diatom-based composite material and preparation method and application thereof | |
| CN111048751A (en) | Zinc manganate/pine needle biomass charcoal composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |