CN116161640A - Spherical long-circulation stable biomass hard carbon material, preparation method and application - Google Patents
Spherical long-circulation stable biomass hard carbon material, preparation method and application Download PDFInfo
- Publication number
- CN116161640A CN116161640A CN202211100799.2A CN202211100799A CN116161640A CN 116161640 A CN116161640 A CN 116161640A CN 202211100799 A CN202211100799 A CN 202211100799A CN 116161640 A CN116161640 A CN 116161640A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- carbon material
- biomass
- spherical
- long
- 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.)
- Pending
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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of biomass charcoal materials, and discloses a preparation method of a spherical long-circulation stable biomass hard charcoal material, which comprises the following steps of S1, preprocessing biomass raw materials, removing impurities, purifying and drying to obtain a precursor sample; s2, heating the precursor sample to a pre-carbonization temperature under a protective atmosphere for calcination, naturally cooling, grinding and crushing to obtain pre-carbonized powder; s3, fully mixing the pre-carbonized powder with thiourea solution, uniformly stirring, centrifugally washing and drying to obtain pre-carbonized powder containing nitrogen and sulfur sources; s4, heating the nitrogen-containing sulfur source pre-carbonized powder to a carbonization temperature under a protective atmosphere for calcination, and naturally cooling to obtain a spherical biomass hard carbon material with long circulation stability; the invention solves the problems of low initial coulombic efficiency, low specific capacity and poor stability of cycle performance of the battery when the hard carbon material is used for sodium ion batteries in the prior art, and is suitable for preparing biomass carbon materials.
Description
Technical Field
The invention relates to the technical field of biomass charcoal materials, in particular to a spherical biomass hard charcoal material with long circulation stability, a preparation method and application.
Background
With the development of society and science and technology, the demand for energy is gradually increased, and lithium batteries have the advantages of high energy density, long service time, environmental friendliness and the like, and are widely applied. Although the lithium ion battery technology is gradually mature, the consumption of lithium resources is continuously increased due to the explosive growth of the demand, and the problems of high social and economic values, scarcity and uneven distribution of the lithium resources are gradually highlighted. Sodium has similar physical and chemical properties to lithium, is abundant in reserves and low in cost, so that sodium ion batteries are increasingly attracting attention in the field as important energy storage devices of the next generation. In recent years, research on the application of hard carbon materials as negative electrode materials in sodium ion batteries has been increasing, and the hard carbon materials are considered as negative electrode materials of sodium ion batteries which are most likely to realize industrialization.
Biomass is used as a hard carbon precursor, and is a focus of attention for preparing hard carbon materials because of the advantages of being ecological, rich in resources, easy to obtain, renewable and the like. The biomass direct carbonization in one step is the simplest and convenient method for preparing biomass hard carbon, and although a certain result is achieved at present, the hard carbon material prepared by the existing method is used as a sodium ion battery, and has low coulombic efficiency, low specific capacity and poor stability of cycle performance for the first time. Therefore, development of a hard carbon material with higher capacity, higher rate capability and longer cycle life, and which has high initial coulombic efficiency and high specific capacity and stable cycle performance when used in sodium ion batteries, is highly demanded in the art.
Disclosure of Invention
The invention aims to provide a spherical biomass hard carbon material with long circulation stability, a preparation method and application thereof, so as to solve the problems of low initial coulomb efficiency, low specific capacity and poor stability of circulation performance of a battery when the hard carbon material is used for a sodium ion battery in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a spherical long-circulation stable biomass hard carbon material comprises the following steps:
s1, sequentially preprocessing, removing impurities, purifying and drying a biomass raw material to obtain a precursor sample;
s2, heating the precursor sample obtained in the step S1 to a pre-carbonization temperature under a protective atmosphere for calcination, naturally cooling, and grinding and crushing to obtain pre-carbonized powder;
s3, fully mixing the pre-carbonized powder obtained by the treatment of S2 with thiourea solution, uniformly stirring, centrifugally washing and drying to obtain pre-carbonized powder containing nitrogen and sulfur sources;
and S4, heating the nitrogen and sulfur source-containing pre-carbonized powder obtained in the step S3 to the carbonization temperature under the protective atmosphere for calcining, and naturally cooling to obtain the spherical biomass hard carbon material with long circulation stability.
Further, in S1, the biomass raw material includes one or more of banana tree, banana leaf, corm, coconut shell, durian shell, mangosteen shell; the pretreatment is to cut and refine the biomass raw material; adding deionized water into the biomass raw material for ultrasonic treatment for not less than 30min, washing off obvious impurities on the surface, adding 0.5-2 mol/L nitric acid into the biomass raw material after ultrasonic treatment, and stirring for 2-6 h at normal temperature; the purification and drying are to wash the biomass raw material after impurity removal with deionized water and then dry.
Further, in S2, the pre-carbonization temperature is 400-600 ℃, the pre-carbonization time is 2-3 h, and the heating rate is 3-5 ℃/min; the protective atmosphere is one or more inert gases selected from nitrogen, argon and nitrogen-argon.
Further, in the S3, the mass ratio of the thiourea solution to the pre-carbonized powder is 0-3:1 in the process of mixing the thiourea solution and the pre-carbonized powder, wherein the concentration of the thiourea solution is 0-3 mol/L, and the stirring time is 6-12 h.
Further, in S4, the carbonization temperature is 1200-1600 ℃, the carbonization time is 2-3 h, and the heating rate is 3-5 ℃/min; the protective atmosphere is one or more inert gases selected from nitrogen, argon and nitrogen-argon.
The principle of the technical scheme is as follows:
pretreating a biomass raw material, sequentially carrying out pre-carbonization and grinding and crushing to obtain pre-carbonized powder, introducing thiourea to carry out nitrogen vulcanization, and finally carrying out carbonization treatment to obtain a spherical biomass hard carbon material with long circulation stability; the pretreatment is to refine the biomass raw material, so that the impurities can be conveniently and subsequently removed to further reduce the impurity content, thereby reducing ash content; on the one hand, the pre-carbonized raw materials are easier to crush, so that the specific surface area of the reaction is increased, and on the other hand, the raw materials are subjected to pore opening treatment, so that nitrogen and sulfur sources are conveniently introduced subsequently; thiourea is selected as a nitrogen-sulfur source because thiourea contains rich nitrogen elements and sulfur elements, two elements can be introduced into the hard carbon material at the same time to form a co-doped system, and sulfur atoms and nitrogen atoms have stronger binding capacity with the hard carbon, so that rich active sites are highlighted, and more sodium storage space is provided.
The biomass hard carbon material prepared by the preparation method of the spherical long-circulation stable biomass hard carbon material.
The application of the spherical long-cycle stable biomass hard carbon material in the sodium ion battery is characterized in that the biomass hard carbon material is used as a negative electrode active material of the sodium ion battery.
Further, the specific method for using the biomass hard carbon material as the negative electrode active material of the sodium ion battery comprises the following steps: and mixing the biomass hard carbon material, the conductive agent and the binder according to the mass ratio of 7:2:1 or 8:1:1 to prepare negative electrode slurry, coating the negative electrode slurry on a current collector, and drying to obtain the negative electrode active material of the sodium ion battery.
Further, the conductive agent is conductive carbon black; the binder is any one of sodium carboxymethyl cellulose, polyvinylidene fluoride and sodium alginate; the current collector is copper foil or aluminum foil.
Further, the drying temperature is 80-120 ℃ and the drying time is 12-24 h.
The beneficial effects of this technical scheme are:
1. the precursor adopted by the invention is biomass material, and has the advantages of abundant resources, low cost, easy acquisition, wide sources, high carbon yield and good economic benefit;
2. the selected nitrogen and sulfur source has the advantages of easily available raw materials, simple and convenient operation, energy consumption saving and suitability for large-scale industrial production;
3. the spherical biomass hard carbon material with long circulation stability has rich active sites, and is beneficial to improving sodium intercalation and sodium deintercalation capability in the circulation process;
4. can meet various performance requirements of the negative electrode material of the sodium ion battery, and has wide application prospect.
Drawings
FIG. 1 is an SEM image of a hard carbon material prepared according to example 2 of the present invention;
FIG. 2 is a first charge-discharge diagram of a hard carbon material-assembled sodium ion battery prepared in example 2 of the present invention;
fig. 3 is a cycle performance chart of a hard carbon material assembled sodium ion battery prepared in example 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and embodiments:
example 1
A spherical long-circulation stable biomass hard carbon material comprises the following steps:
s1, preprocessing a precursor: cutting fresh banana tree leaves into small pieces, then putting the small pieces into water, performing ultrasonic treatment for 30min, washing off obvious impurities, adding 1mol/L nitric acid into the biomass raw materials after ultrasonic treatment, and stirring at normal temperature for 2h; washing the biomass raw material subjected to impurity removal by deionized water; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, precursor pre-carbonization: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, naturally cooling to obtain a pre-carbonized product, taking out, and grinding by using a mortar to obtain pre-carbonized powder;
s3, nitrogen vulcanization: 2g of the pre-carbonized powder obtained in the step S2 is added into the prepared thiourea solution, wherein the method for preparing the thiourea solution comprises the following steps: dissolving 2g of thiourea in 60mL of deionized water, stirring at normal temperature for 6 hours under a magnetic stirrer, centrifugally washing, transferring to an 80 ℃ oven, and drying for 12 hours to obtain dried pre-carbonized powder of a nitrogen-sulfur source;
s4, carbonizing: and (3) putting 1g of the pre-carbonized powder containing the nitrogen and sulfur source obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the spherical biomass hard carbon material with long circulation stability.
And uniformly mixing the prepared spherical biomass hard carbon material with long circulation stability as a negative electrode active substance, sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, adding an aqueous solvent to prepare a negative electrode slurry, coating the negative electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at 100 ℃ for 12 hours, and rolling and blanking to obtain the hard carbon negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial coulomb efficiency is 86%, and the stable cycle can be realized for 500 circles under the current density of 200 mA/g.
Example 2
A spherical long-circulation stable biomass hard carbon material comprises the following steps:
s1, preprocessing a precursor: cutting fresh banana tree leaves into small pieces, then putting the small pieces into water, carrying out ultrasonic treatment for 30min, washing off obvious impurities, adding 1mol/L nitric acid into the biomass raw material after ultrasonic treatment, and stirring at normal temperature for 2h; washing the biomass raw material subjected to impurity removal by deionized water; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, precursor pre-carbonization: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, naturally cooling to obtain a pre-carbonized product, taking out, and grinding by using a mortar to obtain pre-carbonized powder;
s3, nitrogen vulcanization: 2g of the pre-carbonized powder obtained in the step S2 is added into the prepared thiourea solution, and the preparation method of the thiourea solution comprises the following steps: dissolving 4g of thiourea in 60mL of deionized water, stirring for 6 hours at normal temperature under a magnetic stirrer, centrifugally washing, transferring to an 80 ℃ oven, and drying for 12 hours to obtain dried pre-carbonized powder of a nitrogen-sulfur source;
s4, carbonizing: and (3) putting 1g of the pre-carbonized powder containing the nitrogen and sulfur source obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the spherical biomass hard carbon material with long circulation stability.
The prepared spherical biomass hard carbon material with long circulation stability is taken as a negative electrode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare a negative electrode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and blanked to obtain the hard carbon negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
As shown in figures 1 to 3, the prepared spherical material has a first-circle coulomb efficiency as high as 90% and can stably circulate for 1000 circles under the current density of 200 mA/g.
Example 3
A spherical long-circulation stable biomass hard carbon material comprises the following steps:
s1, preprocessing a precursor: cutting fresh banana tree leaves into small pieces, then putting the small pieces into water, carrying out ultrasonic treatment for 30min, washing off obvious impurities, adding 1mol/L nitric acid into the biomass raw material after ultrasonic treatment, and stirring at normal temperature for 2h; washing the biomass raw material subjected to impurity removal by deionized water; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, precursor pre-carbonization: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, naturally cooling to obtain a pre-carbonized product, taking out, and grinding by using a mortar to obtain pre-carbonized powder;
s3, nitrogen vulcanization: 2g of the pre-carbonized powder obtained in the step S2 is added into the prepared thiourea solution, and the method for preparing the thiourea solution comprises the following steps: dissolving 6g of thiourea in 60mL of deionized water, stirring for 6 hours at normal temperature under a magnetic stirrer, centrifugally washing, transferring to an 80 ℃ oven, and drying for 12 hours to obtain dried pre-carbonized powder of a nitrogen-sulfur source;
s4, carbonizing: and (3) putting 1g of the pre-carbonized powder containing the nitrogen and sulfur source obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the spherical biomass hard carbon material with long circulation stability.
The prepared spherical biomass hard carbon material with long circulation stability is taken as a negative electrode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare a negative electrode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and blanked to obtain the hard carbon negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial coulomb efficiency is 88%, and the stable cycle can be realized for 600 circles under the current density of 200 mA/g.
Example 4
A spherical long-circulation stable biomass hard carbon material comprises the following steps:
s1, preprocessing a precursor: cutting fresh banana tree leaves into small pieces, then putting the small pieces into water, carrying out ultrasonic treatment for 30min, washing off obvious impurities, adding 1mol/L nitric acid into the biomass raw material after ultrasonic treatment, and stirring at normal temperature for 2h; washing the biomass raw material subjected to impurity removal by deionized water; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, precursor pre-carbonization: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, naturally cooling to obtain a pre-carbonized product, taking out, and grinding by using a mortar to obtain pre-carbonized powder;
s3, carbonizing: and (2) putting 1g of the pre-carbonized powder obtained in the step (S2) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the biomass hard carbon material.
The prepared biomass hard carbon material is used as a negative electrode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare a negative electrode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and punched to obtain the hard carbon negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial circle coulomb efficiency is 80%, and the initial circle coulomb efficiency can stably circulate for 300 circles under the current density of 200 mA/g.
Comparative example 1
A spherical long-circulation stable biomass hard carbon material comprises the following steps:
s1, preprocessing a precursor: cutting fresh banana tree leaves into small pieces, then putting the small pieces into water, carrying out ultrasonic treatment for 30min, washing off obvious impurities, adding 1mol/L nitric acid into the biomass raw material after ultrasonic treatment, and stirring at normal temperature for 2h; washing the biomass raw material subjected to impurity removal by deionized water; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, precursor pre-carbonization: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, naturally cooling to obtain a pre-carbonized product, taking out, and grinding by using a mortar to obtain pre-carbonized powder;
s3, nitrogen vulcanization: 2g of the pre-carbonized powder obtained in the step S2 is added into the prepared thiourea solution, and the method for preparing the thiourea solution comprises the following steps: dissolving 4g of thiourea in 60mL of deionized water, stirring for 6 hours at normal temperature under a magnetic stirrer, centrifugally washing, transferring to an 80 ℃ oven, and drying for 12 hours to obtain dried pre-carbonized powder of a nitrogen-sulfur source;
s4, carbonizing: and (3) putting 1g of the pre-carbonized powder containing the nitrogen and sulfur source obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the spherical biomass hard carbon material with long circulation stability.
The prepared spherical biomass hard carbon material with long circulation stability is taken as a negative electrode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare a negative electrode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and blanked to obtain the hard carbon negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial coulomb efficiency is 82%, and the stable cycle can be realized for 500 circles under the current density of 200 mA/g.
Comparative example 2
A spherical long-circulation stable biomass hard carbon material comprises the following steps:
s1, preprocessing a precursor: cutting fresh banana tree leaves into small pieces, then putting the small pieces into water, carrying out ultrasonic treatment for 30min, washing off obvious impurities, adding 1mol/L nitric acid into the biomass raw material after ultrasonic treatment, and stirring at normal temperature for 2h; washing the biomass raw material subjected to impurity removal by deionized water; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, precursor pre-carbonization: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, naturally cooling to obtain a pre-carbonized product, taking out, and grinding by using a mortar to obtain pre-carbonized powder;
s3, nitrogen vulcanization: 2g of the pre-carbonized powder obtained in the step S2 is added into the prepared thiourea solution, and the method for preparing the thiourea solution comprises the following steps: dissolving 4g of thiourea in 60mL of deionized water, stirring for 6 hours at normal temperature under a magnetic stirrer, centrifugally washing, transferring to an 80 ℃ oven, and drying for 12 hours to obtain dried pre-carbonized powder of a nitrogen-sulfur source;
s4, carbonizing: and (3) putting 1g of the pre-carbonized powder containing the nitrogen and sulfur source obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1600 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the spherical biomass hard carbon material with long circulation stability.
The prepared spherical biomass hard carbon material with long circulation stability is taken as a negative electrode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare a negative electrode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and blanked to obtain the hard carbon negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial circle coulomb efficiency is 88%, and the initial circle coulomb efficiency can stably circulate for 700 circles under the current density of 200 mA/g.
In summary, it is known that a biomass hard carbon material with long-term spherical stability, which is used as a battery negative electrode active material, can increase the specific capacity of the battery and has excellent cycle stability. The hard carbon material prepared by the method of example 2 has the optimal performance, and the size of the open pores of the hard carbon is suitable for co-doping of nitrogen atoms and sulfur atoms possibly because of the proper pre-carbonization temperature, and the too large or too small open pores are not beneficial to co-doping of nitrogen atoms and sulfur atoms, and if the open pores are too large, the nitrogen atoms and the sulfur atoms are easy to run off, and the doping rate is not high; in addition, the proper thiourea concentration makes the doping ratio of nitrogen atoms and sulfur atoms proper, and too high or too low ratio is not beneficial to the exertion of electrochemical performance, if too high ratio hinders the intercalation of sodium ions, and too low ratio cannot provide larger sodium storage space.
The foregoing is merely exemplary embodiments of the present invention, and detailed technical solutions or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present invention, and these should also be regarded as the protection scope of the present invention, which does not affect the effect of the implementation of the present invention and the practical applicability of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (10)
1. The preparation method of the spherical long-circulation stable biomass hard carbon material is characterized by comprising the following steps of:
s1, sequentially preprocessing, removing impurities, purifying and drying a biomass raw material to obtain a precursor sample;
s2, heating the precursor sample obtained in the step S1 to a pre-carbonization temperature under a protective atmosphere for calcination, naturally cooling, and grinding and crushing to obtain pre-carbonized powder;
s3, fully mixing the pre-carbonized powder obtained by the treatment of S2 with thiourea solution, uniformly stirring, centrifugally washing and drying to obtain pre-carbonized powder containing nitrogen and sulfur sources;
and S4, heating the nitrogen and sulfur source-containing pre-carbonized powder obtained in the step S3 to the carbonization temperature under the protective atmosphere for calcining, and naturally cooling to obtain the spherical biomass hard carbon material with long circulation stability.
2. The method for preparing the spherical long-circulation stable biomass hard carbon material according to claim 1, which is characterized by comprising the following steps: in S1, biomass raw materials comprise one or more of banana trees, banana leaves, porrow leaf honey shells, coconut shells, durian shells and mangosteen shells; the pretreatment is to cut and refine the biomass raw material; adding deionized water into the biomass raw material for ultrasonic treatment for not less than 30min, washing off obvious impurities on the surface, adding 0.5-2 mol/L nitric acid into the biomass raw material after ultrasonic treatment, and stirring for 2-6 h at normal temperature; the purification and drying are to wash the biomass raw material after impurity removal with deionized water and then dry.
3. The method for preparing the spherical long-circulation stable biomass hard carbon material according to claim 1, which is characterized by comprising the following steps: in S2, the pre-carbonization temperature is 400-600 ℃, the pre-carbonization time is 2-3 h, and the heating rate is 3-5 ℃/min; the protective atmosphere is one or more inert gases selected from nitrogen, argon and nitrogen-argon.
4. The method for preparing the spherical long-circulation stable biomass hard carbon material according to claim 1, which is characterized by comprising the following steps: in the S3, in the process of mixing the thiourea solution and the pre-carbonized powder, the mass ratio of the thiourea solution to the pre-carbonized powder is 0-3:1, wherein the concentration of the thiourea solution is 0-3 mol/L, and the stirring time is 6-12 h.
5. The method for preparing the spherical long-circulation stable biomass hard carbon material according to claim 1, which is characterized by comprising the following steps: in S4, the carbonization temperature is 1200-1600 ℃, the carbonization time is 2-3 h, and the heating rate is 3-5 ℃/min; the protective atmosphere is one or more inert gases selected from nitrogen, argon and nitrogen-argon.
6. A biomass hard carbon material prepared by the preparation method of the spherical long-circulation stable biomass hard carbon material according to any one of claims 1 to 5.
7. The use of a long-circulating stable biomass hard carbon material in spherical form in a sodium ion battery according to claim 6, characterized in that: the biomass hard carbon material is used as a negative electrode active material of a sodium ion battery.
8. The use of a long-circulating stable biomass hard carbon material in spherical form in a sodium ion battery according to claim 7, characterized in that: the specific method for using the biomass hard carbon material as the negative electrode active material of the sodium ion battery comprises the following steps: and mixing the biomass hard carbon material, the conductive agent and the binder according to the mass ratio of 7:2:1 or 8:1:1 to prepare negative electrode slurry, coating the negative electrode slurry on a current collector, and drying to obtain the negative electrode active material of the sodium ion battery.
9. The use of a long-circulating stable biomass hard carbon material in spherical form in a sodium ion battery according to claim 8, characterized in that: the conductive agent is conductive carbon black; the binder is any one of sodium carboxymethyl cellulose, polyvinylidene fluoride and sodium alginate; the current collector is copper foil or aluminum foil.
10. The use of a long-circulating stable biomass hard carbon material in spherical form in a sodium ion battery according to claim 8, characterized in that: the drying temperature is 80-120 ℃ and the drying time is 12-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211100799.2A CN116161640A (en) | 2022-09-09 | 2022-09-09 | Spherical long-circulation stable biomass hard carbon material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211100799.2A CN116161640A (en) | 2022-09-09 | 2022-09-09 | Spherical long-circulation stable biomass hard carbon material, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116161640A true CN116161640A (en) | 2023-05-26 |
Family
ID=86417027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211100799.2A Pending CN116161640A (en) | 2022-09-09 | 2022-09-09 | Spherical long-circulation stable biomass hard carbon material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116161640A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117069093A (en) * | 2023-09-15 | 2023-11-17 | 福建省鑫森炭业股份有限公司 | Preparation method of hard carbon anode material |
| CN118239473A (en) * | 2024-05-29 | 2024-06-25 | 四川大学 | Hard carbon anode material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170103113A (en) * | 2016-03-03 | 2017-09-13 | 성균관대학교산학협력단 | Carbon composite, method of manufacturing the carbon composite, sodium-ion capacitor electrode including the carbon composite, and carbon-dioxide absorbent |
| US10010866B1 (en) * | 2017-09-19 | 2018-07-03 | King Saud University | Nitrogen and phosphorus co-doped crystalline carbon materials |
| CN110237818A (en) * | 2019-06-14 | 2019-09-17 | 上海工程技术大学 | A kind of preparation method and application of nitrogen sulphur codope charcoal |
| CN110571432A (en) * | 2019-08-15 | 2019-12-13 | 合肥国轩高科动力能源有限公司 | element-doped biomass hard carbon negative electrode material for sodium ion battery, preparation method and sodium ion battery |
| CN112661153A (en) * | 2020-12-31 | 2021-04-16 | 华南理工大学 | Rhizome traditional Chinese medicine residue-based porous carbon electrode material and preparation and application thereof |
| CN113206246A (en) * | 2021-04-27 | 2021-08-03 | 天津理工大学 | Biomass hard carbon negative electrode material of sodium ion battery and preparation method thereof |
| CN113929083A (en) * | 2021-11-12 | 2022-01-14 | 黑龙江省能源环境研究院 | Nitrogen/sulfur doped porous carbon material and preparation method thereof |
-
2022
- 2022-09-09 CN CN202211100799.2A patent/CN116161640A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170103113A (en) * | 2016-03-03 | 2017-09-13 | 성균관대학교산학협력단 | Carbon composite, method of manufacturing the carbon composite, sodium-ion capacitor electrode including the carbon composite, and carbon-dioxide absorbent |
| US10010866B1 (en) * | 2017-09-19 | 2018-07-03 | King Saud University | Nitrogen and phosphorus co-doped crystalline carbon materials |
| CN110237818A (en) * | 2019-06-14 | 2019-09-17 | 上海工程技术大学 | A kind of preparation method and application of nitrogen sulphur codope charcoal |
| CN110571432A (en) * | 2019-08-15 | 2019-12-13 | 合肥国轩高科动力能源有限公司 | element-doped biomass hard carbon negative electrode material for sodium ion battery, preparation method and sodium ion battery |
| CN112661153A (en) * | 2020-12-31 | 2021-04-16 | 华南理工大学 | Rhizome traditional Chinese medicine residue-based porous carbon electrode material and preparation and application thereof |
| CN113206246A (en) * | 2021-04-27 | 2021-08-03 | 天津理工大学 | Biomass hard carbon negative electrode material of sodium ion battery and preparation method thereof |
| CN113929083A (en) * | 2021-11-12 | 2022-01-14 | 黑龙江省能源环境研究院 | Nitrogen/sulfur doped porous carbon material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117069093A (en) * | 2023-09-15 | 2023-11-17 | 福建省鑫森炭业股份有限公司 | Preparation method of hard carbon anode material |
| CN117069093B (en) * | 2023-09-15 | 2024-06-07 | 福建省鑫森炭业股份有限公司 | Preparation method of hard carbon anode material |
| CN118239473A (en) * | 2024-05-29 | 2024-06-25 | 四川大学 | Hard carbon anode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2999468C (en) | Method of preparing and application of carbon-selenium composites | |
| CN109678130A (en) | A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery | |
| CN110571432A (en) | element-doped biomass hard carbon negative electrode material for sodium ion battery, preparation method and sodium ion battery | |
| CN106299365A (en) | A kind of sodium-ion battery biomass hard carbon cathode material, preparation method and sodium-ion battery | |
| CN114436237B (en) | Hard carbon material and preparation method and application thereof | |
| CN110155983B (en) | Preparation method of cotton-based porous biomass carbon | |
| CN116161640A (en) | Spherical long-circulation stable biomass hard carbon material, preparation method and application | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN104157849A (en) | Method for preparing elemental sulfur and mesoporous carbon composite material | |
| CN105489901A (en) | Preparation method and application of lithium-sulfur battery three-dimensional carbon current collector | |
| EP3953300A1 (en) | Process for preparing and use of hard-carbon containing materials | |
| CN109585832B (en) | Sulfur-doped microcrystalline graphite, preparation method thereof and application of sulfur-doped microcrystalline graphite as negative electrode material of sodium-ion battery | |
| CN112850708A (en) | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area | |
| CN111268677A (en) | Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed | |
| CN109755542B (en) | Sodium-sulfur battery positive electrode material and preparation method thereof | |
| CN109713259B (en) | Lithium ion battery silicon-carbon composite negative electrode material and preparation method and application thereof | |
| CN104157861A (en) | Mesoporous carbon material, elemental sulfur and preparation method for mesoporous carbon composite material | |
| CN112174119B (en) | Method for preparing graphene foam from antibiotic fungi residues | |
| CN116177520A (en) | High-performance hard carbon negative electrode material for low-temperature sodium ion battery and preparation method thereof | |
| CN112299389A (en) | Method for preparing sodium ion carbon negative electrode material by using nitrogen-doped porous biomass carbon | |
| CN116040605A (en) | High-performance hard carbon negative electrode material for high-temperature sodium ion battery and preparation method thereof | |
| CN116854075A (en) | Chemical surface modified biomass hard carbon material and preparation method and application thereof | |
| CN109921030B (en) | Microbial modified lithium-air battery positive electrode material and preparation method thereof | |
| CN112678799A (en) | Carbon-coated silicon negative electrode material with hollow structure and preparation method thereof | |
| CN112310371A (en) | Iron oxyhydroxide/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 |