CN113651307B - Sodium ion battery carbon negative electrode material prepared based on waste wood chips and preparation method thereof - Google Patents

Sodium ion battery carbon negative electrode material prepared based on waste wood chips and preparation method thereof Download PDF

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CN113651307B
CN113651307B CN202110907187.3A CN202110907187A CN113651307B CN 113651307 B CN113651307 B CN 113651307B CN 202110907187 A CN202110907187 A CN 202110907187A CN 113651307 B CN113651307 B CN 113651307B
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hard carbon
ion battery
sodium ion
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CN113651307A (en
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胡章贵
郭帅
龙震
纪效波
陈以蒙
郭世宏
韩华玮
姜修宝
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Tianjin University of Technology
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    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 sodium ion battery carbon cathode material prepared based on waste wood dust and a preparation method thereof. The invention uses the waste wood chips as biomass raw materials, can fully utilize a large amount of scraps generated in the production process of wood products, and has the advantages of environmental protection, low cost and the like; the pyrolysis method with low carbonization heating rate has the functions of reducing defect concentration, increasing interlayer spacing and improving graphitization degree, thereby effectively improving the electrochemical performance of the material; the hard carbon negative electrode material prepared by the method has higher first coulombic efficiency and reversible specific capacity, shows excellent cycle stability and rate capability, and is an ideal sodium ion battery negative electrode material.

Description

Sodium ion battery carbon negative electrode material prepared based on waste wood chips and preparation method thereof
Technical Field
The invention belongs to the field of preparation of sodium ion battery electrode materials, and particularly relates to a method for preparing a high-first-effect sodium ion battery carbon negative electrode material based on waste wood dust and the sodium ion battery carbon negative electrode material obtained by the preparation method.
Background
With the rapid development of human society and the consumption of conventional fossil energy, the problems of energy crisis and environmental pollution continue to be exacerbated, and therefore, it is important to develop efficient energy conversion methods and clean energy systems. At present, the lithium ion battery has become a novel energy system with competitive power due to the advantages of high power and energy density, long cycle life, good safety and the like, and is widely applied to daily life of smart phones, notebook computers, electric automobiles and the like. However, since there is an urgent need to develop large-scale energy storage devices and lithium resources are limited in reserves, there is a need to develop alternatives to lithium ion batteries to meet the needs of future developments. Sodium is an element widely distributed in nature, is more abundant and readily available than lithium in the crust, and is similar in physical and chemical properties to lithium. Sodium Ion Batteries (SIBs) have attracted considerable attention from researchers and are considered a promising alternative to LIBs.
In the study of Sodium Ion Batteries (SIBs), it is of great importance to find high performance electrode materials. There is currently a lack of anode materials suitable for SIBs, a factor limiting their development. In the past, carbon materials have been widely used in electrochemical energy systems due to their excellent conductivity, abundant reserves, and low cost, and are considered as the most promising electrode materials. Graphite, which is a conventional carbon material, has been widely used in lithium ion batteries due to its excellent electrochemical properties. However, due to the large radius of sodium ions and high ionization potential, the graphite anode material has poor sodium storage performance. Hard carbon is carbon that is difficult to graphitize at temperatures above 2500 ℃, and is composed of randomly oriented, defective discrete pieces of graphite, the structure of which is known as a "card house" model. Compared with graphite, hard carbon has larger interlayer spacing and more defects, and shows the advantages of low potential (0.1) and high capacity.
Biomass materials, one of the precursors for the preparation of hard carbon, are considered as reliable large-scale carbon sources due to their low cost, renewable and environmentally friendly advantages. Biomass carbon materials such as rice hulls, shaddock peels, bagasse, banana peels and corncobs have been proved to have good sodium storage performance. The first coulombic efficiency (ICE) determines the available energy density of the anode material in practical applications, and is one of the important factors for realizing industrial applications of hard carbon in SIBs. Most of the hardness is due to irreversible sodium storage sites, side reactions and formation of Solid Electrolyte Interphase (SEI)Carbon exhibits a lower ICE. In order to improve ICE of hard carbon cathode material, cinnamomum of Tianjin university and the like adopts pyrolysis and H 2 The method of combining reduction prepares the hard carbon material. In the study, H 2 The reduction treatment obviously reduces the oxygen content in the hard carbon, reduces the defects of the material and the occurrence of unnecessary side reactions, further improves the sodium storage performance of the material, and effectively improves the ICE of the hard carbon. Researchers find that the reason of low initial coulomb efficiency of the hard carbon material is because of irreversible intercalation of sodium ions in the initial discharge process, the specific surface area, the defect concentration, the heteroatom content and the like are main factors influencing the irreversible intercalation, and the research and development of the high initial biomass hard carbon material have important significance.
Disclosure of Invention
The invention aims to provide a high-first-effect sodium ion battery carbon negative electrode material prepared based on waste wood chips and a preparation method thereof. The prepared hard carbon material has lower defect concentration, proper interlayer spacing and higher graphitization degree, and the special structure is favorable for intercalation and deintercalation of sodium ions, so that the first coulomb efficiency of the material is effectively improved.
To solve the above technical problems, according to one aspect of the present invention, there is provided a method for preparing a carbon negative electrode material of a sodium ion battery based on waste wood chips, comprising:
step one: carrying out ultrasonic washing pretreatment on the waste wood chip biomass raw material to remove dust impurities on the surface, and drying to obtain a biomass precursor;
step two: transferring the treated biomass precursor into a muffle furnace to be pre-carbonized in the atmosphere of air, wherein the pre-carbonization heating rate is 1-20 ℃/min, the pyrolysis temperature is 200-400 ℃, and the heat preservation time is 1-5 hours; naturally cooling, placing in a pulverizer, pulverizing into powder to obtain a pre-carbonized product;
step three: transferring the pre-carbonized product into a high temperature tube furnace, carbonizing at high temperature under the protection of inert gas, wherein the heating rate of high temperature carbonization is 0.25-1 ℃/min, the pyrolysis temperature is 1200-1400 ℃, and the inert gas is selected from nitrogen, argon, helium and hydrogen-argon mixture (5% H) 2 +95% Ar)The heat preservation time is 1-10 hours; naturally cooling, grinding and sieving;
step four: and washing the treated hard carbon material with an acidic solution to remove metal heteroatoms, centrifugally washing with deionized water and ethanol to neutrality, and drying to obtain the hard carbon material.
In the first step, the waste wood chips are one of the following arbor wood chips: camphor wood scraps, walnut tree wood scraps, walnut wood scraps, elm wood scraps and chinaberry wood scraps.
In the first step, the liquid used for washing the biomass raw material is one or more of deionized water, absolute ethyl alcohol and acetone, the ultrasonic washing time is 6-12 hours, and the temperature of the liquid for washing is 30-80 ℃.
Further, in the second step, the temperature rising rate of the pre-carbonization is 3 ℃/min, the pyrolysis temperature is 300 ℃, and the heat preservation time is 2 hours.
Further, in the third step, the heating rate of high-temperature carbonization is 0.25 ℃/min, the pyrolysis temperature is 1300 ℃, and the heat preservation time is 2 hours. In the third step, the flow rate of the inert gas is 10-100 CC/min. The cooling rate is kept at 5 ℃/min.
In the fourth step, the acid solution is selected from one of hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid and sulfuric acid, the concentration of the acid solution is 1-5M, and the soaking and washing time is 1-24 hours.
According to another aspect of the present invention, there is provided a carbon negative electrode material for a sodium ion battery, characterized in that: is prepared by the method described above.
According to another aspect of the invention, a hard carbon material electrode slice is provided, wherein the sodium ion battery carbon negative electrode material, acetylene black, sodium carboxymethyl cellulose and polyacrylic acid are uniformly ground according to a proportion, deionized water is added for magnetic stirring to obtain uniformly mixed electrode slurry, a coating machine is used for uniformly coating the battery slurry on copper foil, the copper foil is placed in a vacuum drying box for vacuum drying for hours, and then a sheet punching machine is used for preparing the copper foil into a wafer electrode, so that the hard carbon material electrode slice is obtained.
Further, the mass ratio of the acetylene black to the sodium carboxymethyl cellulose to the polyacrylic acid is 8:1:0.5:0.5.
According to another aspect of the present invention, there is provided a sodium ion battery comprising the hard carbon material electrode sheet described above.
Arbor type trees are trees with large tree bodies, are mainly distributed in fertile lands and warm areas, are quite widely distributed, and are commonly used for landscaping, building, furniture manufacturing and the like. However, in practice, a large amount of waste wood chips are generally produced, and a low usable value is exhibited. The invention uses the waste wood chips as raw materials, has the advantages of simple preparation process flow, environment protection, low cost and the like, and is convenient for mass production.
The method combines pre-carbonization and low-temperature-rise rate pyrolysis, wherein the pre-carbonization method enables the biomass organic carbon chain to initially form a ring structure, and simultaneously introduces an oxygen functional group; the method for pyrolyzing the hard carbon material at a low temperature rise rate can effectively reduce the defect concentration of the hard carbon material, the partial micropores on the surface of the hard carbon material are closed and the specific surface area is reduced, and can effectively reduce the loss of irreversible capacity of the hard carbon material, and the prepared hard carbon material has proper interlayer spacing and higher graphitization degree, is favorable for intercalation and deintercalation of sodium ions, has high first coulombic efficiency and reversible specific capacity, has a charging curve of a platform type and higher platform capacity ratio, and has excellent cycle stability and rate capability, and is an ideal negative electrode material of a sodium ion battery.
Drawings
FIG. 1 is XRD patterns of negative electrode materials prepared in examples 1,2,4 and comparative examples 1,2 of the present invention;
FIG. 2 is a Raman diagram of the negative electrode materials prepared in examples 1,2,4 and comparative examples 1,2 of the present invention;
fig. 3 is a charge-discharge graph of the negative electrode material prepared in comparative example 1 of the present invention;
fig. 4 is a charge-discharge graph of the anode material prepared in example 4 of the present invention;
FIG. 5 is a graph showing the cycle performance of the anode materials prepared in examples 1,2,4 and comparative examples 1,2 of the present invention;
fig. 6 is a graph showing the rate performance of the anode materials prepared in example 4 and comparative example 1 of the present invention;
fig. 7 is an SEM image of the negative electrode material prepared in example 4 of the present invention;
fig. 8 is an HRTEM of the negative electrode material prepared in example 4 of the present invention.
Detailed Description
The following examples are provided to further illustrate the claimed invention. However, examples and comparative examples are provided for the purpose of illustrating embodiments of the present invention and do not exceed the scope of the inventive subject matter, which is not limited by the examples. Unless specifically indicated otherwise, materials and reagents used in the present invention are available from commercial products in the art.
Example 1
Step one: ultrasonically washing biomass camphorwood chips with deionized water for 6 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried camphorwood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 1 ℃/min under the protection of inert gas argon, preserving heat for 2 hours, cooling to room temperature at a cooling rate of 5 ℃/min along with the furnace, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 2
Step one: ultrasonically washing biomass camphorwood chips with deionized water for 6 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried camphorwood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 0.5 ℃/min under the protection of inert gas argon, preserving heat for 2 hours, cooling to room temperature at a cooling rate of 5 ℃/min along with the furnace, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 3
Step one: ultrasonically washing biomass camphorwood chips with deionized water for 6 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried camphorwood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1200 ℃ at a heating rate of 0.25 ℃/min under the protection of inert gas argon, preserving heat for 2 hours, cooling to room temperature at a cooling rate of 5 ℃/min along with the furnace, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 4
Step one: ultrasonically washing biomass camphorwood chips with deionized water for 6 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried camphorwood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 0.25 ℃/min under the protection of inert gas argon, preserving heat for 2 hours, cooling to room temperature at a cooling rate of 5 ℃/min along with the furnace, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 5
Step one: ultrasonically washing biomass camphorwood chips with deionized water for 6 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried camphorwood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1400 ℃ at a heating rate of 0.25 ℃/min under the protection of inert gas argon, preserving heat for 2 hours, cooling to room temperature at a cooling rate of 5 ℃/min along with the furnace, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 6
Step one: washing biomass juglans mandshurica wood chips with absolute ethyl alcohol for 12 hours by ultrasonic, removing dust impurities, drying the obtained product in a blast drying oven at 30 ℃ for 24 hours, and removing water;
step two: transferring the dried juglans mandshurica wood chips into a muffle furnace, heating to 200 ℃ at a heating rate of 1 ℃/min under the atmosphere of air, preserving heat for 1 hour, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 0.25 ℃/min under the protection of inert gas nitrogen, preserving heat for 2 hours, cooling to room temperature at a cooling rate of 5 ℃/min along with the furnace, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 1M dilute nitric acid solution, soaking for 24 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 7
Step one: washing biomass walnut wood chips with acetone for 8 hours, removing dust impurities, and drying the obtained product in a forced air drying oven at 80 ℃ for 24 hours to remove water;
step two: transferring the dried walnut wood chips into a muffle furnace, heating to 400 ℃ at a heating rate of 20 ℃/min under the atmosphere of air, preserving heat for 5 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: the precarbonated product was placed in a tube furnace in a hydrogen argon mixture (5% H) 2 +95% Ar) from the chamber at a heating rate of 0.25 ℃/minHeating to 1300 ℃ at 25 ℃, preserving heat for 2 hours, cooling to room temperature along with a furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 5M acetic acid solution, soaking for 1 hour, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 8
Step one: washing biomass elm wood chips with deionized water for 8 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried elm wood chips into a muffle furnace, heating to 350 ℃ at a heating rate of 15 ℃/min under the atmosphere of air, preserving heat for 5 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tube furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 0.5 ℃/min under the protection of nitrogen, preserving heat for 2 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 1M sulfuric acid solution, soaking for 3 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 9
Step one: washing biomass chinaberry wood chips with absolute ethyl alcohol for 4 hours, removing dust impurities, and drying the obtained product in a forced air drying oven at 80 ℃ for 24 hours to remove water;
step two: transferring the dried chinaberry wood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 10 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving heat for 2 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 2M nitric acid solution, soaking for 3 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Comparative example 1
Comparative example 4 comparative example 1 provides a method for preparing a hard carbon material having a high heating rate of 5 deg.c/min.
Step one: ultrasonically washing biomass camphorwood chips with deionized water for 6 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried camphorwood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 5 ℃/min under the protection of inert gas argon, preserving heat for 2 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is a dilute hydrochloric acid solution of 2M, soaking for 12 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a forced air drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Comparative example 2
Comparative example 4 comparative example 2 provides a method for preparing a hard carbon material having a high heating rate of 2 deg.c/min.
Step one: ultrasonically washing biomass camphorwood chips with deionized water for 6 hours, removing dust impurities, and drying the obtained product in a blast drying oven at 60 ℃ for 24 hours to remove water;
step two: transferring the dried camphorwood chips into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the atmosphere of air, preserving heat for 2 hours, naturally cooling with the furnace, taking out, and crushing a pre-carbonized product into powder by a crusher for later use;
step three: placing the pre-carbonized product into a tubular furnace, heating from room temperature 25 ℃ to 1300 ℃ at a heating rate of 2 ℃/min under the protection of inert gas argon, preserving heat for 2 hours, cooling to room temperature at a cooling rate of 5 ℃/min along with the furnace, taking out, grinding, and sieving with a 325-mesh sieve;
step four: and (3) carrying out acid washing treatment on the obtained powder, wherein the selected acid washing solution is 2M dilute hydrochloric acid solution, soaking for 12 hours, repeatedly centrifuging and washing with deionized water and ethanol to neutrality, drying the obtained product in a blast drying oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
According to a typical embodiment of the invention, a hard carbon material electrode slice is provided, camphor wood chip hard carbon sodium ion battery anode materials obtained in each example and comparative example, acetylene black, sodium carboxymethylcellulose (CMC) and polyacrylic acid (PAA) are ground uniformly according to the mass ratio of 8:1:0.5:0.5, a proper amount of deionized water is added for magnetically stirring for 12 hours to obtain uniformly mixed electrode slurry, the uniformly mixed electrode slurry is uniformly coated on copper foil by a coating machine, the copper foil is placed in a vacuum drying box for vacuum drying at 80 ℃ for 12 hours, and then a wafer electrode with the diameter of 12mm is prepared by a sheet punching machine, so that the hard carbon material electrode slice is obtained.
The present example provides a half cell of a sodium ion battery, the electrode sheet obtained above was used as a negative electrode, the hard carbon electrode sheet was cut to obtain a wafer with a diameter of 12mm, the wafer was pressed by a tablet press, the cell was assembled in a glove box filled with high purity argon gas according to the construction of a CR2016 standard button cell, wherein a glass fiber (Whitman, GF/a) wafer with a diameter of 19 mm was used as a separator, a sodium metal sheet with a diameter of 12mm thickness of 0.2 mm was used as a counter electrode and a reference electrode, a 1 mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution was used as an electrolyte, and after standing 12 h, the cell was subjected to charge and discharge test with a current density of 20mA/g on a blue cell test platform.
TABLE 1 Main parameters and sodium storage Properties of examples 1-5 and comparative examples 1-2
The XRD patterns shown in fig. 1 can be seen that the five samples of examples 1,2,4 and comparative examples 1,2 all show 2 weak and broad diffraction peaks at 24 ° and 43 ° (2θ), corresponding to diffraction of (002) and (100) crystal planes, respectively, and as the temperature rising rate decreases, the (002) peak shifts to a lower diffraction angle, the 2θ shifts from 24.42 ° to 23.48 °, resulting in average layer spacing d002 of 0.364, 0.367, 0.371, 0.374 and 0.378 nm, respectively, wherein the hard carbon material prepared in example 4 has a larger layer spacing, facilitating intercalation and deintercalation of sodium ions.
As can be seen from the Raman spectra shown in FIG. 2, the five samples of examples 1,2,4 and comparative examples 1,2 are respectively shown in 1340-1340 cm -1 And 1590 cm -1 Two broad peaks are shown representing the D and G peaks, respectively, and the integrated area intensity ratio of the D and G peaks is typically used to characterize the graphitization degree of the carbon material. I as the rate of temperature rise decreases D / I G The value was continuously decreased from 1.63 to 1.48, with the hard carbon material prepared in example 4 having a higher degree of graphitization.
The charge and discharge graph shown in FIG. 3 shows that the material of comparative example 1 shows a first coulombic efficiency of 67.5% and an initial specific capacity of 242.6mAh/g at a current density of 20mA/g and a voltage interval of 0-2V, and has an obvious charge and discharge plateau.
The charge-discharge graph shown in FIG. 4 shows that the material of example 4 shows a higher initial coulombic efficiency (82.8%) and initial specific capacity (324.6 mAh/g) at a current density of 20mA/g and a voltage interval of 0-2V, with a higher plateau capacity fraction.
The cycle performance chart shown in fig. 5 shows that all five hard carbon materials of examples 1,2,4 and comparative examples 1,2 show good cycle stability, wherein the hard carbon material prepared in example 5 has the highest reversible specific capacity, and still has a high capacity retention of 98.4% after 50 cycles at a current density of 20 mA/g.
As can be seen from the SEM image shown in fig. 6, the hard carbon material of example 4 shows a layered porous structure, which is advantageous for intercalation and deintercalation of sodium ions, and shows fewer micropores on the surface thereof, which can reduce the loss of irreversible capacity.
The HRTEM diagram shown in fig. 7 shows that the hard carbon material of example 4 shows a typical amorphous structure and has a large number of short-range ordered graphite layers with a layer spacing of 0.379 nm.
As shown in table 1, it can be seen from comparative examples 3,4,5 that by varying the pyrolysis temperature of the hard carbon material, the reversible specific capacity of the material shows a tendency to increase and decrease with increasing temperature, with 1300 ℃ being the optimal carbonization temperature; as can be seen from comparative examples 1,2,4 and comparative examples 1,2, the initial coulombic efficiency of the material is increased from 67.5% to 82.8% and the initial specific capacity is increased from 242.6mAh/g to 324.6mAh/g by reducing the rate of temperature rise of the material during pyrolysis; by reducing the temperature rising rate in the carbonization process, the defect concentration of the material is reduced, the interlayer spacing and graphitization degree of the material are improved, the first coulomb efficiency and specific capacity of the material can be effectively improved, and the sodium storage performance of the material is improved.
The above-mentioned embodiments 1 to 9 are only preferred embodiments of the present invention, and the basic principle and features of the present invention are described, but the present invention is not limited to the above-mentioned embodiments, and all modifications and optimizations within the method disclosed in the present invention are included in the protection of the present invention.

Claims (9)

1. The method for preparing the sodium ion battery carbon cathode material based on the waste wood chips is characterized by comprising the following steps:
step one: carrying out ultrasonic washing pretreatment on the waste wood chip biomass raw material to remove dust impurities on the surface, and drying to obtain a biomass precursor;
step two: transferring the treated biomass precursor into a muffle furnace to be pre-carbonized in the atmosphere of air, wherein the pre-carbonization heating rate is 1-20 ℃/min, the pyrolysis temperature is 200-400 ℃, and the heat preservation time is 1-5 hours; naturally cooling, placing in a pulverizer, pulverizing into powder to obtain a pre-carbonized product;
step three: transferring the pre-carbonized product into a high-temperature tube furnace for high-temperature carbonization under the protection of inert gas, wherein the heating rate of the high-temperature carbonization is 0.25 ℃/min, the pyrolysis temperature is 1300 ℃, the inert gas is one of nitrogen, argon, helium and hydrogen-argon mixed gas, and the hydrogen-argon mixed gas is 5% H 2 +95% Ar, the incubation time is 2 hours; naturally cooling, grinding and sieving;
step four: and washing the treated hard carbon material with an acidic solution to remove metal heteroatoms, centrifugally washing with deionized water and ethanol to neutrality, and drying to obtain the hard carbon material.
2. The method according to claim 1, characterized in that:
in the first step, the waste wood chips are one of the following arbor wood chips: camphor wood scraps, walnut tree wood scraps, walnut wood scraps, elm wood scraps and chinaberry wood scraps.
3. The method according to claim 1, characterized in that:
in the first step, the liquid used for washing the biomass raw material is one or more of deionized water, absolute ethyl alcohol and acetone, the ultrasonic washing time is 6-12 hours, and the temperature of the liquid for washing is 30-80 ℃.
4. The method according to claim 1, characterized in that:
in the second step, the temperature rising rate of the pre-carbonization is 3 ℃/min, the pyrolysis temperature is 300 ℃, and the heat preservation time is 2 hours.
5. The method according to claim 1, characterized in that: in the fourth step, the acid solution is selected from one of hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid and sulfuric acid, the concentration of the acid solution is 1-5M, and the soaking and washing time is 1-24 hours.
6. A carbon cathode material of a sodium ion battery is characterized in that: obtained by the process of any one of claims 1 to 5.
7. The utility model provides a hard carbon material electrode slice which characterized in that: uniformly grinding the carbon cathode material of the sodium ion battery, acetylene black, sodium carboxymethyl cellulose and polyacrylic acid according to a proportion, adding deionized water, magnetically stirring to obtain uniformly mixed electrode slurry, uniformly coating the battery slurry on copper foil by using a coating machine, placing the copper foil in a vacuum drying oven, vacuum drying for 12 hours, and preparing the copper foil into a wafer electrode by using a sheet punching machine to obtain the hard carbon material electrode sheet.
8. The hard carbon electrode sheet of claim 7, wherein: the mass ratio of the carbon cathode material of the sodium ion battery, the acetylene black, the sodium carboxymethylcellulose and the polyacrylic acid is 8:1:0.5:0.5.
9. A sodium ion battery characterized by: a hard carbon electrode sheet comprising the hard carbon material of claim 7 or 8.
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