CN113044827B - Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof - Google Patents
Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano carbon material composite biomass hard carbon electrode material, which takes biomass as a raw material, and comprises the steps of preliminary crushing, cleaning and drying; heating with alkali solution, cleaning, drying, crushing for the second time, heating with acid solution, removing excessive inorganic salt impurity components, cleaning, and drying; adding uniformly dispersed acid liquor of graphene oxide and carbon nanotubes, stirring and mixing uniformly, treating by a microwave hydrothermal method, and crushing for the third time after drying to obtain a composite biomass hard carbon precursor; carrying out low-temperature pre-carbonization and high-temperature treatment on the composite biomass hard carbon precursor under the protection of inert atmosphere to obtain a composite biomass hard carbon material; the nano carbon material is compounded with biomass hard carbon material, and the crosslinking degree of the carbon structure is adjusted by controlling the pyrolysis speed, so that the distribution, the number, the size and the like of the holes are adjusted; graphene and carbon nanotubes are added to improve the specific surface area, electrical conductivity, thermal conductivity and structural stability of the material.
Description
Technical field:
the invention relates to the field of electrochemical energy storage, in particular to a nano carbon material composite biomass hard carbon electrode material, a preparation method and application thereof.
The background technology is as follows:
electrochemical energy storage devices are important in the aspect of storage and utilization of clean energy, and are widely applied in the fields of automobile industry, aerospace, power grids, military equipment, mobile communication, microelectronics and the like. The carbon material has the characteristics of rich raw materials, low price, simple synthesis, stable chemical property, low working potential, wide working temperature range and the like, and is suitable for being used as an electrode material of an electrochemical energy storage device.
The biomass structure is loose, the primary pore structure is developed, and the carbon material obtained after carbonization treatment can inherit part of the pore structure. The biomass carbon material has the characteristics of wide sources, simple process method, lower cost, environment friendliness, large specific surface area, high chemical stability and the like. However, during the pyrolysis process for preparing biomass carbon materials, carbon atoms are susceptible to agglomeration, and the active sites of the materials are reduced. At present, biomass hard carbon has the defects of large irreversible capacity, low first efficiency, low discharge voltage and the like, and the application of the biomass hard carbon in energy storage is greatly limited.
The invention comprises the following steps:
aiming at the deficiency and the deficiency of the prior art, the invention provides a nano carbon material composite biomass hard carbon electrode material which has larger specific surface area, higher conductivity, higher specific capacity and good multiplying power performance, has excellent energy storage performance and can be widely used in the field of electrochemical energy storage
The invention discloses a preparation method of a nano carbon material composite biomass hard carbon electrode material, which realizes the technical purposes by the following technical means, and comprises the following steps:
a. cleaning a biomass raw material, drying at 60-120 ℃, and primarily crushing after drying to obtain 16-60 mesh particles A;
b. adding the particles A into an alkali solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, then washing with deionized water, carrying out suction filtration or centrifugation until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances at 60-120 ℃ after separation, and carrying out secondary crushing to obtain 100-400 mesh powder B;
c. adding the powder B into an acid solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, then washing with deionized water, carrying out suction filtration or centrifugation until the mixed solution is neutral, then carrying out solid-liquid separation, and drying solid substances at 60-120 ℃ after separation to obtain powder C;
d. uniformly stirring and mixing the powder C and the dispersion liquid D, placing the mixture in a microwave reaction kettle, performing microwave hydrothermal reaction for 0.5-2 hours at 100-220 ℃ in a closed state, drying at 60-120 ℃, and crushing for the third time to obtain a 1000-2000 mesh composite biomass hard carbon precursor E;
e. under the protection of nitrogen or argon inert atmosphere, the composite biomass hard carbon precursor E is pre-carbonized for 1-6 hours at a low temperature of 300-650 ℃ at a heating speed of 1-20 ℃/min to obtain a composite biomass pre-carbonized material F;
f. then the composite biomass pre-carbonized material F is treated for 1 to 6 hours at a high temperature of 850 to 1500 ℃ under the protection of nitrogen or argon inert atmosphere at a heating speed of 1 to 20 ℃/min to obtain a composite biomass hard carbon material G;
g. adding PVDF dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain the composite biomass hard carbon electrode material H, wherein the mass fraction of NMP solution of PVDF is 0.9-5%.
Preferably, the biomass is one or more of coconut shells, straws, bamboo stalks and tobacco stalks.
Preferably, the dispersion liquid D in the step D is prepared by mixing graphene oxide, carbon nano tubes and PVP according to the mass ratio of 1-10:1-10:0.1-1, and particularly by using PVP surfactant as a dispersing agent, and stirring or ultrasonic manner to prepare the uniform dispersion liquid D of the graphene oxide and the carbon nano tubes in 0.05-1mol/L dilute acid.
Preferably, the alkali solution in the step b is potassium hydroxide, sodium hydroxide or ammonia water.
Preferably, the acid solution in the step c is hydrochloric acid or nitric acid.
The nano carbon material composite biomass hard carbon electrode material is prepared by the method.
The application of the nano carbon material composite biomass hard carbon electrode material comprises that the nano carbon material composite biomass hard carbon electrode material is used as a composite biomass hard carbon electrode for electrochemical energy storage.
According to the invention, the biomass material is heated in the alkali solution, so that the chemical bonds among cellulose, hemicellulose and lignin are broken, part of lignin is removed, the formed defects are utilized to strengthen pore etching, and the formation of three-dimensional multistage pore channels is promoted, so that the carbon material not only has abundant energy storage sites, but also has the multiplying power performance of high-current charging and discharging. And carrying out microwave hydrothermal treatment on biomass under an acidic condition to effectively compound graphene, carbon nano tubes and biomass materials, so that the first efficiency of the compound biomass hard carbon material is improved. The nano carbon materials such as graphene, carbon nano tubes and the like are used as dopants, and the excellent electric conductivity and heat conductivity of the graphene can be utilized to improve the electric conductivity and heat conductivity of the material and improve the interface property of hard carbon; the structural stability of the composite material can be enhanced by utilizing the carbon nano tube, the pore structure is increased, and the agglomeration phenomenon and the lamination phenomenon of graphene sheets during biomass carbonization are effectively inhibited. Through the synergistic effect among the graphene, the carbon nano tube and the hard carbon, the respective advantages of the graphene, the carbon nano tube and the hard carbon are fully exerted, and the structure and the property are complementary. The composite biomass hard carbon material has the advantages of the traditional hard carbon material, the nano doping material, the specific surface area is increased, the electrical conductivity is improved, the electrochemical performance is excellent, the thermal conductivity and the structural stability are also enhanced, and the composite biomass hard carbon material has great potential in the application fields of high capacity, high power and high safety.
The beneficial effects are that: the preparation method of the nano carbon material composite biomass hard carbon electrode material disclosed by the invention has the following beneficial effects:
the prepared composite biomass hard carbon material has a three-dimensional multi-stage porous structure, has the advantages of larger specific surface area, good conductivity, high electron migration speed, large stored or adsorbed ion or electron quantity, higher specific capacity, good multiplying power performance and excellent energy storage performance, and can be widely used in the field of electrochemical energy storage, such as super capacitors, lithium ion batteries or sodium ion batteries;
the whole preparation process is simple, is easy for industrial production, has low cost and environment friendliness, and can realize large-scale industrial synthesis.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
The invention relates to a preparation method of a nano carbon material composite biomass hard carbon electrode material, which comprises the following steps:
a. cleaning biomass raw materials such as coconut shells, straws, bamboo stalks and tobacco stalks, drying at 60-120 ℃, and primarily crushing after drying to obtain 16-60 mesh particles A;
b. adding the particles A into a potassium hydroxide, sodium hydroxide or ammonia water solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, then washing with deionized water, carrying out suction filtration or centrifugation until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances at 60-120 ℃ after separation, and carrying out secondary crushing to obtain 100-400 mesh powder B;
c. adding the powder B into 1-5mol/L hydrochloric acid or nitric acid solution, heating and stirring at 90-120 ℃ for 1-12h, then washing with deionized water, carrying out suction filtration or centrifugation until the mixed solution is neutral, then carrying out solid-liquid separation, and drying solid substances at 60-120 ℃ after separation to obtain powder C;
d. preparing uniform dispersion liquid D of graphene oxide and carbon nano tubes in 0.05-1mol/L dilute acid by taking PVP surfactant as a dispersing agent in a stirring or ultrasonic mode, wherein the mass ratio of the graphene oxide to the carbon nano tubes to PVP is 1-10:1-10:0.1-1;
e. uniformly stirring and mixing the powder C and the dispersion liquid D, placing the mixture in a microwave reaction kettle, performing microwave hydrothermal reaction for 0.5-2 hours at 100-220 ℃ in a closed state, drying at 60-120 ℃, and crushing for the third time to obtain a 1000-2000 mesh composite biomass hard carbon precursor E;
f. under the protection of nitrogen or argon inert atmosphere, the composite biomass hard carbon precursor E is pre-carbonized for 1-6 hours at a low temperature of 300-650 ℃ at a heating speed of 1-20 ℃/min to obtain a composite biomass pre-carbonized material F;
g. then the composite biomass pre-carbonized material F is treated for 1 to 6 hours at a high temperature of 850 to 1500 ℃ under the protection of nitrogen or argon inert atmosphere at a uniform heating speed of 1 to 20 ℃/min to obtain a composite biomass hard carbon material G;
h. and adding PVDF dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain the composite biomass hard carbon electrode material H. The NMP solution of PVDF is 0.9-5% by mass.
The nano carbon material composite biomass hard carbon electrode material prepared according to the steps can be used as an electrode material for chemical energy storage, and specifically comprises the following steps: coating a layer of conductive paste (with single-sided thickness of 1-3 μm) formed by one or more conductive agents in CNT, GO, SP on the surface of aluminum or copper foil, perforated foil of aluminum or copper, and perforated foil of aluminum or copper or nickel foam metal, coating a layer of composite biomass hard carbon electrode material H on the surface of the conductive paste, tabletting under the pressure of 5-20MPa, compacting to a thickness of 50-70 μm, and vacuum drying in a dryer at 60 ℃ for 8 hours to ensure complete removal of the solvent, thus obtaining the composite biomass hard carbon electrode with a multi-stage pore canal sheet-shaped sandwich structure.
The button cell test method used in the invention comprises the following steps: takes a composite or pure biomass hard carbon electrode as a negative electrode, takes a lithium sheet as a counter electrode, and takes 1M LiPF 6 The mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with the mass ratio of 1:3 is taken as electrolyte, the diaphragm is PE/PP/PE composite film, the button cell is assembled, and charging and discharging are carried out under the voltage of 0.005-2V at the current density of 0.2C and 5C.
The invention provides a preparation method of a nano carbon material composite biomass hard carbon electrode material, which is characterized in that Graphene (GO) has larger specific surface area and excellent electron conductivity and heat conductivity, but the lamination phenomenon of graphene sheets can obstruct ion transmission, so that the energy density and the power density of the material are reduced. Therefore, graphene and biomass hard carbon are compounded, aggregation of graphene can be effectively reduced, contact sites of active substances can be increased, and interface properties of the hard carbon are improved. Meanwhile, carbon Nanotubes (CNTs) are doped in the carbon material, so that the structural stability of the composite material can be enhanced, the agglomeration phenomenon and the lamination phenomenon of graphene sheets during biomass carbonization can be inhibited, the pore structure can be increased, more ion storage places can be provided, the diffusion kinetics of ions can be accelerated, and the ion conductivity and the electron conductivity can be improved. Through the synergistic effect among the graphene, the carbon nano tube and the hard carbon, the respective advantages of the graphene, the carbon nano tube and the hard carbon are fully exerted, and the structure and the properties are complementary, so that the graphene/carbon composite material has more excellent electrochemical performance than a single material. The obtained composite hard carbon material has rich energy storage sites of the carbon material, has higher mass specific capacitance, improves the electrical conductivity and the thermal conductivity, and improves the first efficiency, the circulation stability and the multiplying power performance.
Example 1
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning coconut shells, vacuum drying at 60 ℃, and crushing by using a crusher to obtain 30-mesh particles A;
b. adding the particles A into a 1mol/L potassium hydroxide aqueous solution, heating and stirring at 100 ℃ for 6 hours, repeatedly flushing with deionized water, centrifuging until the mixed solution is neutral, performing solid-liquid separation, vacuum drying the solid substances at 60 ℃, and crushing for the second time by using a crusher to obtain 100-mesh powder B;
c. adding the powder B into a nitric acid solution with the concentration of 1mol/L, heating and stirring for 6 hours at the temperature of 100 ℃, repeatedly flushing with deionized water, centrifuging until the mixed solution is neutral, performing solid-liquid separation, and vacuum drying solid substances at the temperature of 60 ℃ to obtain powder C;
d. preparing uniform dispersion liquid D of graphene oxide and carbon nano tubes in 1mol/L dilute sulfuric acid by taking PVP surfactant as a dispersing agent through ultrasonic treatment for 1h, wherein the mass ratio of the graphene oxide to the carbon nano tubes to PVP is 10:10:1;
e. uniformly stirring and mixing 20g of powder C and 70mL of dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 1h at 120 ℃ in a closed state, and then carrying out vacuum drying at 60 ℃ and then crushing for the third time by a crusher to obtain a 1500-mesh composite biomass hard carbon precursor E;
f. carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E in a muffle furnace at 600 ℃ for 2 hours under the protection of nitrogen atmosphere at a heating speed of 10 ℃/min to obtain a composite biomass pre-carbonized material F;
g. the composite biomass pre-carbonized material F is treated for 2 hours in a muffle furnace at a high temperature of 1000 ℃ under the protection of nitrogen atmosphere at a heating speed of 10 ℃/min to obtain a composite biomass hard carbon material G;
h. and adding PVDF dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain the composite biomass hard carbon electrode material H. The mass fraction of NMP solution of PVDF was 5%.
Example 2
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning the straw, performing forced air drying at 100 ℃, and then performing preliminary crushing by using a crusher to obtain 50-mesh particles A;
b. adding the particles A into a sodium hydroxide aqueous solution with the concentration of 2mol/L, heating and mechanically stirring for 2 hours at 90 ℃, repeatedly flushing with deionized water, carrying out suction filtration until the mixed solution is neutral, then carrying out solid-liquid separation, carrying out forced air drying on the solid substances at 100 ℃, and carrying out secondary crushing by using a crusher to obtain 150-mesh powder B;
c. adding the powder B into a hydrochloric acid solution with the concentration of 2mol/L, heating and mechanically stirring for 2 hours at 90 ℃, repeatedly flushing with deionized water, carrying out suction filtration until the mixed solution is neutral, then carrying out solid-liquid separation, and carrying out forced air drying on solid substances at 100 ℃ to obtain powder C;
d. preparing uniform dispersion liquid D of graphene oxide and carbon nano tubes in 1mol/L dilute nitric acid by taking PVP surfactant as a dispersing agent through mechanical stirring for 10 hours, wherein the mass ratio of the graphene oxide to the carbon nano tubes to PVP is 5:10:1;
e. uniformly stirring and mixing 20g of powder C and 70mL of dispersion D mechanically, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 0.5h at 150 ℃ in a closed state, and then carrying out forced air drying at 100 ℃ and then crushing for the third time by a crusher to obtain a 1200-mesh composite biomass hard carbon precursor E;
f. carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E in a muffle furnace at 550 ℃ for 1h under the protection of nitrogen atmosphere at a heating speed of 5 ℃/min to obtain a composite biomass pre-carbonized material F;
g. under the protection of nitrogen atmosphere, uniformly heating the composite biomass pre-carbonized material F at a speed of 5 ℃/min, and treating the composite biomass pre-carbonized material F in a muffle furnace at a high temperature of 900 ℃ for 1 hour to obtain a composite biomass hard carbon material G;
h. and adding PVDF dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain the composite biomass hard carbon electrode material H. The mass fraction of NMP solution of PVDF was 2%.
Example 3
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning bamboo stalks, vacuum drying at 80 ℃, and then primarily crushing by a crusher to obtain 60-mesh particles A;
b. putting the particles A into an ammonia water solution with the concentration of 3mol/L, heating and stirring at 90 ℃ for 6 hours, repeatedly flushing with deionized water, carrying out suction filtration until the mixed solution is neutral, carrying out solid-liquid separation, vacuum drying solid substances at 80 ℃, and crushing for the second time by using a crusher to obtain 200-mesh powder B;
c. adding the powder B into a hydrochloric acid solution with the concentration of 3mol/L, heating and stirring at 90 ℃ for 6 hours, repeatedly flushing with deionized water, carrying out suction filtration until the mixed solution is neutral, then carrying out solid-liquid separation, and vacuum drying solid substances at 80 ℃ to obtain powder C;
d. preparing uniform dispersion liquid D of graphene oxide and carbon nano tubes in 0.5mol/L dilute sulfuric acid by taking PVP surfactant as a dispersing agent through ultrasonic treatment for 2 hours, wherein the mass ratio of the graphene oxide to the carbon nano tubes to PVP is 5:10:1;
e. uniformly stirring and mixing 20g of powder C and 70mL of dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 2 hours at 100 ℃ in a closed state, and then carrying out vacuum drying at 80 ℃ and then crushing for the third time by a crusher to obtain 1800-mesh composite biomass hard carbon precursor E;
f. carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E in a tubular furnace at 650 ℃ for 2 hours under the protection of argon atmosphere at a heating speed of 10 ℃/min to obtain a composite biomass pre-carbonized material F;
g. under the protection of argon atmosphere, uniformly heating the composite biomass pre-carbonized material F at a speed of 10 ℃/min, and treating the composite biomass pre-carbonized material F in a tube furnace at a high temperature of 1200 ℃ for 2 hours to obtain a composite biomass hard carbon material G;
h. and adding PVDF dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain the composite biomass hard carbon electrode material H. The NMP solution of PVDF was 1.5% by mass.
Example 4
The embodiment provides a nano carbon material composite biomass hard carbon electrode material, which is prepared by the following steps:
a. cleaning tobacco stems, and performing forced air drying at 100 ℃ and then performing preliminary crushing by using a crusher to obtain 20-mesh particles A;
b. adding the particles A into a sodium hydroxide solution with the concentration of 2mol/L, heating and stirring at 100 ℃ for 3 hours, repeatedly flushing with deionized water, centrifuging until the mixed solution is neutral, performing solid-liquid separation, drying solid substances by air blast at 100 ℃, and crushing for the second time by using a crusher to obtain 100-mesh powder B;
c. adding the powder B into a nitric acid solution with the concentration of 2mol/L, heating and stirring for 3 hours at the temperature of 100 ℃, repeatedly flushing with deionized water, centrifuging until the mixed solution is neutral, performing solid-liquid separation, and drying solid substances by blowing at the temperature of 100 ℃ to obtain powder C;
d. preparing uniform dispersion liquid D of graphene oxide and carbon nano tubes in 0.5mol/L dilute nitric acid by taking PVP surfactant as a dispersing agent through ultrasonic treatment for 2 hours, wherein the mass ratio of the graphene oxide to the carbon nano tubes to PVP is 10:10:1;
e. uniformly stirring and mixing 20g of powder C and 70mL of dispersion liquid D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 1h at 150 ℃ in a closed state, and then carrying out forced air drying at 100 ℃ and then carrying out third crushing by a crusher to obtain 1600-mesh composite biomass hard carbon precursor E;
f. carrying out low-temperature pre-carbonization on the composite biomass hard carbon precursor E in a tubular furnace for 3 hours at a heating speed of 5 ℃/min under the protection of argon atmosphere at 500 ℃ to obtain a composite biomass pre-carbonized material F;
g. under the protection of argon atmosphere, uniformly heating the composite biomass pre-carbonized material F at a speed of 5 ℃/min, and treating the composite biomass pre-carbonized material F in a tubular furnace at a high temperature of 1300 ℃ for 1 hour to obtain a composite biomass hard carbon material G;
h. and adding PVDF dissolved in N-methyl pyrrolidone into the composite biomass hard carbon material G according to the mass ratio of 95:5, and uniformly mixing to obtain the composite biomass hard carbon electrode material H. The NMP solution of PVDF was 0.9% by mass.
Comparative example 1
The comparative example provides a nano carbon material composite biomass hard carbon electrode material, and the preparation method comprises the steps of adding 20g of powder C and 70mL of dispersion liquid D into a common hydrothermal reaction kettle for reaction, and keeping the same as in example 1 except that in the step e, the powder C and the dispersion liquid D are uniformly stirred and mixed.
Comparative example 2
This comparative example provides a pure biomass hard carbon electrode material prepared in the same manner as in example 1 except that steps d and e were not included.
Comparative example 3
Carrying out low-temperature pre-carbonization on the powder C in the embodiment 1 in a muffle furnace at a heating speed of 10 ℃/min under the protection of nitrogen atmosphere for 2 hours at 600 ℃ to obtain a biomass pre-carbonized material I; mixing and grinding the biomass pre-carbonized material I with graphene oxide and carbon nano tubes, or mixing the biomass pre-carbonized material I with graphene oxide and carbon nano tubes by adding water and stirring; then under the protection of nitrogen atmosphere, treating for 2 hours in a muffle furnace at a high temperature of 1000 ℃ at a heating speed of 10 ℃/min; composite biomass hard carbon material G can not be prepared.
The results of the electrochemical performance test of each example and comparative example are shown in table 1.
Table 1 results of electrochemical performance test of examples, comparative examples
From the test results, the battery prepared by adopting the nano carbon material composite biomass hard carbon material as the lithium ion battery anode material has higher specific capacity, higher first charge and discharge efficiency and excellent multiplying power performance compared with the composite biomass hard carbon material and the pure biomass hard carbon material obtained after common hydrothermal reaction treatment.
The foregoing is a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variations and modification made to the above embodiment according to the technology of the present invention are within the scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of the nano carbon material composite biomass hard carbon electrode material is characterized by comprising the following steps of:
a. cleaning a biomass raw material, drying at 60-120 ℃, and primarily crushing after drying to obtain 16-60 mesh particles A;
b. adding the particles A into an alkali solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, then washing with deionized water, carrying out suction filtration or centrifugation until the mixed solution is neutral, then carrying out solid-liquid separation, drying solid substances at 60-120 ℃ after separation, and carrying out secondary crushing to obtain 100-400 mesh powder B;
c. adding the powder B into an acid solution with the concentration of 1-5mol/L, heating and stirring at 90-120 ℃ for 1-12h, then washing with deionized water, carrying out suction filtration or centrifugation until the mixed solution is neutral, then carrying out solid-liquid separation, and drying solid substances at 60-120 ℃ after separation to obtain powder C;
d. uniformly stirring and mixing powder C and dispersion D, placing the mixture in a microwave reaction kettle, carrying out microwave hydrothermal reaction for 0.5-2h at 100-220 ℃ in a closed state, drying at 60-120 ℃ and then crushing for the third time to obtain a 1000-2000 mesh composite biomass hard carbon precursor E, wherein the dispersion D is prepared by mixing graphene oxide, carbon nano tubes and PVP according to the mass ratio of 1-10:1-10:0.1-1, and particularly preparing uniform dispersion D of graphene oxide and carbon nano tubes in 0.05-1mol/L dilute acid in a stirring or ultrasonic mode by taking PVP surfactant as a dispersing agent;
e. under the protection of nitrogen or argon inert atmosphere, the composite biomass hard carbon precursor E is pre-carbonized for 1-6 hours at a low temperature of 300-650 ℃ at a heating speed of 1-20 ℃/min to obtain a composite biomass pre-carbonized material F;
f. then the composite biomass pre-carbonized material F is treated for 1 to 6 hours at a high temperature of 850 to 1500 ℃ under the protection of nitrogen or argon inert atmosphere at a heating speed of 1 to 20 ℃/min to obtain a composite biomass hard carbon material G;
g. the composite biomass hard carbon material G is prepared by the following steps of: and 5, adding PVDF dissolved in N-methyl pyrrolidone in a proportion, and uniformly mixing to obtain the composite biomass hard carbon electrode material H, wherein the mass fraction of NMP solution in the PVDF is 0.9-5%.
2. The method for preparing the nano carbon material composite biomass hard carbon electrode material according to claim 1, which is characterized in that: the biomass is one or more of coconut shells, straws, bamboo stalks and tobacco stalks.
3. The method for preparing the nano carbon material composite biomass hard carbon electrode material according to claim 1, which is characterized in that: the alkali solution in the step b is potassium hydroxide, sodium hydroxide or ammonia water.
4. The method for preparing the nano carbon material composite biomass hard carbon electrode material according to claim 1, which is characterized in that: the acid solution in the step c is hydrochloric acid or nitric acid.
5. The nano carbon material composite biomass hard carbon electrode material is characterized in that: the nano carbon material composite biomass hard carbon electrode material is prepared by the method of any one of claims 1 to 4.
6. The application of the nano carbon material composite biomass hard carbon electrode material is characterized in that: a composite biomass hard carbon electrode comprising the nano carbon material composite biomass hard carbon electrode material according to any one of claims 1 to 4 as an electrochemical energy storage.
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| CN114388737B (en) * | 2021-12-24 | 2022-12-02 | 西安理工大学 | Self-supporting electrode, preparation method thereof and lithium-sulfur battery |
| CN116940522A (en) * | 2021-12-31 | 2023-10-24 | 宁德时代新能源科技股份有限公司 | Hard carbon, preparation method thereof, secondary battery containing hard carbon and electric device |
| CN114824225A (en) * | 2022-05-12 | 2022-07-29 | 复旦大学 | Composite negative electrode material doped with nano graphite and preparation method thereof |
| CN115036473A (en) * | 2022-05-19 | 2022-09-09 | 福州大学 | Hard carbon precursor and doped phase-based sodium ion battery negative electrode material and preparation method thereof |
| CN115557486B (en) * | 2022-11-10 | 2024-02-02 | 泰安市法拉第能源科技有限公司 | Hard carbon negative electrode material, preparation method thereof, negative electrode plate and sodium ion battery |
| CN115557487A (en) * | 2022-11-10 | 2023-01-03 | 泰安市法拉第能源科技有限公司 | Hard carbon negative electrode material for sodium ion battery, preparation method of hard carbon negative electrode material and sodium ion battery |
| CN116216691A (en) * | 2023-02-02 | 2023-06-06 | 湖北万润新能源科技股份有限公司 | Hard carbon and preparation method and application thereof |
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