CN115304052A - Wood-based composite hard carbon negative electrode material and preparation method and application thereof - Google Patents
Wood-based composite hard carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- CN115304052A CN115304052A CN202211254210.4A CN202211254210A CN115304052A CN 115304052 A CN115304052 A CN 115304052A CN 202211254210 A CN202211254210 A CN 202211254210A CN 115304052 A CN115304052 A CN 115304052A
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- 239000002023 wood Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 94
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 19
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 4
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
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- 210000004027 cell Anatomy 0.000 description 8
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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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
- 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
- H01M2004/026—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 embodiment of the invention relates to a wood-based composite hard carbon negative electrode material and a preparation method and application thereof. The preparation method comprises the following steps: crushing the wood hard carbon substrate material to 100-300 meshes, mixing the crushed wood hard carbon substrate material with polyhydroxy aldehyde according to a proportion, and adding the mixture into a carboxylic acid solution with the mass concentration of 1-20% to obtain a mixed solution; heating the mixed solution at 60-120 ℃, drying the mixed solution after 6-48 hours, carrying out hot pressing treatment on the dried material, and pressing the material into a block material; putting the block-shaped material into a reaction device, heating to 400-600 ℃ under protective atmosphere, preserving heat for 1-20 hours, carrying out pre-carbonization treatment, then further heating to 1100-1600 ℃, carrying out carbonization treatment under protective atmosphere, preserving heat for 1-10 hours, discharging, and then crushing and sieving again to obtain the wood-based composite hard carbon cathode material which is irregular in shape and has a sandwich structure formed by two hard carbons of wood-based hard carbon and filled hard carbon.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of sodium ion batteries, in particular to a wood-based composite hard carbon negative electrode material and a preparation method and application thereof.
Background
With the development and popularization of new energy, secondary batteries typified by lithium ion batteries are widely used in electric vehicles, consumer electronics, and energy storage fields. The method has the advantages of high energy density, long cycle life, high energy conversion efficiency and the like. But the scarcity of lithium ore resources causes the price of the lithium resources to be continuously high, so that the cost of the lithium ion battery is greatly increased, and the application of the lithium ion battery in the field of large-scale energy storage is limited.
Sodium as an element of the same main group has similar physicochemical properties to lithium, particularly, the resource is widely distributed, the cost is low, and aluminum foil can be used as a current collector, so that the production cost of the sodium-ion battery is further reduced.
However, the lithium ion battery is limited by the radius of sodium ions, and is difficult to be embedded into the graphite negative electrode of the lithium ion battery widely used in the prior art to form a stable compound, so that the development of a low-cost high-performance negative electrode material suitable for the sodium ion battery is always one direction of the research of the sodium ion battery.
Disclosure of Invention
The invention aims to provide a wood-based composite hard carbon negative electrode material and a preparation method and application thereof. The invention obtains the wood-based composite hard carbon cathode material with a sandwich structure formed by two hard carbons of wood-based hard carbon and filled hard carbon through infiltration and esterification reaction of the wood-based material, polyhydroxy aldehyde and carboxylic acid solution. Compared with a composite material formed by mixing a wood base material and a high polymer material through a liquid phase or a solid phase, the high polymer material can be better filled in the gaps of the wood cells in the wood base material, so that the carbonization yield is improved, the special-shaped structure of wood-based hard carbon is improved, the specific surface area is reduced, and the capacity and the circulation stability of the hard carbon material are improved.
To this end, in a first aspect, an embodiment of the present invention provides a preparation method of a wood-based composite hard carbon negative electrode material, where the preparation method includes:
crushing the wood hard carbon substrate material to 100-300 meshes, mixing the crushed wood hard carbon substrate material with polyhydroxy aldehyde according to a proportion, and adding the mixture into a carboxylic acid solution with the mass concentration of 1-20% to obtain a mixed solution;
heating the mixed solution at 60-120 ℃, drying the mixed solution after 6-48 hours, carrying out hot pressing treatment on the dried material, and pressing into a block material;
and putting the blocky material into a reaction device, heating to 400-600 ℃ under a protective atmosphere, preserving heat for 1-20 hours, carrying out pre-carbonization treatment, further heating to 1100-1600 ℃, carrying out carbonization treatment under the protective atmosphere, preserving heat for 1-10 hours, discharging, and crushing and sieving again to obtain the wood-based composite hard carbon cathode material which is irregular in shape and has a sandwich structure formed by wood-based hard carbon and filled hard carbon.
Preferably, the wood hard carbon base material is specifically: one or more of pine, cedar, poplar and birch; the polyhydroxyaldehydes include: one or more of glucose, sucrose and fructose; the carboxylic acids include: tartaric acid, citric acid and oxalic acid.
Preferably, the mixing ratio of the wood hard carbon base material to the polyhydroxy aldehyde is 1.
Preferably, the mass ratio of the mixture of the wood hard carbon base material and the polyhydroxy aldehyde to the carboxylic acid solution is 1.
Preferably, the set pressure range of the hot pressing treatment is 2MPa to 4MPa, the pressing time is 5S to 30S, and the temperature is 80 ℃ to 120 ℃.
Preferably, the protective atmosphere is nitrogen or argon, the temperature rise rate in the pre-carbonization stage is 1-5 ℃/min, the gas flow rate of the protective atmosphere is 10-20L/min, the temperature rise rate in the carbonization stage is 3-10 ℃/min, and the gas flow rate of the protective atmosphere is 2-5L/min.
In a second aspect, an embodiment of the present invention provides a wood-based composite hard carbon negative electrode material prepared by the preparation method in the first aspect.
In a third aspect, an embodiment of the present invention provides a sodium ion battery negative electrode, where the negative electrode includes the wood-based composite hard carbon negative electrode material described in the second aspect.
In a fourth aspect, embodiments of the present invention provide a sodium ion battery including the sodium ion battery negative electrode of the third aspect.
The wood-based composite hard carbon negative electrode material provided by the embodiment of the invention has an interlayer structure formed by wood-based hard carbon and filled hard carbon, the pore space of the filled hard carbon is more developed, the structural strength of the wood-based hard carbon is higher, the high capacity is ensured, and the cycle stability is improved. The wood-based composite hard carbon negative electrode material provided by the embodiment of the invention is low in cost, simple in preparation method and easy for mass production. Can be used in liquid, semi-solid, quasi-solid and all-solid electrolyte sodium ion batteries.
Drawings
FIG. 1 is a flow chart of a method of preparation provided by an embodiment of the present invention;
FIG. 2 is a graph showing the charge and discharge curves of the sodium ion batteries of example 1, example 2 and comparative example 1 according to the present invention;
fig. 3 is a Scanning Electron Microscope (SEM) image of the wood-based composite hard carbon negative electrode material provided in embodiment 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
The embodiment of the invention provides a preparation method of a wood-based composite hard carbon negative electrode material, which mainly comprises the following steps as shown in figure 1:
specifically, the wood hard carbon base material includes: pine, cedar, poplar, birch and the like or a combination of a plurality of pine, cedar, poplar, birch and the like; polyhydroxy aldehydes include: glucose, sucrose, fructose, etc. or their combination; the carboxylic acids include: tartaric acid, citric acid, oxalic acid, etc.
The addition amount is as follows:
the mixing ratio of the wood hard carbon base material to the polyhydroxy aldehyde is 1-10; the mass ratio of the mixture of the wood hard carbon base material and the polyhydroxy aldehyde to the carboxylic acid solution is 1.
the set pressure range of the hot pressing treatment is 2MPa to 4MPa, the pressing time is 5S to 30S, and the temperature is 80 ℃ to 120 ℃.
Wherein the protective atmosphere is nitrogen or argon, the temperature rise rate is 1-5 ℃/min during the pre-carbonization treatment stage, the gas flow rate of the protective atmosphere is 10-20L/min, the temperature rise rate is 3-10 ℃/min during the carbonization treatment stage, and the gas flow rate of the protective atmosphere is 2-5L/min.
The wood-based composite hard carbon negative electrode material is obtained by the preparation method. As shown in fig. 3, the wood-based composite hard carbon negative electrode material can be seen to have irregular morphology by Scanning Electron Microscopy (SEM).
The obtained material is prepared by mixing a wood hard carbon base material with polyhydroxy aldehyde, infiltrating and permeating the mixture by a carboxylic acid solution, fixing the polyhydroxy aldehyde in the cell surrounded by the cell wall of each cell of the wood base material and between the cell walls of adjacent cells through esterification, performing curing, drying and hot-pressing treatment, and carbonizing and cracking the mixture under the protection of inert atmosphere to form a hard carbon complex with two hard carbon structures of wood hard carbon and filled hard carbon; in the composite material, the filled hard carbon and the wood-based hard carbon form a sandwich structure.
According to the invention, the high polymer material can be better filled in the wooden cell gaps in the wooden base material, so that the carbonization yield is improved, the special-shaped structure of the wooden base hard carbon is improved, the interlayer structure formed by the wooden base hard carbon and the filled hard carbon is formed, the specific surface area is reduced, the pores of the filled hard carbon are more developed, the strength of the wooden base hard carbon structure is higher, the high capacity of the hard carbon material is improved, and the cycle stability is also improved.
In order to better understand the technical solutions provided by the present invention, the following description respectively illustrates specific processes of the preparation method of the wood-based composite hard carbon negative electrode material by using the method provided by the above embodiments of the present invention, and characteristics of the application of the wood-based composite hard carbon negative electrode material to a sodium ion battery by using a plurality of specific examples.
Example 1
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of pine wood is taken, crushed, sieved by a 300-mesh material, mixed with 100g of sucrose and then added into 500g of a solution with the mass concentration of citric acid of 20 percent, the mixed solution is heated at 120 ℃, and after being soaked for 6 hours, the mixed solution is dried.
Step 2: and carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 30S and the temperature to be 120 ℃, and pressing the material into a block material.
And step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at the gas flow rate of 10L/min, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at the speed of 5L/min, heating to 1100 ℃ at the speed of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again and sieving to obtain the irregular wood-based composite hard carbon negative electrode material.
In order to test the electrochemical performance of the material, the prepared wood-based composite hard carbon negative electrode material is used as an active material. According to the active substance: conductive carbon black (SP): polyvinylidene fluoride (PVDF) =90.0:5.0:5.0, taking the total amount of 15g as an example. 0.75g PVDF is added into 24.25g N Methyl Pyrrolidone (NMP), the rotating speed of a dispersion disc is 2000r/min, and the dispersion is carried out for 30min until the glue solution is clear. Adding 0.75g SP into the glue solution, rotating the dispersion plateThe speed is 2000r/min, and the dispersion time is 40min. Adding 13.5g of active substances into the slurry, dispersing for 40min at the rotating speed of a dispersion disc of 2000r/min, and adding a proper amount of NMP to adjust the viscosity to be 2000mPa.s. The slurry was screened through a 180 mesh screen prior to coating. And drying the coated pole piece at 110 ℃. After drying, the sheet was cut into circular pieces having a diameter of 8 mm. The pole pieces were dried at 120 ℃ for 6 hours under vacuum and immediately transferred to a glove box for use. The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1 mole of NaPF 6 A button cell was prepared using as electrolyte a solution of ethylene carbonate and diethyl carbonate dissolved in 1L volume ratio of 1. The electricity deduction test procedure comprises the following steps: 1. standing for 8 hours; 2. multiplying power discharge (0.1C, 0V), multiplying power discharge (0.02C, 0V), standing for 5min; 3. charging at multiplying power (0.1C, 2V), and standing for 5min. The structural and electrochemical properties were evaluated by testing.
For better comparison, we prepared a comparative sample as follows.
Comparative example 1
This comparative example provides a comparative wood-based hard carbon material prepared as follows:
step 1: and (3) crushing and sieving 100g of pine wood by a 300-mesh sieve, putting the crushed pine wood into a reaction device, introducing protective nitrogen at a flow rate of 10L/min, heating to 600 ℃ at a speed of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at a speed of 5L/min, heating to 1100 ℃ at a speed of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing and sieving again to obtain the wood-based hard carbon material of the comparison sample.
Comparative example 2
This comparative example provides a comparative wood-based hard carbon material prepared as follows:
step 1: 100g of pine wood is taken, crushed, sieved by a 300-mesh material, mixed with 100g of cane sugar and then added into 500g of aqueous solution, the mixed solution is heated at 120 ℃, soaked for 6 hours and dried.
Step 2: and (3) putting the dried material into a reaction device, introducing protective nitrogen at a gas flow rate of 10L/min, heating to 600 ℃ at a rate of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at a rate of 5L/min, heating to 1100 ℃ at a rate of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again, and sieving to obtain a contrast sample which is an irregular wood-based composite hard carbon negative electrode material.
Example 2
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of pine is taken, crushed and sieved with a 300-mesh material, mixed with 10g of fructose and then added into 110g of a solution with the citric acid mass concentration of 1 percent, the mixed solution is heated at 120 ℃, and after the mixed solution is soaked for 48 hours, the mixed solution is dried.
And 2, step: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 4MPa, the pressing time to be 5S and the temperature to be 80 ℃, and pressing the material into a block material.
And 3, step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at a gas flow rate of 20L/min, heating to 600 ℃ at a rate of 5 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen to 2L/min, heating to 1100 ℃ at a rate of 10 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, and crushing and sieving again to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 3
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of pine is taken, crushed and sieved by a 300-mesh material, mixed with 100g of cane sugar and then added into 200g of a solution with the tartaric acid mass concentration of 20 percent, the mixed solution is heated at 120 ℃, and after being soaked for 6 hours, the mixed solution is dried.
And 2, step: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 30S and the temperature to be 120 ℃, and pressing the material into a block material.
And 3, step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at the gas flow rate of 10L/min, heating to 500 ℃ at the gas flow rate of 3 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the nitrogen gas flow rate to 10L/min, heating to 1100 ℃ at the gas flow rate of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again and sieving to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 4
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of pine is taken, crushed and sieved by a 300-mesh material, and is mixed with 100g of cane sugar, then the mixture is added into 500g of solution with the citric acid mass concentration of 10 percent, the mixed solution is heated at 100 ℃, and the mixed solution is dried after being soaked for 48 hours.
Step 2: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 30S and the temperature to be 120 ℃, and pressing the material into a block material.
And step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at the gas flow rate of 10L/min, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at the speed of 5L/min, heating to 1200 ℃ at the speed of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again and sieving to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 5
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of cypress is taken, crushed and sieved by a 300-mesh material, and is mixed with 100g of cane sugar, then the mixture is added into 500g of solution with the oxalic acid mass concentration of 20 percent, the mixed solution is heated at 120 ℃, and the mixed solution is dried after being soaked for 6 hours.
Step 2: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 4MPa, the pressing time to be 20S and the temperature to be 100 ℃, and pressing the material into a block material.
And step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at the gas flow rate of 10L/min, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at the speed of 5L/min, heating to 1100 ℃ at the speed of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again and sieving to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 6
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of cypress is taken, crushed, sieved by a material of 300 meshes, mixed with 100g of cane sugar and then added into 500g of solution with the mass concentration of citric acid of 20 percent, the mixed solution is heated at 120 ℃, and the mixed solution is dried after being soaked for 6 hours.
And 2, step: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 30S and the temperature to be 120 ℃, and pressing the material into a block material.
And step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at the gas flow rate of 10L/min, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at the speed of 5L/min, heating to 1100 ℃ at the speed of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again and sieving to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 7
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of pine is taken, crushed and sieved by a 300-mesh material, mixed with 100g of fructose and then added into 500g of solution with the citric acid mass concentration of 20 percent, the mixed solution is heated at 120 ℃, and after being soaked for 6 hours, the mixed solution is dried.
Step 2: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 20S and the temperature to be 120 ℃, and pressing the material into a block material.
And step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at the gas flow rate of 10L/min, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at the speed of 5L/min, heating to 1100 ℃ at the speed of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again and sieving to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 8
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of pine is taken, crushed and sieved by a 100-mesh material, and is mixed with 100g of cane sugar, then the mixture is added into 500g of solution with the citric acid mass concentration of 20 percent, the mixed solution is heated at 120 ℃, and the mixed solution is dried after being soaked for 20 hours.
Step 2: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 30S and the temperature to be 120 ℃, and pressing the material into a block material.
And 3, step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at a gas flow rate of 10L/min, heating to 600 ℃ at a rate of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen to be 5L/min, heating to 1300 ℃ at a rate of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, and crushing and sieving again to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 9
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: pulverizing 100g birch, sieving with 300 mesh sieve, mixing with 100g fructose, adding into 500g citric acid 20% solution, heating the mixture at 120 deg.C, soaking for 10 hr, and oven drying.
Step 2: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 30S and the temperature to be 120 ℃, and pressing the material into a block material.
And 3, step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at a gas flow rate of 10L/min, heating to 600 ℃ at a rate of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen to be 5L/min, heating to 1300 ℃ at a rate of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, and crushing and sieving again to obtain the irregular wood-based composite hard carbon negative electrode material.
Example 10
The embodiment provides a wood-based composite hard carbon negative electrode material, which is prepared by the following steps:
step 1: 100g of poplar is taken, crushed and sieved by a 300-mesh material, mixed with 100g of glucose and then added into 500g of a solution with the citric acid mass concentration of 15 percent, the mixed solution is heated at 120 ℃, and after the mixed solution is soaked for 6 hours, the mixed solution is dried.
Step 2: and (3) carrying out hot pressing treatment on the dried material, setting the pressure to be 2MPa, the pressing time to be 30S and the temperature to be 120 ℃, and pressing the material into a block material.
And step 3: and putting the block material obtained by hot pressing into a reaction device, introducing protective nitrogen at the gas flow rate of 10L/min, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour for pre-carbonization, further adjusting the flow rate of the nitrogen at the speed of 5L/min, heating to 1100 ℃ at the speed of 3 ℃/min for high-temperature carbonization, preserving heat for 10 hours, discharging, crushing again and sieving to obtain the irregular wood-based composite hard carbon negative electrode material.
Cell assembly and testing were performed in the same manner as in example 1. Fig. 2 is a charge-discharge curve diagram of the sodium ion batteries of example 1, example 2 and comparative example 1 of the present invention. The specific test results of each example, comparative example 1 and comparative example 2 are shown in table 1 below.
According to the test results of the above examples 1-10 and comparative examples 1 and 2, it can be seen that the capacity and first cycle efficiency of the wood-based composite hard carbon anode material obtained by carbonization are greatly improved through the processes of compounding, esterification and pressing. In a circulation test, compared with a comparative example 1 and a comparative example 2 which are not subjected to hot pressing and polycarboxylic acid esterification treatment, the material prepared by the method has more excellent circulation performance, because the structure is complicatedly reinforced through the hot pressing and esterification processes, the interlayer structure is still kept after carbonization, and the two different structures form an interlayer, so that the hard carbon composite can keep excellent stability in the process of sodium ion extraction, and the circulation performance is ensured. In addition, as seen from comparison of data of comparative example 1 and comparative example 2, the hard carbon particles of comparative example 1 formed by firing a wood-based material alone have a large number of large pores and a high specific surface area, resulting in poor non-uniformity and stability of a solid electrolyte interface film (SEI) during charge and discharge, resulting in poor capacity and cycle performance. The comparative example 2 adopts high molecular polymer to carry out liquid phase mixing, can play the effect of filling pores and coating surfaces to a certain extent, and the carbon layer formed after carbonization can reduce the specific surface area, but the stress action exists in the compounding process of the two materials, and in the process of charging and discharging for many times, phenomena such as peeling separation and the like are formed between wood-based carbon and high molecular carbon, so that the later cycle performance is poor. According to the invention, the negative electrode material formed by adopting the hot pressing and polycarboxylic acid esterification treatment method in the embodiment has the sandwich structure formed by the wood-based hard carbon and the filled hard carbon, so that the specific surface area is reduced, the pore space of the filled hard carbon is more developed, the structural strength of the wood-based hard carbon is higher, the high capacity of the hard carbon material is improved, and the cycle stability is also improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the wood-based composite hard carbon negative electrode material is characterized by comprising the following steps:
crushing the wood hard carbon substrate material to 100-300 meshes, mixing the crushed material with polyhydroxy aldehyde according to a proportion, and adding the mixture into a carboxylic acid solution with the mass concentration of 1-20% to obtain a mixed solution;
heating the mixed solution at 60-120 ℃, drying the mixed solution after 6-48 hours, carrying out hot pressing treatment on the dried material, and pressing the material into a block material;
and putting the blocky material into a reaction device, heating to 400-600 ℃ under a protective atmosphere, preserving heat for 1-20 hours, carrying out pre-carbonization treatment, further heating to 1100-1600 ℃, carrying out carbonization treatment under the protective atmosphere, preserving heat for 1-10 hours, discharging, and crushing and sieving again to obtain the wood-based composite hard carbon cathode material which is irregular in shape and has an interlayer structure formed by wood-based hard carbon and filled hard carbon.
2. The method according to claim 1, wherein the wood-based hard carbon base material is in particular: one or more of pine, cedar, poplar and birch; the polyhydroxy aldehyde comprises: one or more of glucose, sucrose and fructose; the carboxylic acids include: one or more of tartaric acid, citric acid and oxalic acid.
3. The production method according to claim 1, wherein the mixing ratio of the woody hard carbon base material to the polyhydroxyaldehyde is 1 to 10 by mass.
4. The preparation method according to claim 1, wherein the mass ratio of the mixture of the woody hard carbon base material and the polyhydroxyaldehyde to the carboxylic acid solution is 1.
5. The production method according to claim 1, wherein the set pressure range of the hot pressing treatment is 2MPa to 4MPa, the pressing time period is 5S to 30S, and the temperature is 80 ℃ to 120 ℃.
6. The method according to claim 1, wherein the protective atmosphere is nitrogen or argon, the temperature increase rate in the pre-carbonization step is 1 to 5 ℃/min, the gas flow rate in the protective atmosphere is 10 to 20L/min, the temperature increase rate in the carbonization step is 3 to 10 ℃/min, and the gas flow rate in the protective atmosphere is 2 to 5L/min.
7. A wood-based composite hard carbon negative electrode material prepared by the preparation method of any one of claims 1 to 6.
8. A negative electrode for sodium ion battery, characterized in that it comprises the wood-based composite hard carbon negative electrode material of claim 7.
9. A sodium-ion battery comprising the negative electrode for a sodium-ion battery according to claim 8.
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