CN114388736B - Method for preparing hard carbon negative electrode of lithium/sodium ion battery by biomass charcoal - Google Patents
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- 239000002028 Biomass Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 18
- 239000003610 charcoal Substances 0.000 title claims description 64
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000000197 pyrolysis Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 12
- 230000000630 rising effect Effects 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 6
- VTTUKXZEJFCOIL-UHFFFAOYSA-N (3-aminophenyl)urea;hydron;chloride Chemical compound Cl.NC(=O)NC1=CC=CC(N)=C1 VTTUKXZEJFCOIL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 238000005087 graphitization Methods 0.000 abstract description 3
- 230000002860 competitive effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 provides a method for preparing a hard carbon anode of a lithium/sodium ion battery by biomass carbon, which comprises the following steps: s1, pretreatment of biomass carbon, preparation of a precursor material in S2, pyrolysis carbonization in S3, modification of the biomass carbon, setting carbonization temperature and carbonization time, and controlling cooling rate, so that the obtained biomass carbon is carbonized to generate amorphous carbon, the graphitization degree is low, surface defects are few, the specific charge capacity is larger, and the performance is stable in the cyclic charge and discharge process; meanwhile, the process is relatively simple, reduces special complex processes, does not need special regulation and control on the morphology, and is suitable for large-scale industrial production; the product has relatively good performance and certain competitive advantage.
Description
Technical Field
The invention relates to the field of biological materials, in particular to a method for preparing a hard carbon negative electrode of a lithium/sodium ion battery by biomass carbon.
Background
In recent years, mobile phones, tablet computers, notebook computers and other portable electronic products are rapidly developed, new energy electric vehicles are continuously popularized, and demands for energy storage systems are continuously increasing. Graphite is widely used as a negative electrode material of a lithium ion battery because of the advantages of good stability, long cycle life and the like. However, since the theoretical specific capacity of graphite is only 372mAh/g, the graphite anode material cannot meet the increasing demands for high energy density and power density; and the coated graphite anode material obtained by coating and other processes has slightly poorer long-cycle stability; biomass charcoal is formed by pyrolysis of various natural raw materials, and a microstructure is formed by disordered stacking of graphite sheets, so that the biomass charcoal is a good raw material for preparing a negative electrode material, but the charcoal negative electrode material prepared by the current method is irregular in appearance, high in surface defect, small in capacitance, poor in performance in a long-cycle charge and discharge process, long in preparation method time, complex in steps and the like, and high in cost.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a hard carbon negative electrode of a lithium/sodium ion battery by using biomass carbon, so as to solve the above problems.
The technical scheme of the invention is realized as follows: a method for preparing a hard carbon anode of a lithium/sodium ion battery by biomass charcoal comprises the following steps:
s1, pretreatment of biomass charcoal: adding hydrochloric acid into the modified biomass charcoal for pickling for 3-12 hours, and then washing the biomass charcoal with deionized water to be neutral; residual biomass and impurities in biomass carbon are removed through an acid washing step, hydrochloric acid is reserved in the acid-washed biomass, and a large amount of deionized water is used for washing to achieve the purposes of adjusting pH and removing impurities;
s2, preparing a precursor material: pouring the washed biomass charcoal into a ball milling tank, adding absolute ethyl alcohol, ball milling and crushing, and filtering and drying after ball milling is completed to obtain a precursor material; the biomass material is required to be subjected to ball milling in a stainless steel ball milling tank, and ball milling can be divided into wet ball milling and dry ball milling;
s3, pyrolysis carbonization: placing the obtained precursor material in a tube furnace, carbonizing at 1200-1300 ℃ for 0.5-3 h under argon atmosphere, keeping the temperature for 1-3 h after carbonizing, cooling to 800-1100 ℃, and naturally cooling to 25-30 ℃ under argon to obtain a hard carbon anode material; the heat preservation time is not too long, otherwise, the performance of the product is reduced, and if too short, incomplete carbonization is caused, and the performance is reduced.
Further, the modified biomass charcoal is prepared by immersing biomass charcoal in a modifying solution for 0.2-2.5 h at 20-40 ℃ and then drying at 150-200 ℃, cellulose is swelled by immersing the biomass charcoal in the modifying solution to form fine pores, in the process, the biomass charcoal undergoes intramolecular crosslinking reaction, internal molecules undergo aromatization reaction to continuously form new carbon molecules, and meanwhile, hydrogen and oxygen elements in the biomass charcoal are easily removed in the form of water under the condition of high-temperature drying by the modifying solution with certain dehydration effect, so that the biomass charcoal is activated.
Further, the modifying liquid is N-N dimethylformamide and m-amino phenylurea hydrochloride solution with the volume ratio of 1-5:3.
Further, the concentration of hydrochloric acid in S1 is 0.5 to 1.5M.
Further, the mass volume ratio g/mL of the biomass charcoal and the hydrochloric acid in the S1 is 1:0.077 to 0.13.
Further, the mass volume ratio g/mL of the biomass charcoal and the absolute ethyl alcohol in the S2 is 0.6-1.3:3-5.
Further, the rotating speed of the ball mill in the step S2 is 200-500 rpm, and the ball milling time is 3-12 h.
Further, the temperature rise program of the tube furnace in the step S3 is 30-1000℃: the temperature rising rate is 4-6 ℃/min, and the temperature is 1000-1300℃: the heating rate is 3-5 ℃/min, the heating rate is not too high, otherwise, the internal structure is easy to damage.
Further, the cooling rate of the tube furnace in the step S3 is 3-5 ℃/min, the temperature of the product is kept to be slowly reduced, otherwise, the product is cracked, the performance is reduced and the like.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for preparing the hard carbon cathode of the lithium/sodium ion battery by using the biomass carbon, the process treatment is optimized, the biomass carbon is modified, the biomass carbon is pyrolyzed and carbonized after being activated, argon is added for treatment, the carbonization temperature and the carbonization time are set, and the cooling rate is controlled, so that the obtained biomass carbon generates amorphous carbon after carbonization, the graphitization degree is low, the surface defects are few, the specific charge capacity of charge and discharge is larger, and the performance is stable in the cyclic charge and discharge process; meanwhile, the process is relatively simple, reduces special complex processes, does not need special regulation and control on the morphology, and is suitable for large-scale industrial production; the product has relatively good performance and certain competitive advantage.
Drawings
FIG. 1 is a Raman diagram in example 3;
fig. 2 is a long-cycle charge-discharge capacity in example 3;
FIG. 3 is an XRD pattern for example 3;
fig. 4 is a plot of voltage versus capacity for the first three turns in example 3.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
A method for preparing a hard carbon anode of a lithium/sodium ion battery by biomass charcoal comprises the following steps:
s1, pretreatment of biomass charcoal: adding 0.5M hydrochloric acid to the modified biomass charcoal for pickling for 3 hours, wherein the mass volume ratio g/mL of the biomass charcoal to the hydrochloric acid is 1:0.077, and then washing with deionized water to neutrality; the modified biomass charcoal is prepared by immersing biomass charcoal in a modifying solution, wherein the modifying solution is N-N dimethylformamide and m-amino phenylurea hydrochloride solution with the volume ratio of 1:3, immersing for 0.2h at 20 ℃, and drying at 150 ℃;
s2, preparing a precursor material: pouring the washed biomass charcoal into a stainless steel ball milling tank, adding absolute ethyl alcohol, performing wet ball milling and crushing, wherein the mass volume ratio g/mL of the biomass charcoal and the absolute ethyl alcohol is 0.6:3, the rotating speed of the ball milling is 200rpm, and the ball milling time is 3 hours;
s3, pyrolysis carbonization: placing the obtained precursor material in a tube furnace, carbonizing at 1200 ℃ for 0.5h under argon atmosphere, keeping the temperature for 1h after carbonizing at 10mL/min, wherein the temperature of the tube furnace is 30-1000 ℃: the temperature rising rate is 4 ℃/min, and the temperature is 1000-1200℃: the temperature rising rate is 3 ℃/min; cooling to 800 ℃, wherein the cooling rate is 3 ℃/min, continuously introducing argon, and naturally cooling to 25 ℃ to obtain the hard carbon anode material.
Example 2
A method for preparing a hard carbon anode of a lithium/sodium ion battery by biomass charcoal comprises the following steps:
s1, pretreatment of biomass charcoal: adding 1.5M hydrochloric acid to the modified biomass charcoal for pickling for 12 hours, wherein the mass volume ratio g/mL of the biomass charcoal to the hydrochloric acid is 1:0.13, and then washing with deionized water to neutrality; the modified biomass charcoal is prepared by immersing biomass charcoal in a modifying liquid, wherein the modifying liquid is N-N dimethylformamide and m-amino phenylurea hydrochloride solution with the volume ratio of 5:3, immersing for 2.5 hours at 40 ℃, and drying at 200 ℃;
s2, preparing a precursor material: pouring the washed biomass charcoal into a stainless steel ball milling tank, adding absolute ethyl alcohol, carrying out dry ball milling and crushing, wherein the mass volume ratio g/mL of the biomass charcoal and the absolute ethyl alcohol is 1.3:5, the rotating speed of the ball milling is 500rpm, and the ball milling time is 12 hours;
s3, pyrolysis carbonization: placing the obtained precursor material in a tube furnace, carbonizing at 1300 ℃ for 3h in argon atmosphere, keeping the temperature for 3h after carbonizing at 30mL/min, wherein the temperature of the tube furnace is 30-1000 ℃ in a heating program: the temperature rising rate is 6 ℃/min, and the temperature is 1000-1300℃: the temperature rising rate is 5 ℃/min; cooling to 1100 ℃, wherein the cooling rate is 5 ℃/min, continuously introducing argon, and naturally cooling to 30 ℃ to obtain the hard carbon anode material.
Example 3
A method for preparing a hard carbon anode of a lithium/sodium ion battery by biomass charcoal comprises the following steps:
s1, pretreatment of biomass charcoal: adding 1M hydrochloric acid into the modified biomass charcoal for pickling for 8 hours, wherein the mass volume ratio g/mL of the biomass charcoal to the hydrochloric acid is 1:0.12, and then washing with deionized water to neutrality; the modified biomass charcoal is prepared by immersing biomass charcoal in a modifying solution, wherein the modifying solution is N-N dimethylformamide and m-amino phenylurea hydrochloride solution with the volume ratio of 4:3, immersing for 1.3h at 30 ℃, and drying at 180 ℃;
s2, preparing a precursor material: pouring the washed biomass charcoal into a stainless steel ball milling tank, adding absolute ethyl alcohol, performing wet ball milling and crushing, wherein the mass volume ratio g/mL of the biomass charcoal and the absolute ethyl alcohol is 0.9:4, the rotating speed of the ball milling is 400rpm, and the ball milling time is 7 hours;
s3, pyrolysis carbonization: placing the obtained precursor material in a tube furnace, carbonizing at 1250 ℃ for 2h in argon atmosphere, wherein the ventilation amount is 20mL/min, and keeping the temperature for 2h after carbonizing, wherein the temperature of the tube furnace is 30-1000 ℃ in a heating program: the temperature rising rate is 5 ℃/min, and the temperature is 1000-1250℃: the temperature rising rate is 4 ℃/min; cooling to 1000 ℃, wherein the cooling rate is 4 ℃/min, continuously introducing argon, and naturally cooling to 25-30 ℃ to obtain the hard carbon anode material.
Example 4
The difference between this embodiment and embodiment 3 is that the biomass charcoal is not modified, specifically a method for preparing a hard carbon anode of a lithium/sodium ion battery by using biomass charcoal, comprising the following steps:
s1, pretreatment of biomass charcoal: adding 1M hydrochloric acid into biomass charcoal for pickling for 8 hours, wherein the mass volume ratio g/mL of the biomass charcoal to the hydrochloric acid is 1:0.12, and then washing with deionized water to neutrality;
s2, preparing a precursor material: pouring the washed biomass charcoal into a stainless steel ball milling tank, adding absolute ethyl alcohol, performing wet ball milling and crushing, wherein the mass volume ratio g/mL of the biomass charcoal and the absolute ethyl alcohol is 0.9:4, the rotating speed of the ball milling is 400rpm, and the ball milling time is 7 hours;
s3, pyrolysis carbonization: placing the obtained precursor material in a tube furnace, carbonizing at 1250 ℃ for 2h in argon atmosphere, wherein the ventilation amount is 20mL/min, and keeping the temperature for 2h after carbonizing, wherein the temperature of the tube furnace is 30-1000 ℃ in a heating program: the temperature rising rate is 5 ℃/min, and the temperature is 1000-1250℃: the temperature rising rate is 4 ℃/min; cooling to 1000 ℃, wherein the cooling rate is 4 ℃/min, continuously introducing argon, and naturally cooling to 25-30 ℃ to obtain the hard carbon anode material.
1. Performance testing
(1) The hard carbon anode materials prepared in examples 1 to 4 were subjected to Raman performance test, and then subjected to 1 c=400 ma·g -1 Firstly, constant-current and constant-voltage discharge is carried out to 5mV, then constant-current charge is carried out to 1.5V, 100 circles of constant-current performance test are circulated, 100 circles of charge and discharge are carried out, and the test results show that the capacitance is:
from the above results, it is understood that amorphous carbon is formed after carbonization of biomass carbon, wherein the appearance of two characteristic peaks of carbon material, namely D peak and G peak of example 3, is shown in FIG. 1 to indicate that the material is converted from pure biomass to carbon material, I of example 3 D /I G A value of 0.64 indicates that the resulting material is very low graphitized, demonstrating the intrinsic amorphous and amorphizing properties of hard carbon; as can be seen from FIG. 2, the capacitance is 196.0 mAh.g at 100 cycles -1 The performance stability in the cyclic charge and discharge process is illustrated;
example 3 shows that the carbonization temperature and carbonization time have a larger influence on the biomass carbon compared with examples 1 to 2, and that the biomass carbon modified by the method has a remarkable activation effect, a lower graphitization degree and fewer surface defects compared with example 4.
(2) The hard carbon anode material prepared in example 3 was subjected to XRD characterization, and the kind and content of the phase were analyzed from fig. 3, resulting in a pure phase.
(3) The hard carbon negative electrode material prepared in example 3 was tested for voltage-capacity, and the curve was smoother as can be seen in fig. 4, indicating that the negative electrode material was relatively stable.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. A method for preparing a hard carbon anode of a lithium/sodium ion battery by biomass charcoal is characterized by comprising the following steps: the method comprises the following steps:
s1, pretreatment of biomass charcoal: adding hydrochloric acid into the modified biomass charcoal for pickling for 3-12 hours, and then washing the modified biomass charcoal with deionized water to be neutral; the modified biomass charcoal is prepared by immersing biomass charcoal in a modifying liquid at 20-40 ℃ for 0.2-2.5 h and then drying at 150-200 ℃; the modifying solution is an N-N dimethylformamide and m-amino phenylurea hydrochloride solution with the volume ratio of 1-5:3;
s2, preparing a precursor material: pouring the biomass charcoal washed by the deionized water into a ball milling tank, adding absolute ethyl alcohol, ball milling and crushing, and filtering and drying after ball milling is completed to obtain a precursor material;
s3, pyrolysis carbonization: and (3) placing the precursor material in a tube furnace, carbonizing at 1200-1300 ℃ for 0.5-3 h under the argon atmosphere, keeping the temperature for 1-3 h after carbonizing, cooling to 800-1100 ℃, and naturally cooling to 25-30 ℃ under the argon atmosphere to obtain the hard carbon anode material.
2. The method for preparing the hard carbon cathode of the lithium/sodium ion battery by using the biomass charcoal according to claim 1, wherein the method comprises the following steps of: the concentration of hydrochloric acid in the S1 is 0.5-1.5M.
3. The method for preparing the hard carbon cathode of the lithium/sodium ion battery by using the biomass charcoal according to claim 1, wherein the method comprises the following steps of: in the S1, the mass volume ratio g/mL of the biomass charcoal and the hydrochloric acid is 1:0.077 to 0.13.
4. The method for preparing the hard carbon cathode of the lithium/sodium ion battery by using the biomass charcoal according to claim 1, wherein the method comprises the following steps of: and the mass volume ratio g/mL of the biomass charcoal and the absolute ethyl alcohol in the S2 is 0.6-1.3:3-5.
5. The method for preparing the hard carbon cathode of the lithium/sodium ion battery by using the biomass charcoal according to claim 1, wherein the method comprises the following steps of: and the rotating speed of the ball mill in the step S2 is 200-500 rpm, and the ball milling time is 3-12 h.
6. The method for preparing the hard carbon cathode of the lithium/sodium ion battery by using the biomass charcoal according to claim 1, wherein the method comprises the following steps of: the temperature rise program of the tubular furnace in the step S3 is 30-1000℃: the temperature rising rate is 4-6 ℃/min, and the temperature is 1000-1300℃: the temperature rising rate is 3-5 ℃/min.
7. The method for preparing the hard carbon cathode of the lithium/sodium ion battery by using the biomass charcoal according to claim 1, wherein the method comprises the following steps of: and the cooling rate of the tube furnace in the step S3 is 3-5 ℃/min.
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WO2020103140A1 (en) * | 2018-11-23 | 2020-05-28 | 辽宁星空钠电电池有限公司 | Biomass-based hard carbon negative electrode material for sodium ion battery, preparation method therefor and use thereof |
CN109678130A (en) * | 2018-12-20 | 2019-04-26 | 电子科技大学 | A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery |
CN111009659A (en) * | 2019-10-14 | 2020-04-14 | 桂林理工大学 | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material |
CN111564630A (en) * | 2020-06-09 | 2020-08-21 | 厦门理工学院 | Hard carbon material and preparation method thereof |
CN113571703A (en) * | 2021-09-26 | 2021-10-29 | 天津市职业大学 | Sodium ion battery carbon-based negative electrode material and preparation method thereof |
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