CN116854075A - Chemical surface modified biomass hard carbon material and preparation method and application thereof - Google Patents
Chemical surface modified biomass hard carbon material and preparation method and application thereof Download PDFInfo
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- CN116854075A CN116854075A CN202310916471.6A CN202310916471A CN116854075A CN 116854075 A CN116854075 A CN 116854075A CN 202310916471 A CN202310916471 A CN 202310916471A CN 116854075 A CN116854075 A CN 116854075A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 56
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 53
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 50
- 239000000126 substance Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 50
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 43
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 38
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 38
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 38
- 239000011425 bamboo Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 38
- 238000010000 carbonizing Methods 0.000 claims description 31
- 238000009832 plasma treatment Methods 0.000 claims description 27
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 235000014676 Phragmites communis Nutrition 0.000 claims description 6
- 238000009656 pre-carbonization Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 31
- 239000005539 carbonized material Substances 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 125000000524 functional group Chemical group 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 241001330002 Bambuseae Species 0.000 description 37
- 239000000843 powder Substances 0.000 description 33
- 238000001816 cooling Methods 0.000 description 22
- 239000012300 argon atmosphere Substances 0.000 description 18
- 238000000227 grinding Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000010405 anode material Substances 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000007605 air drying Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 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 8
- 239000011149 active material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000000691 measurement method Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- H01M4/36—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
-
- 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 chemical surface modified biomass hard carbon material, a preparation method and application thereof, and relates to the technical field of sodium ion battery electrode materials. The method takes biomass as a raw material, and the biomass raw material is dried, crushed and pre-carbonized, then is placed in an atmosphere plasma sintering furnace, and is carbonized at a high temperature after being treated; the pre-carbonized material is treated by a plasma reducing atmosphere, so that the oxygen-containing functional groups on the surface can be effectively reduced. On the one hand, the hydrophobicity of the surface of the hard carbon material can be improved, the problem of battery gas production and bulge in the charge and discharge process caused by the fact that hydrophilic groups on the surface are easy to adsorb water molecules is solved, and the circulation stability is improved. On the other hand, irreversible adsorption of sodium ions in the first charge and discharge process can be reduced, and the first coulomb efficiency of the hard carbon material is effectively improved. The sodium ion battery hard carbon negative electrode material obtained by modification has higher first coulombic efficiency and cycle stability. The invention also has the advantages of simple process, environmental protection and the like.
Description
Technical Field
The invention relates to the technical field of sodium ion battery electrode materials, in particular to a chemical surface modified biomass hard carbon material, a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in the fields of consumer electronics, new energy automobiles, large-scale energy storage power stations, and the like due to their excellent energy storage properties. Along with the rapid improvement of the productivity of the lithium ion battery, the price and water rise of the lithium raw material greatly influence the lithium ion battery industry due to the scarcity of lithium resources. The sodium ion battery and the lithium ion battery have similar energy storage mechanisms, and the sodium element has high abundance in the crust, low cost and no resource shortage problem, so the sodium ion battery is the next generation alkali metal ion battery which is focused at present.
Because sodium ions have larger ionic radius and can not form stable intercalation compounds with a graphite carbon layer, the traditional graphite negative electrode material has low sodium storage capacity, and development of a novel negative electrode sodium storage material is needed.
Hard carbon is carbon that is difficult to graphitize at 2500 c and is composed of random, crimped graphite domain fragments. Compared with graphite, the carbon layer spacing of the hard carbon is larger, a closed-pore structure exists, sodium ions can be effectively stored, the sodium storage capacity is higher, and the material is expected to become the low-cost sodium ion battery anode material with the highest potential. However, the carbonization temperature of the hard carbon is low, more oxygen-containing functional groups still exist on the surface and have certain hydrophilicity, so that under the traditional aqueous slurry system, a large number of water molecules are easily captured on the surface of rich pore structures and are difficult to discharge, so that the gas production bulges in the circulation process, the circulation performance and the safety performance of the battery are seriously influenced, and the industrial application cannot be satisfied.
The invention designs a chemical surface modified biomass hard carbon material capable of reducing oxygen-containing functional groups on the surface of the hard carbon material and improving side reactions such as water gas absorption and the like of a hard carbon negative electrode material, and a preparation method and application thereof.
Disclosure of Invention
The invention provides a chemical surface modified biomass hard carbon material, a preparation method and application thereof, and aims to solve the problems in the prior art.
In order to achieve the above purpose, the embodiment of the invention provides a chemical surface modified biomass hard carbon material, a preparation method and application thereof, the method takes biomass as a raw material, the biomass raw material is dried, crushed and pre-carbonized, and then is placed in an atmosphere plasma sintering furnace, and the biomass raw material is carbonized at a high temperature after being treated; the oxygen-containing functional groups on the surface of the carbon material are reduced by plasma treatment in a reducing atmosphere, so that the problems of easy gas production, low first warehouse and poor cycle performance of the hard carbon material are solved. The prepared sodium ion battery cathode has excellent electrochemical performance, the initial cycle coulomb efficiency is more than 90%, the initial cycle charging specific capacity is 300mAh/g, and the 100-cycle retention rate of the sodium half battery is more than 80%.
One aspect of the invention provides a method for preparing a chemical surface modified biomass hard carbon material, comprising the following steps:
s1, pretreatment: washing and drying biomass raw materials; washing the surface dust of the biomass raw material by clear water, and then placing the biomass raw material in a blast oven for drying to remove water;
s2, pre-carbonization: pre-carbonizing the pretreated biomass raw material at a low temperature; placing in a tube furnace or a box-type atmosphere furnace, wherein the protective atmosphere is N 2 At least one of Ar.
S3, plasma treatment: placing the pre-carbonized biomass raw material into a cavity of a plasma chemical vapor deposition device, and performing plasma treatment in a reducing atmosphere; and cooling to room temperature along with the furnace after the plasma treatment is completed. If the power is too high, a large number of defects are easy to generate, and the first coulomb efficiency of the material is reduced; if the content of the reducing atmosphere is too low, the reaction of the gas molecules with the oxygen-containing functional groups on the surface of the hard carbon is insufficient, and the removal is not thorough.
S4, high-temperature carbonization: carbonizing the biomass raw material subjected to plasma treatment at high temperature to obtain the biomass. The protective atmosphere used in the tube furnace or the box-type atmosphere furnace is N 2 At least one of Ar.
Preferably, the biomass feedstock is a variety of plant organisms that are naturally synthesized using the atmosphere, water, and soil.
Preferably, the biomass raw material is at least one of bamboo, reed, straw, cotton and coconut shell.
Preferably, the drying temperature is 70-80 ℃ and the drying time is 2-3 h.
Preferably, the reducing atmosphere is H 2 At least one of CO. By introducing the reducing atmosphere, the hydroxyl and carboxyl on the surface can be removed, the irreversible adsorption of sodium ions is reduced, the surface hydrophobicity is improved, and the effect of optimizing the performance of the sodium ion battery cathode is finally achieved.
Preferably, the pre-carbonization conditions are: the temperature is 300-900 ℃, the treatment time is 0.5-5 h, and the heating rate is 0.5-5 ℃/min.
Preferably, the plasma treatment conditions are: the temperature is room temperature-900 ℃, the input power of the plasma is 100-1000W, the input flow is 10-100 mL/s, the heating rate is 0.5-5 ℃/min, and the heat preservation time is 0.5-12 h.
Preferably, the high temperature carbonization conditions are: the temperature is 1000-2000 ℃, and the carbonization time is 0.5-5 h.
In another aspect, the invention provides the chemical surface modified biomass hard carbon material prepared by the preparation method.
The invention also provides an application of the chemical surface modified biomass hard carbon material in a sodium ion battery, wherein the chemical surface modified biomass hard carbon material is used as a negative electrode material of the sodium ion battery.
Preferably, the initial cycle coulombic efficiency of the negative electrode material of the sodium ion battery is up to more than 90%, the initial cycle charging specific capacity is 300mAh/g, and the 100-cycle retention rate of the sodium half battery is more than 80%.
Reaction mechanism:
the preparation method is based on the synergistic effect among the steps, and the hard carbon material with low oxygen-containing functional groups is obtained while the rich sodium storage sites are ensured to be obtained. The surface oxygen-containing functional groups can be removed by reducing atmosphere plasma treatment, so that irreversible loss of sodium ions in the first charge and discharge process is reduced, and the hydrophobicity of the hard carbon surface is improved. The gas production of the battery is reduced while maintaining high first coulombic efficiency and excellent cycle performance.
The scheme of the invention has the following beneficial effects:
(1) According to the invention, biomass is used as a raw material, and through plasma surface modification in a reducing atmosphere, oxygen-containing functional groups on the surface of hard carbon are reduced while the rich sodium storage sites are ensured, so that the problem that the functional groups irreversibly adsorb sodium ions and have high affinity to water molecules is effectively solved. The plasma surface modification in the reducing atmosphere is particularly performed by performing physical and chemical surface modification on the hard carbon structure, so that the problems of low initial coulomb efficiency, poor cycle performance, easiness in gas production and the like of the hard carbon negative electrode material of the sodium ion battery in the prior art are solved.
(2) According to the invention, biomass is used as a carbon source, and is firstly dried, pre-carbonized, then subjected to plasma treatment in a reducing atmosphere, and finally subjected to high-temperature pyrolysis to obtain the hard carbon with rich closed pore structure, proper interlayer spacing and low surface oxygen functional group content. The method has the advantages of wide raw material sources, simple process and the like, and is suitable for large-scale industrial production.
(3) The biomass hard carbon material prepared by the method has low oxygen-containing functional groups on the surface, can effectively reduce irreversible adsorption of sodium ions in the first charge and discharge process, and can improve the hydrophobicity of the hard carbon surface, so that the capture of water molecules in the air or water system slurry preparation process is reduced, and the gas production phenomenon caused by the reaction of trace water on the hard carbon surface and electrolyte in the battery cycle process is solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a first-cycle charge-discharge curve of a sodium ion battery of example 1 of the present invention;
FIG. 2 is a first-cycle charge-discharge curve of the sodium-ion battery of example 2 of the present invention;
FIG. 3 is a first-cycle charge-discharge curve of the sodium-ion battery of example 3 of the present invention;
FIG. 4 is a first-cycle charge-discharge curve of the sodium-ion battery of example 4 of the present invention;
FIG. 5 is a first-cycle charge-discharge curve of the sodium-ion battery of example 5 of the present invention;
FIG. 6 is a first-cycle charge-discharge curve of the sodium-ion battery of example 6 of the present invention;
FIG. 7 is a first-cycle charge-discharge curve of the sodium-ion battery of example 7 of the present invention;
fig. 8 is a first-turn charge-discharge curve of the sodium-ion battery of comparative example 1 of the present invention;
fig. 9 is a first-turn charge-discharge curve of the sodium-ion battery of comparative example 2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Aiming at the existing problems, the invention provides a chemical surface modified biomass hard carbon material, and a preparation method and application thereof.
Example 1
A preparation method of a chemical surface modified biomass hard carbon material comprises the following steps:
step 1: drying, namely placing 10g of bamboo powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: pre-carbonizing, namely placing the bamboo powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: plasma treatment, namely placing the bamboo powder pre-carbonized material obtained after the step 2 into a cavity of a plasma device, and introducing 95% Ar+5% H at an input flow rate of 20mL/s 2 The input power of the plasma is 200W, the temperature is raised to 600 ℃ at 5 ℃/min, the temperature is kept for 2 hours, and the sample is cooled to the room temperature along with the furnace after the temperature is kept;
step 4: carbonizing at high temperature, namely placing the bamboo charcoal subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the prepared carbon material is used as an active substance of a battery anode material for preparing a sodium ion battery.
According to the mass ratio of 92 percent to 3 percent to 1.5 percent to 3.5 percent, 184mg of carbon material powder, 6mg of conductive carbon black, 17.5mg of carboxymethyl cellulose solution with the concentration of 2 percent (w/w) and 17.5mg of styrene-butadiene rubber with the concentration of 40 percent (w/w) are weighed, a proper amount of deionized water is added dropwise, stirring is carried out for 20 minutes until the slurry is uniform, a scraper with the thickness of 100 mu m is utilized to uniformly coat the surface of copper (Cu) foil, the copper foil is dried for 2 hours in a 105 ℃ blast drying box, the Cu foil with active materials is cut into disc-shaped negative pole pieces, and then the disc-shaped negative pole pieces are transferred to a glove box for standby.
The assembly of the simulated cell was performed in a MIKROUNA glove box filled with Ar atmosphere, using the prepared carbon material pole piece as negative electrode, commercial electrolyte 1.0mol/LNaPF 6 DMC (1:1) (V: V) as electrolyte, na metal sheet as counter electrode, 2016 button cell was assembled.
Gas yield of batteryThe measurement of (2) requires first assembly into a pouch cell. The positive electrode uses commercial nickel-iron-manganese layered oxide, and the negative electrode uses the prepared hard carbon. The cathode is prepared by stirring slurry, coating, drying, die cutting, laminating, injecting liquid and soft package according to the mass ratio of 92% to 3% to 1.5% to 3.5%, and the single soft package battery with the capacity of 1Ah is assembled. Measurement of the volume of the pouch cell was based mainly on archimedes' principle, hanging the pouch cell on a universal tester, recording the readings, and then slowly immersing the cell completely in a non-conductive vacuum pump oil (density 0.8595cm -3 ) And after the instrument is stable, recording the indication number of the tension instrument again, namely the volume of the soft package battery, and the volume difference before and after circulation is the gas production.
The assembled half cell has a first coulombic efficiency of 90.05% and a first charge specific capacity of 316.2mAh/g at a current density of 20mA/g, and a capacity retention rate of 84.3% after 100 cycles. The gas yield of the 1Ah soft package battery for 100 times is 2.6mL. The first-cycle charge-discharge curve of the sodium ion battery is shown in figure 1.
Example 2
A preparation method of a chemical surface modified biomass hard carbon material comprises the following steps:
step 1: drying, namely placing 10g of bamboo powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: pre-carbonizing, namely placing the bamboo powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: plasma treatment, namely placing the bamboo powder pre-carbonized material obtained after the step 2 into a cavity of a plasma device, and introducing 95% Ar+5% H at an input flow rate of 20mL/s 2 The input power of the plasma is 400w, the temperature is raised to 600 ℃ at 5 ℃/min, the temperature is kept for 2 hours, and the sample is cooled to the room temperature along with the furnace after the temperature is kept;
step 4: carbonizing at high temperature, namely placing the bamboo charcoal subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the carbon material prepared above is used as an active material of a battery anode material for preparing a sodium ion battery, and the specific method is the same as in example 1. The assembled half-cell has a first coulombic efficiency of 85.79% and a first charge specific capacity of 334.7mAh/g at a current density of 20mA/g, and a capacity retention rate of 80.9% after 100 cycles. The specific measurement method of the gas production rate is 3.3mL with 100 times of circulation gas production rate of the 1Ah soft package battery in the embodiment 1. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 2.
Example 3
A preparation method of a chemical surface modified biomass hard carbon material comprises the following steps:
step 1: drying, namely placing 10g of bamboo powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: pre-carbonizing, namely placing the bamboo powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: plasma treatment, namely placing the bamboo powder pre-carbonized material obtained after the step 2 into a cavity of a plasma device, and introducing 90% Ar+10% H at an input flow rate of 20mL/s 2 The input power of the plasma is 200w, the temperature is raised to 600 ℃ at 5 ℃/min, the temperature is kept for 2 hours, and the sample is cooled to the room temperature along with the furnace after the temperature is kept;
step 4: carbonizing at high temperature, namely placing the bamboo charcoal subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the carbon material prepared above is used as an active material of a battery anode material for preparing a sodium ion battery, and the specific method is the same as in example 1. The assembled half-cell has a first coulombic efficiency of 92.37% and a first charge specific capacity of 319.3mAh/g at a current density of 20mA/g, and a capacity retention rate of 87.2% after 100 cycles. The specific measurement method of the gas production rate is the same as that of the 100-cycle gas production rate of the 1Ah soft package battery in the example 1, and the gas production rate is 1.9mL. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 3.
Example 4
A preparation method of a chemical surface modified biomass hard carbon material comprises the following steps:
step 1: drying, namely placing 10g of bamboo powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: pre-carbonizing, namely placing the bamboo powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: surface reduction treatment, namely placing the bamboo powder pre-carbonized material obtained after the step 2 is finished into a cavity of a plasma device, and introducing 95% Ar+5% H at an input flow rate of 20mL/s 2 Turning off the plasma generator, heating to 600 ℃ at 5 ℃/min, preserving heat for 2 hours, and cooling the sample to room temperature along with the furnace after the heat preservation is finished;
step 4: carbonizing at high temperature, namely placing the bamboo charcoal subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the carbon material prepared above is used as an active material of a battery anode material for preparing a sodium ion battery, and the specific method is the same as in example 1. The assembled half cell has a first coulombic efficiency of 87.45% and a first charge specific capacity of 292.8mAh/g at a current density of 20mA/g, and a capacity retention rate of 78.5% after 100 cycles. The specific measurement method of the gas production rate is 3.5mL with 100 times of circulation gas production rate of the 1Ah soft package battery in the embodiment 1. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 4.
Example 5
A preparation method of a chemical surface modified biomass hard carbon material comprises the following steps:
step 1: drying, namely placing 10g of bamboo powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: pre-carbonizing, namely placing the bamboo powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: plasma treatment, namely placing the bamboo powder pre-carbonized material obtained after the step 2 into a cavity of a plasma device, introducing CO at an input flow of 20mL/s, heating to 600 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling a sample to room temperature along with a furnace after the heat preservation is finished;
step 4: carbonizing at high temperature, namely placing the bamboo charcoal subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the carbon material prepared above is used as an active material of a battery anode material for preparing a sodium ion battery, and the specific method is the same as in example 1. The assembled half cell has a first coulombic efficiency of 88.64% and a first charge specific capacity of 326.5mAh/g at a current density of 20mA/g, and a capacity retention rate of 77.5% after 100 cycles. The specific measurement method of the gas production rate is 2.5mL with 100 times of circulating gas production rate of the 1Ah soft package battery in the embodiment 1. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 5.
Example 6
A preparation method of a chemical surface modified biomass hard carbon material comprises the following steps:
step 1: drying, namely placing 10g of reed powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: pre-carbonizing, namely placing reed powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: plasma treatment, namely placing the reed pre-carbonized material obtained after the step 2 into a cavity of a plasma device, and introducing 90% Ar+10% H at an input flow rate of 20mL/s 2 Hydrogen argon mixing of (2)The input power of the gas and the plasma is 200w, the temperature is raised to 600 ℃ at 5 ℃/min, the temperature is kept for 6 hours, and the sample is cooled to the room temperature along with the furnace after the heat preservation is finished;
step 4: carbonizing at high temperature, namely placing reed carbon subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the carbon material prepared above is used as an active material of a battery anode material for preparing a sodium ion battery, and the specific method is the same as in example 1. The assembled half-cell has a first coulombic efficiency of 87.73% and a first charge specific capacity of 298.9mAh/g at a current density of 20mA/g, and a capacity retention rate of 80.1% after 100 cycles. The specific measurement method of the gas production rate is 3.1mL with 100 times of circulation gas production rate of the 1Ah soft package battery in the embodiment 1. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 6.
Example 7
A preparation method of a chemical surface modified biomass hard carbon material comprises the following steps:
step 1: drying, namely placing 10g of starch into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: pre-carbonizing, namely placing the starch obtained after the step 1 in a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: plasma treatment, namely placing the starch pre-carbonized material obtained after the step 2 is completed into a cavity of a plasma device, and introducing 90% Ar+10% H at an input flow rate of 20mL/s 2 The input power of the plasma is 200w, the temperature is raised to 600 ℃ at 5 ℃/min, the temperature is kept for 6 hours, and the sample is cooled to the room temperature along with the furnace after the heat preservation is finished;
step 4: carbonizing at high temperature, namely placing the starch carbon subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the carbon material prepared above is used as an active material of a battery anode material for preparing a sodium ion battery, and the specific method is the same as in example 1. The assembled half cell has a first coulombic efficiency of 84.64% and a first charge specific capacity of 344.7mAh/g at a current density of 20mA/g, and a capacity retention rate of 75.1% after 100 cycles. The specific measurement method of the gas production rate is 3.7mL with 100 times of circulation gas production rate of the 1Ah soft package battery in the embodiment 1. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 7.
Comparative example 1
A preparation method of biomass-based hard carbon anode material for sodium ion batteries comprises the following steps:
step 1: drying, namely placing 10g of bamboo powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: carbonizing, namely placing the bamboo powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: carbonizing at high temperature, namely placing the pre-carbonized bamboo carbon into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 4: the prepared carbon material is used as an active substance of a battery anode material for preparing a sodium ion battery.
According to the mass ratio of 92 percent to 3 percent to 1.5 percent to 3.5 percent, 184mg of carbon material powder, 6mg of conductive carbon black, 17.5mg of carboxymethyl cellulose solution with the concentration of 2 percent (w/w) and 17.5mg of styrene-butadiene rubber with the concentration of 40 percent (w/w) are weighed, a proper amount of deionized water is added dropwise, stirring is carried out for 20 minutes until the slurry is uniform, a scraper with the thickness of 100 mu m is utilized to uniformly coat the surface of copper (Cu) foil, the copper foil is dried for 2 hours in a 105 ℃ blast drying box, the Cu foil with active materials is cut into disc-shaped negative pole pieces, and then the disc-shaped negative pole pieces are transferred to a glove box for standby.
The assembly of the simulated cell was performed in a MIKROUNA glove box filled with Ar atmosphere, using the prepared carbon material pole piece as negative electrode, commercial electrolyte 1.0mol/LNaPF 6 EC DMC (1:1) (V: V) as electrolyteThe 2016 type cell was assembled with the Na plate as the counter electrode. The assembled half cell has a first coulombic efficiency of 75.22% and a first charge specific capacity of 261.2mAh/g at a current density of 20mA/g, and a capacity retention rate of 73.5% after 100 cycles. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 8.
The measurement of the gas production of the battery requires the assembly into a soft-pack battery. The positive electrode uses commercial nickel-iron-manganese layered oxide, and the negative electrode uses the prepared hard carbon. The cathode is prepared by stirring slurry, coating, drying, die cutting, laminating, injecting liquid and soft package according to the mass ratio of 92% to 3% to 1.5% to 3.5%, and the single soft package battery with the capacity of 1Ah is assembled. Measurement of the volume of the pouch cell was based mainly on archimedes' principle, hanging the pouch cell on a universal tester, recording the readings, and then slowly immersing the cell completely in a non-conductive vacuum pump oil (density 0.8595cm -3 ) And after the instrument is stable, recording the indication number of the tension instrument again, namely the volume of the soft package battery, and the volume difference before and after circulation is the gas production. The gas yield after 100 cycles was 6.7mL.
Comparative example 2
A preparation method of biomass-based hard carbon anode material for sodium ion batteries comprises the following steps:
step 1: drying, namely placing 10g of bamboo powder into a forced air drying oven, drying at 80 ℃ for 2 hours, and drying to remove water;
step 2: carbonizing, namely placing the bamboo powder obtained after the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under argon atmosphere, pre-carbonizing for 3 hours, cooling to room temperature, and grinding and crushing to obtain a bamboo powder pre-carbonized material;
step 3: plasma treatment, namely placing the bamboo powder pre-carbonized material obtained after the step 2 into a cavity of a plasma device, introducing Ar at an input flow of 15mL/s, heating to 600 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling a sample to room temperature along with a furnace after the heat preservation is finished;
step 4: carbonizing at high temperature, namely placing the bamboo charcoal subjected to plasma treatment into a tube furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, cooling to room temperature, grinding and crushing;
step 5: the carbon material prepared by the method is used as an active substance of a battery anode material for preparing a sodium ion battery, and the specific method is the same as that of comparative example 1. The assembled half cell has a first coulombic efficiency of 71.09% and a first charge specific capacity of 283.7mAh/g at a current density of 20mA/g, and a capacity retention rate of 69.7% after 100 cycles. The specific measurement method of the gas production rate is 5.1mL with the 100-cycle gas production rate of the comparative example 1,1Ah soft package battery. The first-cycle charge-discharge curve of the sodium ion battery is shown in fig. 9.
Table 1 is a table of the relevant electrochemical performance parameters of the assembled half-cells of comparative examples 1-2 and examples 1-7
Table 2 shows the gas production of the 1Ah soft pack assembled in comparative examples 1-2 and examples 1-8 for 100 cycles
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the chemical surface modified biomass hard carbon material is characterized by comprising the following steps of:
s1, pretreatment: washing and drying biomass raw materials;
s2, pre-carbonization: pre-carbonizing the pretreated biomass raw material at a low temperature;
s3, plasma treatment: carrying out plasma treatment on the pre-carbonized biomass raw material in a reducing atmosphere;
s4, high-temperature carbonization: carbonizing the biomass raw material subjected to plasma treatment at high temperature to obtain the biomass.
2. The method for producing a chemically surface-modified biomass hard carbon material according to claim 1, wherein the biomass raw material is various plant organisms synthesized naturally by using the atmosphere, water and soil.
3. The method for producing a chemically surface-modified biomass hard carbon material according to claim 2, wherein the biomass raw material is at least one of bamboo, reed, straw, cotton, and coconut shell.
4. The method for preparing a chemically surface-modified biomass hard carbon material according to claim 3, wherein the drying temperature is 70-80 ℃ and the drying time is 2-3 hours.
5. The method for preparing a chemically surface-modified biomass hard carbon material according to claim 4, wherein the reducing atmosphere is H 2 At least one of CO.
6. The method for preparing a chemically surface-modified biomass hard carbon material according to claim 5, wherein the pre-carbonization conditions are: the temperature is 300-900 ℃, the treatment time is 0.5-5 h, and the heating rate is 0.5-5 ℃/min.
7. The method for preparing a chemically surface-modified biomass hard carbon material according to claim 6, wherein the plasma treatment conditions are: the temperature is room temperature-900 ℃, the input power of the plasma is 100-1000W, the input flow is 10-100 mL/s, the heating rate is 0.5-5 ℃/min, and the heat preservation time is 0.5-12 h.
8. The method for preparing a chemically surface-modified biomass hard carbon material according to claim 7, wherein the high-temperature carbonization conditions are as follows: the temperature is 1000-2000 ℃, and the carbonization time is 0.5-5 h.
9. A chemically surface-modified biomass hard carbon material produced by the production method according to any one of claims 1 to 8.
10. The use of a chemical surface modified biomass hard carbon material according to claim 9 in a sodium ion battery, wherein the chemical surface modified biomass hard carbon material is used as a negative electrode material of the sodium ion battery.
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| CN117293312B (en) * | 2023-11-24 | 2024-03-12 | 深圳市贝特瑞新能源技术研究院有限公司 | Hard carbon material, preparation method and application thereof, and sodium ion battery |
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