CN117623270A - Sodium ion battery hard carbon negative electrode material prepared by biomass-based crosslinking and application thereof - Google Patents
Sodium ion battery hard carbon negative electrode material prepared by biomass-based crosslinking and application thereof Download PDFInfo
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- CN117623270A CN117623270A CN202311623993.3A CN202311623993A CN117623270A CN 117623270 A CN117623270 A CN 117623270A CN 202311623993 A CN202311623993 A CN 202311623993A CN 117623270 A CN117623270 A CN 117623270A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 76
- 239000002028 Biomass Substances 0.000 title claims abstract description 46
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 39
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004132 cross linking Methods 0.000 title claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 108
- 229920001661 Chitosan Polymers 0.000 claims abstract description 92
- 239000000243 solution Substances 0.000 claims abstract description 90
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 37
- 229920002678 cellulose Polymers 0.000 claims abstract description 31
- 239000001913 cellulose Substances 0.000 claims abstract description 31
- 238000003763 carbonization Methods 0.000 claims abstract description 30
- 238000000197 pyrolysis Methods 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 25
- 230000035484 reaction time Effects 0.000 claims description 23
- 239000010405 anode material Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011267 electrode slurry Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000010382 chemical cross-linking Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 description 38
- 239000012300 argon atmosphere Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 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 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
- 239000002023 wood Substances 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
- H01M4/13—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a sodium ion battery hard carbon negative electrode material prepared by biomass-based crosslinking and application thereof, and the preparation method comprises the following steps: (1) Dissolving chitosan with a certain mass in acetic acid solution, stirring to fully dissolve the chitosan, and preparing chitosan solution. (2) Adding cellulose with a certain mass into chitosan solution, and stirring to uniformly mix the cellulose and the chitosan solution. (3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment for a certain time, and centrifuging, washing and drying the hydrothermal product after the reaction kettle is cooled to room temperature. (4) Transferring the treated hydrothermal product into a high-temperature tube furnace, and performing high-temperature pyrolysis carbonization treatment under inert atmosphere to obtain the hard carbon material. The hard carbon material prepared by carrying out chemical crosslinking treatment on the biomass base after pyrolysis carbonization has excellent multiplying power performance, and the first week coulomb efficiency is as high as 83.0%.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, in particular relates to the technical field of sodium ion battery cathodes, and particularly relates to a sodium ion battery hard carbon cathode material prepared by biomass-based crosslinking and application thereof.
Background
With the rapid development of electric automobiles, electronic products and energy storage devices, lithium ion batteries have been dominant in the energy storage technology field due to high energy density and good cycle stability. However, the high cost and the imbalance of the distribution of lithium resources greatly limit the application of the lithium resources in large-scale energy storage power grids and low-cost energy storage devices. In contrast, sodium with chemical properties similar to those of lithium gradually enters the field of vision of people, and the sodium ion battery can relieve the problem of lithium resource shortage to a certain extent due to low cost, wide sodium distribution and rich reserves in China, and can gradually replace lead-acid batteries with potential safety hazards.
Achieving high performance, low cost sodium ion batteries at this stage remains a significant challenge, especially sodium ion battery hard carbon anode materials are considered to be the best choice for electrochemical performance, cost control, and sustainable development of resources. The hard carbon is one of non-graphite carbon, has larger interlayer spacing, abundant defects and porosity, and can be Na + And more importantly, the hard carbon serving as the negative electrode material of the sodium ion battery has lower working voltage and higher capacity, and meets the safety and the functionality of battery application.
The Chinese petroleum university (Huadong) provides a hard carbon material in CN115124025A, a preparation method thereof and application thereof in sodium ion batteries, firstly, the particle size of a carbon source is controlled to ensure uniform particle size, then, a salt crystal hydrothermal-flash combustion synergistic method is adopted, transition metal salt is permeated into a carbon source precursor through a salt crystal hydrothermal process, and the microscopic pore structure, the surface chemical components and the graphitization degree of the hard carbon material are accurately regulated and controlled by taking salt crystals as templates in the flash combustion carbonization process, so that a more stable structure beneficial to improving electrochemical performance is formed; the local temperature around the salt crystal can be higher than that of the hard carbon matrix material through the flash carbonization process, and metal cations can catalyze carbon atoms to undergo atomic rearrangement at high temperature, so that the local graphitization degree around the salt crystal is improved, the graphitization degree of the hard carbon material is instantaneously improved, defects of the hard carbon material are limited, and the specific capacity of the sodium ion battery is improved.
A hard carbon material doped with heteroatoms including N atoms and M atoms including a combination of at least two of As, se, sb or Te, and a method of making and using the same, are provided by hewlett-packard lithium energy stock in CN115321514 a. The hard carbon material can be prepared by a simple synthesis process, is doped with at least three hetero atoms, and can not only increase the interlayer spacing of the hard carbon material, but also introduce defect sites through the synergistic effect among the hetero atoms, so that the structure of the hard carbon material is greatly distorted, the embedding capacity and the adsorption capacity of sodium ions are increased, and the hard carbon material has high gram capacity and high multiplying power.
Overall, the methods of using biomass-derived hard carbon materials in the prior art are not numerous, and there are characteristics of low hard carbon structure control and poor performance. The invention aims to overcome the problems, select a proper method to crosslink the biomass material, reasonably control the defect of the hard carbon surface and improve the reversible capacity and the first-week coulomb efficiency of the hard carbon anode material.
Disclosure of Invention
The invention aims to provide the hard carbon material with simple preparation process, economical and feasible applicability, application prospect for large-scale industrial production, excellent rate capability and high first week coulomb efficiency up to 83.0%. Specifically, two biomass-based materials are subjected to crosslinking treatment by a hydrothermal reaction method, so that the crosslinked biomass macromolecular structure can prevent release of micromolecular gas in the pyrolysis process, reduce formation of hard carbon surface defects, facilitate transfer of electrons, and improve reversible capacity and first-week coulomb efficiency of the hard carbon anode material.
The technical scheme adopted by the invention is as follows:
a method for preparing a hard carbon negative electrode material of a sodium ion battery by biomass-based crosslinking comprises the following steps:
(1) Dissolving chitosan with a certain mass in acetic acid solution, stirring to fully dissolve the chitosan, and preparing chitosan solution.
(2) Adding cellulose with a certain mass into chitosan solution, and stirring to uniformly mix the cellulose and the chitosan solution.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment for a certain time, and centrifuging, washing and drying the hydrothermal product after the reaction kettle is cooled to room temperature.
(4) Transferring the treated hydrothermal product into a high-temperature tube furnace, and performing high-temperature pyrolysis carbonization treatment under inert atmosphere to obtain the hard carbon material.
Further, the concentration of the acetic acid solution is 1-2g/L, and the concentration of the chitosan solution is 5-12g/L.
Further, the mass ratio of cellulose to chitosan is 3:1-6:1.
Further, the mass ratio of cellulose to chitosan is 5:1.
Further, the hydrothermal reaction temperature of the mixed solution of cellulose and chitosan is 180-250 ℃, and the hydrothermal reaction time is 12-48h.
Further, the hydrothermal reaction temperature of the mixed solution of cellulose and chitosan is 200-240 ℃, and the hydrothermal reaction time is 24-36h.
Further, the high-temperature pyrolysis carbonization temperature is 1000-1800 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 2-10h.
Further, the high-temperature pyrolysis carbonization temperature is 1300-1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 3-5h.
The sodium ion battery hard carbon anode material prepared according to the method.
A method for preparing a hard carbon electrode material of a sodium ion battery, comprising the steps of:
grinding the hard carbon anode material of the sodium ion battery prepared by biomass-based crosslinking and a conductive agent of acetylene black and a binder of sodium carboxymethyl cellulose into uniform slurry according to a mass ratio of 8:1:1, and scraping and coating the slurry on a copper foil by a coater to ensure that the mass of an active substance is 1-1.5mg/cm 2 And obtaining the hard carbon negative electrode plate of the sodium ion battery.
Compared with the prior art, the beneficial effects are that:
(1) The raw materials adopted by the invention are all biomass-based materials, and the method has the advantages of wide sources, low price, environmental protection and the like, and the adopted method has simple preparation process, economical and feasible applicability and application prospect for large-scale industrial production.
(2) According to the invention, the biomass base is subjected to chemical crosslinking treatment, so that the hard carbon material prepared after pyrolysis carbonization has excellent rate capability, and the first-week coulomb efficiency is as high as 83.0%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent 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 an SEM image of a hard carbon negative electrode material of a sodium ion battery prepared by biomass-based crosslinking prepared in example 2.
FIG. 2 is a charge and discharge curve of the biomass-based cross-linking prepared sodium ion battery hard carbon negative electrode material prepared in example 2 at a current density of 50 mA/g.
FIG. 3 is a graph showing the rate performance of the biomass-based cross-linking prepared sodium ion battery hard carbon negative electrode material prepared in example 2 at a current density of 0.05A/g-1A/g.
FIG. 4 is a charge and discharge curve of the biomass-based cross-linking preparation sodium ion battery hard carbon anode material prepared in example 2 at a current density of 0.05A/g-1A/g.
FIG. 5 is a long cycle chart of the biomass-based cross-linking preparation of a hard carbon negative electrode material for sodium ion batteries prepared in example 2 at a current density of 1A/g.
Detailed Description
In order to better understand the technical solution in the embodiments of the present invention and make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the present invention will be further described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
Example 1
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1100 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 2
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 3
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1500 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 4
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 180 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 5
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 1.5g of cellulose was added to the chitosan solution and stirred at 80℃for 3 hours to mix the two uniformly.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 6
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 250 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 7
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 200 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 8
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 240 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 9
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1000 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 10
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of cellulose is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1800 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 11
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.0g of cellulose was added to the chitosan solution and stirred at 80℃for 3 hours to mix the two uniformly.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 12
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 3.0g of cellulose was added to the chitosan solution and stirred at 80℃for 3 hours to mix the two uniformly.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 13
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 1.0g of cellulose was added to the chitosan solution and stirred at 80℃for 3 hours to mix the two uniformly.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 2
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of bamboo powder is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 15
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of wood flour was added to the above chitosan solution and stirred at 80℃for 3 hours to mix the two evenly.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Example 16
(1) 0.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) 2.5g of peanut shell powder is added into the chitosan solution and stirred for 3 hours at 80 ℃ to uniformly mix the two.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
Comparative example 1
(1) 2.5g of cellulose was added to the deionized water solution and stirred at 80℃for 3 hours to disperse it uniformly.
(2) Transferring the solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(3) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3 hours to obtain the cellulose-based hard carbon material.
Comparative example 2
(1) 2.5g of chitosan was dissolved in 2g/L of 50mL of acetic acid solution, and the solution was stirred at 80℃for 1 hour to sufficiently dissolve the chitosan, thereby preparing 10g/L of chitosan solution.
(2) Transferring the solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(3) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3 hours to obtain the cellulose-based hard carbon material.
Comparative example 3
(1) 0.5g glucose was dissolved in 50mL deionized water solution and stirred at room temperature for 1h to allow sufficient dissolution.
(2) 2.5g of cellulose was added to the above glucose solution and stirred at 80℃for 3 hours to mix them uniformly.
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal reaction temperature is 220 ℃, the hydrothermal reaction time is 24 hours, and after the reaction is completed and cooled to room temperature, centrifuging, washing and drying the hydrothermal reaction product.
(4) Transferring the treated hydrothermal reaction product into a high-temperature tube furnace, performing high-temperature pyrolysis carbonization treatment under the argon atmosphere, heating to 1300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the biomass-based crosslinked hard carbon material.
The above is only a preferred example of a method for preparing a hard carbon negative electrode material of a sodium ion battery by biomass-based crosslinking, and the protection scope of the invention is not limited to the example. The technical scheme of the invention is to improve and optimize the preparation condition of the hard carbon material under the same condition, and the protection scope of the invention is provided on the basis of the invention again.
Application and performance test
The hard carbon materials prepared by the above examples and comparative examples were used as negative electrode active materials for sodium ion batteries to prepare a pole piece, and the specific method is as follows: grinding a hard carbon anode material of a sodium ion battery and a conductive agent of acetylene black and a binder of sodium carboxymethyl cellulose into uniform slurry according to a mass ratio of 8:1:1, and scraping and coating the slurry on a copper foil through a coater to ensure that the surface load of an active substance is 1-1.5g/cm 2 And obtaining a hard carbon negative electrode plate of the sodium ion battery, preparing the sodium ion button battery in a glove box, and detecting the electrochemical performance of the button battery.
Table 1 shows the properties of the hard carbon negative electrode materials of sodium ion batteries prepared in examples and comparative examples, and the examples have higher reversible capacity and first cycle coulombic efficiency compared with the comparative examples, because the biomass base as a macromolecule prolongs the molecular chain structure through chemical crosslinking, can effectively prevent release of small molecule gas in the process of thermal pyrolysis, minimize formation of defects on the surface of hard carbon, promote transfer of electrons, and make the biomass base possess excellent rate capability. Table 2 shows the electrochemical properties of example 2 at different current densities (50-1000 mA/g), as shown in Table 2, example 2 still has a reversible capacity of 227mAh/g at a current density of 500mA/g, and still has a reversible capacity of 209mAh/g at a current density of 1000mA/g, showing the superiority of the invention at large current densities. Fig. 1 shows that the sem image of example 2 is in an amorphous shape, fig. 2 and 4 show that the battery prepared by the invention has a longer plateau region, and fig. 3 shows the rate performance of example 2, showing that the invention has good cycling stability at different current densities. FIG. 5 shows the long cycle performance of example 2 at a large current density (1A/g), which retains 80% of its capacity even after 750 cycles, demonstrating its excellent cycle stability.
Table 1 electrochemical properties (current density 50mAg -1 )
TABLE 2 electrochemical Properties at different current densities (50-1000 mA/g) example 2
| Current density (mA/g) | 50 | 100 | 200 | 300 | 500 | 800 | 1000 |
| Specific discharge capacity (mAh/g) | 330 | 265 | 252 | 241 | 233 | 221 | 212 |
| Specific charge capacity (mAh/g) | 274 | 258 | 246 | 237 | 227 | 217 | 209 |
The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims (10)
1. The method for preparing the hard carbon anode material of the sodium ion battery by biomass-based crosslinking is characterized by comprising the following steps of:
(1) Dissolving chitosan with a certain mass in acetic acid solution, stirring to fully dissolve the chitosan, and preparing chitosan solution;
(2) Adding cellulose with a certain mass into chitosan solution, and stirring to uniformly mix the cellulose and the chitosan solution;
(3) Transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal treatment for a certain time, and centrifuging, washing and drying the hydrothermal product after the reaction kettle is cooled to room temperature;
(4) Transferring the treated hydrothermal product into a high-temperature tube furnace, and performing high-temperature pyrolysis carbonization treatment under inert atmosphere to obtain the hard carbon material.
2. The method for preparing the hard carbon anode material of the sodium ion battery by biomass-based crosslinking of claim 1, wherein the acetic acid solution is 1-2g/L and the chitosan solution concentration is 5-12g/L.
3. The method for preparing the hard carbon negative electrode material of the sodium ion battery by biomass-based crosslinking according to claim 1, wherein the mass ratio of added cellulose to chitosan is 3:1-6:1.
4. The method for preparing a hard carbon negative electrode material of a sodium ion battery by biomass-based crosslinking according to claim 1 or 3, wherein the mass ratio of cellulose to chitosan is 5:1.
5. The method for preparing the hard carbon negative electrode material of the sodium ion battery by biomass-based crosslinking of claim 1, wherein the hydrothermal reaction temperature of the mixed solution of cellulose and chitosan is 180-250 ℃ and the hydrothermal reaction time is 12-48h.
6. The method for preparing the hard carbon negative electrode material of the sodium ion battery by biomass-based crosslinking according to claim 1 or 5, wherein the hydrothermal reaction temperature of the mixed solution of cellulose and chitosan is 200-240 ℃ and the hydrothermal reaction time is 24-36h.
7. The method for preparing the hard carbon negative electrode material of the sodium ion battery by biomass-based crosslinking according to claim 1, wherein the pyrolysis carbonization temperature is 1000-1800 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 2-10h.
8. The method for preparing the hard carbon anode material of the sodium ion battery by biomass-based crosslinking according to claim 1 or 7, wherein the high-temperature pyrolysis carbonization temperature is 1300-1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 3-5h.
9. A sodium ion battery hard carbon anode material prepared according to the method of any one of claims 1-8.
10. A hard carbon negative electrode of a sodium ion battery, which is characterized in that the electrode slurry comprises the hard carbon negative electrode material of the sodium ion battery as claimed in claim 9, an electroconductive agent of acetylene black and a binder of sodium carboxymethyl cellulose.
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