CN110719891A - Biomass-based hard carbon negative electrode material of sodium ion battery and preparation method and application thereof - Google Patents
Biomass-based hard carbon negative electrode material of sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN110719891A CN110719891A CN201880036321.3A CN201880036321A CN110719891A CN 110719891 A CN110719891 A CN 110719891A CN 201880036321 A CN201880036321 A CN 201880036321A CN 110719891 A CN110719891 A CN 110719891A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 61
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 59
- 239000002028 Biomass Substances 0.000 title claims abstract description 58
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007833 carbon precursor Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 235000000832 Ayote Nutrition 0.000 claims description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000002950 deficient Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 244000198134 Agave sisalana Species 0.000 claims description 2
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001474374 Blennius Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 241000219146 Gossypium Species 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000014676 Phragmites communis Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 240000000111 Saccharum officinarum Species 0.000 claims description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims description 2
- 244000126002 Ziziphus vulgaris Species 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910002096 lithium permanganate Inorganic materials 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 244000144730 Amygdalus persica Species 0.000 claims 1
- 240000004244 Cucurbita moschata Species 0.000 claims 1
- 244000280244 Luffa acutangula Species 0.000 claims 1
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims 1
- 235000006040 Prunus persica var persica Nutrition 0.000 claims 1
- 241000219492 Quercus Species 0.000 claims 1
- 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 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 239000011734 sodium Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 8
- 239000010406 cathode material Substances 0.000 abstract description 5
- 239000012467 final product Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000010298 pulverizing process Methods 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 240000001980 Cucurbita pepo Species 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010902 straw Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 239000011229 interlayer Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
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- 239000007770 graphite material Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000002687 Caesalpinia echinata Nutrition 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001424361 Haematoxylum brasiletto Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- -1 perchloroethylene, trichloroethylene, benzene Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a biomass-based hard carbon negative electrode material of a sodium ion battery, and a preparation method and application thereof, wherein the preparation method comprises the following steps: washing and drying the biomass material, and heating the biomass material for 1 to 24 hours in an anoxic atmosphere at the temperature of 100-800 ℃ in an isolated manner to obtain a carbon precursor; pulverizing the obtained carbon precursor and soaking the carbon precursor in a permanganate solution to oxidize the carbon material and generate more sodium storage sites; drying and sieving the treated carbon precursor, then performing secondary sintering, preserving the heat at 800-2500 ℃ for 0.5-48 hours under the inert atmosphere, then washing the product with acid liquor, washing the product with clear water until the pH value is 7, and drying the product to obtain the final product. The method has the advantages of simple and easy operation process, low price, higher energy density and good rate capability, and the hard carbon cathode material of the sodium-ion battery obtained by the method is an excellent cathode material of the sodium-ion battery.
Description
Technical Field
The invention belongs to the field of negative electrode materials of sodium-ion batteries, and particularly relates to a biomass-based hard carbon negative electrode material of a sodium-ion battery, and a preparation method and application thereof.
Background
In recent decades, the rapid development of lithium ion batteries has made them the most important energy storage devices in daily life. With the wide application of electric automobiles and intelligent electronic equipment, the demand of lithium is greatly increased, the reserve of lithium is limited, and the distribution resources are uneven, so that the price of lithium-related materials is increased, and the cost of batteries is increased. Therefore, the development of non-lithium-based electrochemical energy storage devices with excellent performance and low cost is an urgent task. Similar to the working principle of lithium ion batteries, sodium ion batteries with more abundant resources are receiving wide attention. The sodium metal can not be used as a negative electrode in an actual sodium ion battery because the formation of sodium dendrites easily causes short circuit of a liquid battery, and metal sodium is more active than metal lithium and is easy to ignite and explode when meeting water. What is worse, the widely used graphite negative electrode of the lithium ion battery has no sodium storage performance due to thermodynamic reasons. The carbon-based negative electrode material of the sodium ion battery is greatly different from the carbon-based negative electrode material of the lithium ion battery, and the difference is mainly caused by the larger ionic radius of sodium ions. Traditional graphite-based negative electrode widely applied to lithium ion batteryThe interlayer distance of the electrode material is smaller than the diameter of sodium ions, so that the traditional graphite material is difficult to store sodium effectively, and previous researches show that the graphite material can only be used according to NaC64The sodium can be stored in the form of sodium salt, and only extremely low specific capacity can be shown. Wang et al, which oxidize and partially reduce graphite to enlarge the interlayer spacing of graphite to 0.43 nm; the problem that sodium ions are difficult to be embedded into graphite layers is solved by increasing the distance between the graphite layers.
Biomass is an important renewable resource, is clean and environment-friendly, and has abundant reserves of biomass resources in China, so that how to fully utilize the biomass resources and turn waste into wealth becomes a hot spot of research of workers in various countries. The biomass material which has wide sources, low cost, reproducibility and no pollution and is suitable for large-scale industrialization is an ideal precursor for preparing the hard carbon material of the cathode of the high-performance sodium-ion battery. The preparation of the hard carbon material by using the biomass as the precursor provides an effective thinking method for preparing the hard carbon material in large batch at low cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a biomass-based hard carbon negative electrode material of a sodium ion battery by using a biomass material. The preparation method disclosed by the invention has the advantages that the operation process is simple and feasible, the supplied materials are wide, the cost is low, the interlayer spacing of the hard carbon negative electrode material of the sodium-ion battery prepared according to the preparation method disclosed by the invention is enlarged through chemical treatment, the distribution of holes is adjusted, the energy density is high, the rate capability is good, various indexes of the negative electrode material of the sodium-ion battery can be met, the hard carbon negative electrode material is an excellent negative electrode material of the sodium-ion battery, and meanwhile, the preparation method disclosed by the invention has an important significance for recycling agricultural wastes.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a biomass-based hard carbon anode material for a sodium-ion battery, comprising the following steps:
(1) washing and drying the biomass material;
(2) sintering the biomass material obtained in the step (1) for 1-24 hours at the temperature of 100-800 ℃ in an oxygen-deficient atmosphere to obtain a carbon precursor subjected to primary pyrolysis;
(3) crushing the carbon precursor powder obtained in the step (2);
(4) dipping the carbon precursor powder crushed in the step (3) in a permanganate solution with the concentration of 0.00001-5mol/L, washing with water and drying;
(5) sieving the carbon precursor powder obtained in the step (4);
(6) sintering the powder obtained in the step (5) at the temperature of 800-2500 ℃ for 0.5-48 hours in an inert atmosphere to obtain a carbon material;
(7) and (3) washing the carbon material obtained in the step (6) with an acid solution, then washing with clear water until the pH value is 7, and drying to obtain the final hard carbon negative electrode material.
Further, the biomass in the step (1) is biological agricultural waste, preferably, the biomass material is at least one of rice, sugarcane, rape, cotton, wheat, corn, reed, sisal, bamboo, peanut, seaweed, towel gourd, pumpkin, jujube wood, oak, peach wood and machine-made wood as a carbon source. More specifically, corn stalks, pumpkin vines, and straw stalks, for example.
Further preferably, the drying temperature in the step (1) is 80-300 ℃, and the drying time is 4-48 hours; the drying is done in an oven, kiln, muffle or tube furnace.
Further, in the step (2), the sintering time may be 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 20 hours, 24 hours, 30 hours, 40 hours, or 48 hours. Preferably, the sintering temperature may be 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃.
Further, the sintering in the step (2) may be performed in an oven, a kiln, a muffle furnace or a tube furnace.
Further, the particle size after the pulverization in the step (3) is between 1 and 100 microns. The machine used for the pulverization may be one or more of a ball mill, a jaw crusher, a cone crusher, a roll crusher, a hammer crusher, an edge runner mill, an impact crusher, a roll-over ring mill, a colloid mill, a vibration mill, and a jet mill.
Further, in the step (4), the permanganate solution is prepared as follows: the solid permanganate is dissolved in a first solvent. The concentration of the permanganate solution is preferably 0.00001 to 3mol/L, and may be, for example, 0.00001mol/L, 0.0001mol/L, 0.001mol/L, 0.01mol/L, 0.1mol/L, 1mol/L, 2mol/L, or 3 mol/L.
Further preferably, the permanganate in step (4) is selected from at least one of lithium permanganate, sodium permanganate and potassium permanganate.
Further preferably, the weight ratio of the permanganate to the carbon precursor in the step (4) is 0.00001 to 3: 1, preferably 0.0001 to 2.5: 1, more preferably 0.001 to 2: 1, more preferably 0.01 to 1: 1.
further preferably, the drying temperature in the step (4) is 80-300 ℃, and the drying time is 4-48 hours. The drying may be accomplished in an oven, kiln, muffle or tube furnace.
Further preferably, the number of the sieve meshes in the step (5) is 50 to 1000 meshes.
The sieving can adopt one or more of the following devices, including a vibrating powder sieving machine, a rotary vibrating sieve, a suspension type partial gravity sieving machine, an electromagnetic shaking sieving machine and an electromagnetic vibrating sieving machine.
Further, in the step (6), preferably, the sintering time is 0.5 hour, 2 hours, 4 hours, 12 hours, 6 hours, 10 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours, 30 hours, 40 hours, or 48 hours. Preferably, the sintering temperature is 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃, 1800 ℃, 1900 ℃, 2000 ℃, 2100 ℃, 2200 ℃, 2300 ℃, 2400 ℃, 2500 ℃.
Further, in the step (6), the sintering is performed in an apparatus including an oven, a kiln, a muffle furnace, a tube furnace, and the like.
Further, in the step (7), the acid solution is selected from one or more of sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid. Preferably, the acid solution is selected from dilute sulfuric acid, dilute nitric acid or dilute hydrochloric acid.
Further, in the step (7), the acid solution is prepared as follows: dissolving concentrated acid in the second solvent. The concentration of the acid solution can be 0.001mol/L, 0.01mol/L, 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L and 5 mol/L.
Still further, the first solvent and the second solvent are each independently water, alcohol, styrene, perchloroethylene, trichloroethylene, benzene, toluene, xylene, or a combination thereof.
A second aspect of the invention provides a biomass-based sodium-ion battery hard carbon anode material prepared by the above method.
The invention also provides application of the biomass-based hard carbon negative electrode material of the sodium-ion battery in the negative electrode material of the sodium-ion battery. Specifically, the invention provides a sodium ion battery cathode which is prepared by taking the biomass-based sodium ion battery hard carbon cathode material as a raw material.
Further, the invention provides a battery comprising the negative electrode of the sodium-ion battery.
The invention provides a biomass-based hard carbon negative electrode material of a sodium ion battery and a preparation method thereof, and the preparation method comprises the following steps: washing and drying the biomass material, and isolating air and heating in an anoxic atmosphere to obtain a carbon precursor; pulverizing the obtained carbon precursor and soaking the carbon precursor in a permanganate solution to oxidize the carbon material and generate more sodium storage sites; and drying and sieving the treated carbon precursor, then performing secondary sintering, wherein the temperature of the secondary sintering is higher than that of the primary sintering, then washing the product with acid liquor, washing the product with clear water to be neutral, and drying the product to obtain the final product.
The method comprises the steps of pre-carbonizing biomass, oxidizing a carbon precursor into a carbon material matrix by using a permanganate solution to enable the carbon material matrix to have more sodium storage sites, performing secondary sintering, and washing out MnO on the surface2And preparing the biomass-based hard carbon negative electrode material of the sodium ion battery. The hard carbon cathode material of the sodium ion battery is prepared by adopting a twice sintering method, the cost of the raw materials is low, and the electrochemistry of the obtained materialThe performance is excellent.
The method of the invention has the following advantages:
(1) the hard carbon cathode material of the sodium ion battery is prepared by taking cheap, environment-friendly, renewable and easily-obtained biomass as a raw material, and has the advantage of obvious low cost compared with a manually-prepared carbon material.
(2) The two-stage carbonization process is adopted, so that impurities in the biomass can be fully removed, and meanwhile, a porous carbon material with high carbon content is formed by utilizing the hole structure of the biomass;
(3) the carbon material is treated by the permanganate solution, so that the carbon material is oxidized, the interlayer spacing of the carbon material is enlarged, the embedding of sodium ions is promoted, and the capacity of the material is improved. And more holes are generated by the carbon material, and the rate capability of the material is further improved.
(4)MnO2The volume change is severe in the charging and discharging process, and the first charging and discharging efficiency and the cycle performance are improved. MnO remaining after treatment with acid-washing permanganate solution2And impurities, the charge-discharge efficiency of the material is further improved, and the excellent performance of the hard carbon material is ensured.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings 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 it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic XRD diagram of the hard carbon anode material of the biomass-based sodium-ion battery in example 1.
Fig. 2 is a SEM schematic of the biomass-based sodium ion battery hard carbon negative electrode material of example 1.
Fig. 3 is a particle size distribution diagram of the hard carbon anode material of the biomass-based sodium-ion battery in example 1.
FIG. 4 is a first charge-discharge curve diagram of the hard carbon negative electrode material of the biomass-based sodium-ion battery in example 1 at 20 mA/g.
FIG. 5 is a graph comparing the cycling performance at 50mA/g for the hard carbon anode material of the biomass-based Na-ion battery of example 1.
Fig. 6 is a schematic XRD diagram of the hard carbon anode material of the biomass-based sodium-ion battery in example 2.
Fig. 7 is a SEM schematic of the biomass-based sodium ion battery hard carbon negative electrode material of example 2.
FIG. 8 is a first charge-discharge curve diagram of the hard carbon negative electrode material of the biomass-based sodium-ion battery in example 2 at 20 mA/g.
FIG. 9 is a graph comparing the cycling performance at 50mA/g for the hard carbon anode material of the biomass-based Na-ion battery of example 2.
Fig. 10 is a SEM schematic of the biomass-based sodium ion battery hard carbon negative electrode material of example 3.
FIG. 11 is a first charge-discharge curve diagram of the hard carbon negative electrode material of the biomass-based sodium-ion battery in example 3 at 20 mA/g.
FIG. 12 is a graph comparing the cycling performance at 50mA/g for the hard carbon anode material of the biomass-based Na-ion battery of example 3.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Unless otherwise defined, all terms of art 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 limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1
This example is used to illustrate a method for preparing a biomass-based hard carbon negative electrode material for a sodium ion battery according to the present invention, and includes the following steps:
1) 1000g of corn straws are taken as raw materials, washed for three times by deionized water, and dried for 5 hours in a muffle furnace at 100 ℃.
2) Heating the corn straws obtained in the step 1) at 800 ℃ for 4 hours in an anoxic atmosphere to obtain a primary pyrolyzed carbon precursor.
3) The carbon precursor obtained in step 2) is pulverized by a ball mill until D50 reaches 10 μm and the particle size distribution is narrow.
4) The crushed carbon precursor is immersed in 1L of 0.1mol/L high lithium manganate solution and stirred for 1 hour, and then the carbon precursor is taken out.
5) The treated carbon precursor was dried at 110 ℃ for 5 hours and sieved through a 160 mesh sieve.
6) The material was incubated at 1300 ℃ for 25 hours under a nitrogen atmosphere.
7) And washing the material subjected to secondary sintering once by using a 0.1mol/L nitric acid solution, washing the material to be neutral by using clean water, and drying the material in a muffle furnace at 102 ℃ for 6 hours to obtain a final product.
It can be seen from fig. 1 that there is a broad peak around 23 °, corresponding to the (100) plane of the hard carbon material. There is a broad peak at about 45 degrees, corresponding to the (001) plane of the hard carbon material, and the absence of a hetero peak in the figure indicates that the hard carbon material has less impurities.
An SEM image of the hard carbon material is shown in fig. 2.
The particle size distribution of the material is shown in figure 3 with a D10 of 3.63 microns, a D50 of 9.52 microns and a D90 of 20.9 microns.
As shown in fig. 4, a button cell is assembled in a glove box filled with argon and strictly controlled in water-oxygen index by using a metal sodium sheet as a negative electrode and a hard carbon negative electrode material of the embodiment as a positive electrode, and is charged and discharged at a current density of 20mA/g under a voltage of 0-2V, with a first charging specific capacity of 297mAh g-1The first coulombic efficiency was 81.05%. As shown in FIG. 5, the capacity of the material after 24 cycles at a current density of 50mA/g was 237mAh g-1The capacity retention rate was 79.87%.
Example 2
This example is used to illustrate a method for preparing a biomass-based hard carbon negative electrode material for a sodium ion battery according to the present invention, and includes the following steps:
1) 200g of pumpkin vine is taken as a raw material, washed for three times by using distilled water and dried for 5 hours in a blast oven at 130 ℃.
2) Heating the pumpkin vine obtained in the step 1) at 600 ℃ for 10 hours under argon atmosphere to obtain a primary pyrolyzed carbon precursor.
3) And (3) crushing the carbon precursor obtained in the step 2) by using a jet mill until D50 reaches 20 microns and the particle size distribution is narrow.
4) The pulverized carbon precursor was immersed in 500mL of a 1mol/L sodium permanganate solution and stirred for 1 hour, and then the carbon precursor was taken out.
5) The treated carbon precursor was dried at 200 ℃ for 5 hours and sieved through a 300 mesh sieve.
6) The material was incubated at 1500 ℃ for 20 hours under argon atmosphere.
7) And washing the twice-fired material once by using 0.5mol/L hydrochloric acid solution, washing the material to be neutral by using clean water, and drying the material in a muffle furnace at 102 ℃ for 6 hours to obtain a final product.
It can be seen from fig. 6 that there is a broad peak around 23 °, corresponding to the (100) plane of the hard carbon material. There is a broad peak at about 45 degrees, corresponding to the (001) plane of the hard carbon material, and the absence of a hetero peak in the figure indicates that the hard carbon material has less impurities.
An SEM image of the hard carbon material is shown in fig. 7.
As shown in fig. 8, a button cell is assembled in a glove box filled with argon and strictly controlled in water-oxygen index by using a metal sodium sheet as a negative electrode and a hard carbon negative electrode material of the embodiment as a positive electrode, and is charged and discharged at a current density of 20mA/g under a voltage of 0-2V, with a first charging specific capacity of 288mAh g-1The first coulombic efficiency was 76.60%. As shown in FIG. 9, the capacity of the material after 100 cycles at a current density of 50mA/g was 228mAh g-1The capacity retention rate was 79.17%.
Example 3
This example is used to illustrate a method for preparing a biomass-based hard carbon negative electrode material for a sodium ion battery according to the present invention, and includes the following steps:
1) 1000g of straw is taken as a raw material, washed for three times by distilled water and dried for 48 hours in a tubular furnace at the temperature of 201 ℃.
2) Heating the straw obtained in the step 1) at 300 ℃ for 24 hours in a helium atmosphere to obtain a primary pyrolyzed carbon precursor.
3) Crushing the carbon precursor obtained in the step 2) by using a jaw crusher until D50 reaches 50 microns and the particle size distribution is narrow.
4) The crushed carbon precursor is immersed in 2L of 0.5mol/L potassium permanganate solution and stirred for 1 hour, and then the carbon precursor is taken out.
5) The treated carbon precursor was dried at 200 ℃ for 5 hours and sieved through a 300 mesh sieve.
6) The material was incubated at 1800 ℃ for 25 hours under argon atmosphere.
7) Washing the material after the secondary sintering once by using 0.5mol/L hydrochloric acid solution, washing the material to be neutral by using clean water, and drying the material in a tubular furnace at 102 ℃ for 6 hours to obtain a final product.
An SEM image of the hard carbon material is shown in fig. 10.
As shown in fig. 11, a button cell is assembled in a glove box filled with argon and strictly controlled in water-oxygen index by using a metal sodium sheet as a negative electrode and a hard carbon negative electrode material of the embodiment as a positive electrode, and is charged and discharged at a current density of 20mA/g under a voltage of 0-2V, with a first charging specific capacity of 324mAh g-1The first coulombic efficiency was 75.21%. As shown in FIG. 12, the capacity of the material after 200 cycles at a current density of 50mA/g was 274mAh g-1The capacity retention was 85.63%.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (13)
1. A preparation method of a biomass-based hard carbon negative electrode material of a sodium ion battery is characterized by comprising the following steps:
(1) washing and drying the biomass material;
(2) sintering the biomass material obtained in the step (1) for 1-48 hours at the temperature of 100-800 ℃ in an oxygen-deficient atmosphere to obtain a carbon precursor subjected to primary pyrolysis;
(3) crushing the carbon precursor powder obtained in the step (2);
(4) dipping the carbon precursor powder crushed in the step (3) in a permanganate solution with the concentration of 0.00001-5mol/L, washing with water and drying;
(5) sieving the carbon precursor powder obtained in the step (4);
(6) sintering the powder obtained in the step (5) at the temperature of 800-2500 ℃ for 0.5-48 hours in an inert atmosphere to obtain a carbon material;
(7) and (3) washing the carbon material obtained in the step (6) with an acid solution, then washing with clear water until the pH value is 7, and drying to obtain the final hard carbon negative electrode material.
2. The method of claim 1, wherein the biomass material is at least one of rice, sugar cane, rape, cotton, wheat, corn, reed, sisal, bamboo, peanut, seaweed, loofah, pumpkin, jujube, oak, peach and machine-made wood.
3. The preparation method of the biomass-based hard carbon anode material for the sodium-ion battery of the claim 1, wherein the drying temperature in the step (1) is 80-300 ℃, and the drying time is 4-48 hours; the drying is done in an oven, kiln, muffle or tube furnace.
4. The preparation method of the biomass-based hard carbon anode material for the sodium-ion battery of the claim 1, wherein the sintering in the step (2) is completed in an oven, a kiln, a muffle furnace or a tube furnace.
5. The preparation method of the biomass-based hard carbon anode material for the sodium-ion battery of the claim 1, wherein the particle size of the crushed material in the step (3) is 1-100 microns.
6. The method for preparing the hard carbon anode material of the biomass-based sodium-ion battery according to claim 1, wherein the permanganate in the step (4) is at least one selected from the group consisting of lithium permanganate, sodium permanganate and potassium permanganate; the weight ratio of the permanganate to the carbon precursor in the step (4) is 0.00001-3: 1.
7. the preparation method of the biomass-based hard carbon anode material for the sodium-ion battery of the claim 1, wherein the drying temperature in the step (4) is 80-300 ℃, and the drying time is 4-48 hours; the drying is done in an oven, kiln, muffle or tube furnace.
8. The preparation method of the biomass-based hard carbon anode material for the sodium-ion battery of the claim 1, wherein the number of the sieve meshes in the step (5) is 50-1000 meshes.
9. The method for preparing the hard carbon anode material of the biomass-based sodium-ion battery according to claim 1, wherein the sintering time in the step (6) is 0.5-48 hours; the sintering is done in an oven, kiln, muffle or tube furnace.
10. The method for preparing the hard carbon anode material of the biomass-based sodium-ion battery according to claim 1, wherein the acid solution in the step (7) is one or more selected from sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; the concentration of the acid liquor is between 0.001 and 5 mol/L.
11. The preparation method of the biomass-based hard carbon anode material for the sodium-ion battery of the sodium-ion battery as claimed in claim 1, wherein the drying temperature in the step (7) is 80-300 ℃; the drying time is 4-48 hours; the drying is completed in an oven, a kiln, a muffle furnace or a tubular furnace; the dry atmosphere is air or an oxygen-deficient atmosphere.
12. A biomass-based sodium-ion battery hard carbon anode material prepared by the method of any one of claims 1-11.
13. Use of the biomass-based sodium-ion battery hard carbon anode material of claim 12 in a sodium-ion battery anode material.
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