CN117790732A - Biomass hard carbon material for negative electrode of sodium ion battery and preparation method thereof - Google Patents
Biomass hard carbon material for negative electrode of sodium ion battery and preparation method thereof Download PDFInfo
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- CN117790732A CN117790732A CN202311798711.3A CN202311798711A CN117790732A CN 117790732 A CN117790732 A CN 117790732A CN 202311798711 A CN202311798711 A CN 202311798711A CN 117790732 A CN117790732 A CN 117790732A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 110
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 96
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 48
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 17
- 238000010306 acid treatment Methods 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 239000007833 carbon precursor Substances 0.000 claims description 57
- 238000001035 drying Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000010902 straw Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 241000209140 Triticum Species 0.000 claims description 12
- 235000021307 Triticum Nutrition 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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 relates to the technical field of negative electrode materials, in particular to a biomass hard carbon material for a negative electrode of a sodium ion battery and a preparation method thereof. The invention comprises the following steps: firstly, carrying out alkali treatment and acid treatment on a biomass raw material, then compounding under high-temperature high-pressure hydrothermal conditions, and finally carrying out high-temperature treatment under inert atmosphere, thereby obtaining the biomass hard carbon material which can be used for the negative electrode material of the sodium ion battery. The material obtained by the invention not only has excellent sodium ion storage capacity, but also has rich pore structure and excellent conductivity, thus having wide application prospect in the field of sodium ion batteries.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a biomass hard carbon material for a negative electrode of a sodium ion battery and a preparation method thereof.
Background
Since the commercialization of lithium ion batteries, energy storage technologies have revolutionized tremendous. Rechargeable alkali metal ion batteries (e.g., lithium, sodium, and potassium ion batteries) are widely used in portable scientific and technological products, new energy automobiles, and the like because of their high energy density, long cycle performance, excellent stability, and the like. However, with the over-development of global lithium resources and the ever-expanding market energy demands, the cost of lithium ion batteries has increased in recent years, and lithium resources are not renewable and have non-recyclability. In this case, an alkali metal ion battery, sodium ion battery, which is promising as a substitute has been attracting attention successfully because of its cleanliness, low cost, and abundant content in the crust of earth, and environmental friendliness.
At present, a carbonaceous material is one of the anode materials with the most potential application through a large number of experiments. For sodium ion batteries, it is important to find a sustainable, environmentally friendly, easy to prepare and inexpensive anode carbon material. The use of biomass as a precursor for the anode carbon material of sodium ion batteries is a very good research concept. A large number of biomass materials, such as soybean roots, sorghum stalks, rice hulls, and the like, are used as precursors for the preparation of carbonaceous materials. In addition, the wheat straw contains rich natural channels and pore structures, and shows excellent electrochemical performance. At the same time MoS 2 The composition of (2) can promote the sodium storage capacity of the material and promote the electron transmission rate. Therefore, the biomass hard carbon material is prepared by taking the wheat straw as the carbon precursor of the negative electrode material, so that a new thought is provided for reducing environmental pollution, relieving energy crisis and other problems, and the biomass hard carbon material has good economic benefit and market prospect.
In order to overcome the defects of the prior art, the invention provides a biomass hard carbon material for a sodium ion battery cathode and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a biomass hard carbon material for a sodium ion battery cathode and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the biomass hard carbon material for the negative electrode of the sodium ion battery comprises the following steps:
step one: washing, drying, crushing and sieving the biomass material in sequence to obtain a biomass hard carbon precursor material;
step two: sequentially performing alkali treatment, washing and drying on the biomass hard carbon precursor material to obtain an alkali treated biomass hard carbon precursor material; sequentially carrying out acid treatment, washing and drying on the alkali-treated biomass hard carbon precursor material to obtain an acid-treated biomass hard carbon precursor material;
step three: adding an acid-treated biomass hard carbon precursor material, a molybdenum source and a sulfur source into an ethanol solution, stirring for 30-50min, adding ammonium persulfate, stirring for 60-80min, transferring into a reaction kettle, and preserving heat for 12-36h at 120-200 ℃ in an oven to obtain a pre-composite biomass hard carbon precursor material;
step four: and (3) carbonizing the pre-composite biomass hard carbon precursor material in an argon atmosphere, and cooling to room temperature after the reaction is finished to obtain a finished product.
More preferably, in the first step, the biomass material is wheat straw, and the particle size of the biomass hard carbon precursor material is 50-600 meshes.
More optimally, in the second step, the solution selected by alkali treatment is any one of potassium hydroxide solution and sodium hydroxide solution, and the concentration is 1mol/L-3mol/L.
More preferably, in the second step, the alkali treatment temperature is 120-200 ℃ and the alkali treatment time is 6-18h.
More optimally, in the second step, the solution selected by acid treatment is any one of hydrochloric acid solution and sulfuric acid solution, and the concentration is 0.5mol/L-2mol/L.
More preferably, in the second step, the temperature of the acid treatment is 60-95 ℃ and the acid treatment time is 1-6h.
More optimally, in the third step, the molybdenum source is any one of sodium molybdate and ammonium molybdate tetrahydrate, and the sulfur source is any one of thiourea, sublimed sulfur and ammonium thiocyanate; the mass ratio of acid treated biomass hard carbon precursor material, molybdenum source and sulfur source is (1:1:2) - (1:3:5); the mass ratio of ammonium persulfate to molybdenum source is (5:1) - (10:1); the ethanol solution is formed by mixing absolute ethanol and deionized water, wherein the volume ratio of the absolute ethanol is 50-80%.
More optimally, in the fourth step, the carbonization treatment temperature is 500-900 ℃, the time is 2-4h, and the heating speed is 5-10 ℃/min.
The invention has the beneficial effects that:
according to the invention, wheat straw is washed, dried, crushed and sieved in sequence to obtain a biomass hard carbon precursor material, and dirt such as soil on the straw is cleaned; and sequentially carrying out alkali treatment, washing and drying on the biomass carbon precursor material to ensure that cellulose, lignin and hemicellulose in the biomass material wheat straw are subjected to preliminary decomposition, so as to obtain the form of the preliminary sheet material. Sequentially performing acid treatment, washing and drying on the biomass hard carbon precursor material subjected to alkali treatment, so as to be beneficial to sufficiently removing metal ion impurities such as K contained in the material + 、Ca 2+ 、Na + And Mg (magnesium) 2+ Etc. And uniformly mixing the biomass hard carbon precursor material subjected to acid treatment with a molybdenum source and a sulfur source according to a certain mass ratio, and then placing the mixture in a reaction kettle for compounding at high temperature and high pressure. Finally, high-temperature treatment is carried out in the inert gas atmosphere, and the high-temperature treatment not only can promote MoS 2 Firmly anchored with the flaky biomass hard carbon material, the graphitization degree of the material can be improved, a large interlayer spacing is formed, and the specific surface area is increased. As can be seen from the nitrogen adsorption and desorption curves measured in FIG. 1, the prepared biomass hard carbon material has a large specific surface area, and the scanning electron microscope diagrams of the biomass hard carbon material measured in FIGS. 2-6 illustrate MoS 2 Firmly anchored on the surface of the flaky biomass hard carbon material. The method not only ensures that sodium ions have rich active sites in the storage process, but also can promote the intercalation and deintercalation of sodium ions, thereby improving the reversible specific capacity and long-cycle stability of the material and finally obtaining the biomass hard carbon material for the sodium ion battery anode material.
The invention is characterized in that: (1) By adding the alkali solution, the biomass hard carbon material of the porous sheet layer can be obtained by utilizing the stripping action of alkali metal ions, and the biomass hard carbon material has higher specific surface area and reasonable pore size distribution. (2) The biomass hard carbon material obtained by compounding through hydrothermal reaction and high-temperature treatment has good sodium ion storage capacity, larger interlayer spacing and better electric conduction capacity, has excellent electrochemical performance when being used for the negative electrode material of the sodium ion battery, has the specific capacity of 309mAh/g after 100 times of circulation, and has the coulombic efficiency of 97 percent, and the biomass hard carbon material is sufficient for meeting various performance requirements of the negative electrode material of the sodium ion battery. (3) The method provided by the invention takes the wheat straw with low cost and wide sources as biomass raw materials, has simple preparation process, low requirements on production equipment, low cost and environmental protection, is easy to realize mass preparation, and has huge future application prospect.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a graph showing the nitrogen adsorption and desorption curves of the biomass hard carbon material prepared in example 2 of the present invention;
FIG. 2 is a scanning electron microscope image of the biomass hard carbon material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the biomass hard carbon material prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of the biomass hard carbon material prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of the biomass hard carbon material prepared in example 4 of the present invention;
FIG. 6 is a scanning electron microscope image and an EDS element distribution diagram of the biomass hard carbon material prepared in example 2 of the present invention;
FIG. 7 is a graph showing the rate capability of the biomass hard carbon material prepared in example 2 of the present invention at a current density of 0.2-10C;
FIG. 8 is a graph showing the cycle performance of the biomass hard carbon material prepared in example 2 of the present invention at a current density of 0.2C.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely in connection with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw material sources are as follows:
wheat straw is provided by standing-horse shop grazing straw processing Co., ltd, and the quality grade is grade A.
Example 1: step one: washing, drying, crushing and sieving the biomass material wheat straw in sequence to obtain a biomass hard carbon precursor material with the particle size of 100 meshes;
step two: mixing 10g of biomass hard carbon precursor material with 30mL of 1mol/L potassium hydroxide solution, reacting for 12 hours at 180 ℃, and washing and drying to obtain alkali-treated biomass hard carbon precursor material; refluxing the alkali-treated biomass hard carbon precursor material for 2 hours at 80 ℃ by using a 1moL/L hydrochloric acid solution, and washing and drying to obtain an acid-treated biomass hard carbon precursor material;
step three: adding 5g of acid-treated biomass hard carbon precursor material, 5g of ammonium molybdate tetrahydrate and 10g of thiourea into 20mL of 50% ethanol solution, stirring for 30min, adding 25g of ammonium persulfate, stirring for 60min, transferring into a 30mL reaction kettle, and preserving heat for 12h at 180 ℃ in an oven to obtain a pre-composite biomass hard carbon precursor material;
step four: and (3) in the argon atmosphere, heating the pre-composite biomass hard carbon precursor material from room temperature to 600 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to room temperature after the reaction is finished to obtain a finished product.
Example 2: step one: washing, drying, crushing and sieving the biomass material wheat straw in sequence to obtain a biomass hard carbon precursor material with the particle size of 200 meshes;
step two: mixing 10g of biomass hard carbon precursor material with 30mL of 2mol/L potassium hydroxide solution, reacting for 6 hours at 180 ℃, and washing and drying to obtain alkali-treated biomass hard carbon precursor material; refluxing the alkali-treated biomass hard carbon precursor material for 2 hours at 80 ℃ by using a 1moL/L hydrochloric acid solution, and washing and drying to obtain an acid-treated biomass hard carbon precursor material;
step three: adding 5g of acid-treated biomass hard carbon precursor material, 10g of ammonium molybdate tetrahydrate and 15g of sublimed sulfur into 20mL of 50% ethanol solution, stirring for 30min, adding 80g of ammonium persulfate, stirring for 60min, transferring into a 30mL reaction kettle, and preserving heat for 12h at 200 ℃ in an oven to obtain a pre-composite biomass hard carbon precursor material;
step four: and (3) in the argon atmosphere, heating the pre-composite biomass hard carbon precursor material from room temperature to 700 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to room temperature after the reaction is finished to obtain a finished product.
Example 3: step one: washing, drying, crushing and sieving the biomass material wheat straw in sequence to obtain a biomass hard carbon precursor material with the particle size of 200 meshes;
step two: mixing 10g of biomass hard carbon precursor material with 30mL of 3mol/L potassium hydroxide solution, reacting for 6 hours at 180 ℃, and washing and drying to obtain alkali-treated biomass hard carbon precursor material; refluxing the alkali-treated biomass hard carbon precursor material for 2 hours at 80 ℃ by using a 1moL/L hydrochloric acid solution, and washing and drying to obtain an acid-treated biomass hard carbon precursor material;
step three: adding 5g of acid-treated biomass hard carbon precursor material, 15g of sodium molybdate and 20g of sublimed sulfur into 20mL of 50% ethanol solution, stirring for 30min, adding 150g of ammonium persulfate, stirring for 60min, transferring into a 30mL reaction kettle, and preserving heat for 24h at 200 ℃ in an oven to obtain a pre-composite biomass hard carbon precursor material;
step four: and (3) in the argon atmosphere, heating the pre-composite biomass hard carbon precursor material from room temperature to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to room temperature after the reaction is finished to obtain a finished product.
Example 4: step one: washing, drying, crushing and sieving the biomass material wheat straw in sequence to obtain a biomass hard carbon precursor material with the particle size of 300 meshes;
step two: mixing 12g of biomass hard carbon precursor material with 30mL of 2mol/L potassium hydroxide solution, reacting for 6 hours at 120 ℃, and washing and drying to obtain alkali-treated biomass hard carbon precursor material; refluxing the alkali-treated biomass hard carbon precursor material for 2 hours at 80 ℃ by using a 1moL/L hydrochloric acid solution, and washing and drying to obtain an acid-treated biomass hard carbon precursor material;
step three: adding 5g of acid-treated biomass hard carbon precursor material, 15g of sodium molybdate and 25g of ammonium thiocyanate into 20mL of 80% ethanol solution, stirring for 30min, adding 150g of ammonium persulfate, stirring for 60min, transferring into a 30mL reaction kettle, and preserving heat for 24h at 200 ℃ in an oven to obtain a pre-composite biomass hard carbon precursor material;
step four: and (3) in the argon atmosphere, heating the pre-composite biomass hard carbon precursor material from room temperature to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to room temperature after the reaction is finished to obtain a finished product.
Detection test:
rate performance and cycle performance test: the biomass hard carbon material for the sodium ion battery, which is prepared in the embodiment 2, is taken as a carbon material, the carbon material, acetylene black and PVDF are uniformly mixed according to the mass ratio of 8:1:1, NMP is taken as a solvent, stirring is carried out for 6 hours to form uniform slurry, the slurry is uniformly coated on copper foil, the copper foil is dried for 12 hours at 80 ℃ in a vacuum drying oven, and a punching machine is used for punching the copper foil into a circular sheet with the diameter of 12mm after the drying; the wafer is used as a negative electrode of a sodium ion battery, a metal sodium sheet is used as a counter electrode, the wafer is assembled in the CR-2032 type sodium ion battery, a glass fiber membrane (Whatman GF/D) is used as a diaphragm, and 1mol/L NaClO is used as electrolyte 4 The mixed solution is formed by mixing Ethylene Carbonate (EC) and Propylene Carbonate (PC) according to a volume ratio of 1:1, the test is carried out on a blue CT2001A multichannel blue battery test system, the termination voltage range is 0.01-3.0V, the current density of the rate performance test is 0.2-10C, and the test is carried out for 10 periods under each current density; the current density for cycle performance test was 0.2C, testing 100 cycle periods.
Nitrogen adsorption and desorption test: the biomass hard carbon material for sodium ion battery prepared in example 2 was used as a carbon material. Prior to testing, the samples were ensured to be dry and of appropriate particle size. And placing the sample in an adsorption instrument to gradually adsorb nitrogen on the surface of the sample, and further measuring important parameters such as specific surface area of the sample.
Conclusion: as can be seen from FIG. 8, the MoS for sodium ion battery prepared in example 2 at a current density of 0.2C 2 After 100 circles of circulation, the flaky biomass hard carbon material still has 309mAh/g reversible specific capacity, and the coulomb efficiency is kept at 97%. As can be seen from the nitrogen adsorption and desorption curves measured in FIG. 1, the prepared biomass hard carbon material has a large specific surface area.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a biomass hard carbon material for a sodium ion battery cathode is characterized by comprising the following steps of: the method comprises the following steps:
step one: washing, drying, crushing and sieving the biomass material in sequence to obtain a biomass hard carbon precursor material;
step two: sequentially performing alkali treatment, washing and drying on the biomass hard carbon precursor material to obtain an alkali treated biomass hard carbon precursor material; sequentially carrying out acid treatment, washing and drying on the alkali-treated biomass hard carbon precursor material to obtain an acid-treated biomass hard carbon precursor material;
step three: adding an acid-treated biomass hard carbon precursor material, a molybdenum source and a sulfur source into an ethanol solution, stirring for 30-50min, adding ammonium persulfate, stirring for 60-80min, and preserving heat at 120-200 ℃ for 12-36h to obtain a pre-composite biomass hard carbon precursor material;
step four: and (3) carbonizing the pre-composite biomass hard carbon precursor material in an argon atmosphere, and cooling to room temperature after the reaction is finished to obtain a finished product.
2. The method for preparing the biomass hard carbon material for the negative electrode of the sodium ion battery according to claim 1, which is characterized in that: in the first step, the biomass material is wheat straw, and the particle size of the biomass hard carbon precursor material is 50-600 meshes.
3. The method for preparing the biomass hard carbon material for the negative electrode of the sodium ion battery according to claim 1, which is characterized in that: in the second step, the solution selected by alkali treatment is any one of potassium hydroxide solution and sodium hydroxide solution, and the concentration is 1mol/L-3mol/L.
4. The method for preparing the biomass hard carbon material for the negative electrode of the sodium ion battery according to claim 1, which is characterized in that: in the second step, the temperature of the alkali treatment is 120-200 ℃, and the time of the alkali treatment is 6-18h.
5. The method for preparing the biomass hard carbon material for the negative electrode of the sodium ion battery according to claim 1, which is characterized in that: in the second step, the solution selected by acid treatment is any one of hydrochloric acid solution and sulfuric acid solution, and the concentration is 0.5mol/L-2mol/L.
6. The method for preparing the biomass hard carbon material for the negative electrode of the sodium ion battery according to claim 1, which is characterized in that: in the second step, the temperature of the acid treatment is 60-95 ℃ and the acid treatment time is 1-6h.
7. The method for preparing the biomass hard carbon material for the negative electrode of the sodium ion battery according to claim 1, which is characterized in that: in the third step, the molybdenum source is any one of sodium molybdate and ammonium molybdate tetrahydrate, and the sulfur source is any one of thiourea, sublimed sulfur and ammonium thiocyanate; the mass ratio of acid treated biomass hard carbon precursor material, molybdenum source and sulfur source is (1:1:2) - (1:3:5); the mass ratio of ammonium persulfate to molybdenum source is (5:1) - (10:1); the ethanol solution is formed by mixing absolute ethanol and deionized water, wherein the volume ratio of the absolute ethanol is 50-80%.
8. The method for preparing the biomass hard carbon material for the negative electrode of the sodium ion battery according to claim 1, which is characterized in that: in the fourth step, the carbonization treatment is carried out at 500-900 ℃ for 2-4 hours at a heating rate of 5-10 ℃/min.
9. A biomass hard carbon material prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the biomass hard carbon material according to claim 9 in a negative electrode material of a sodium ion battery.
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