CN116761776A - Biomass hard carbon material and preparation method and application thereof - Google Patents
Biomass hard carbon material and preparation method and application thereof Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 80
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 73
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 83
- 238000010438 heat treatment Methods 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 238000005245 sintering Methods 0.000 claims abstract description 44
- 239000013522 chelant Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 15
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 229920001568 phenolic resin Polymers 0.000 claims description 15
- 244000060011 Cocos nucifera Species 0.000 claims description 13
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 244000183278 Nephelium litchi Species 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 description 81
- 238000001914 filtration Methods 0.000 description 37
- 239000000706 filtrate Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 25
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000003513 alkali Substances 0.000 description 9
- 238000010000 carbonizing Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 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 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 230000004069 differentiation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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Abstract
The application belongs to the technical field of sodium ion batteries, and particularly relates to a biomass hard carbon material and a preparation method and application thereof. The preparation method of the biomass hard carbon material comprises the following steps: sintering the biomass raw material to obtain a sintered material, and then ball-milling the sintered material to obtain a ball-milled product; adding an acid washing solution into a ball-milling product, heating, stirring, washing, immersing the washed material into an alkaline washing solution, stirring at normal temperature, and washing to obtain a washing product; adding a chelating agent into the washing product, heating and stirring, carrying out suction filtration, washing and drying to obtain a chelating product; and mixing the chelate product with the modified material by a wet method, drying and sintering to obtain the biomass hard carbon material. The biomass hard carbon material prepared by the preparation method has the advantages of less impurity content and low porosity, and can normalize biomass material components of different batches, thereby improving the electrochemical performance of the biomass hard carbon material.
Description
Technical Field
The application belongs to the technical field of sodium ion batteries, and particularly relates to a biomass hard carbon material and a preparation method and application thereof.
Background
Due to the rapid development of clean energy, there is a growing need for large, efficient, inexpensive energy storage systems. The lithium ion battery has the characteristics of high energy density and long cycle life, and is widely applied to portable electronic products and electric automobile markets. However, the limited and unbalanced distribution of lithium resources has limited its application in large-scale energy storage. Sodium Ion Batteries (SIBs) are receiving considerable attention as a potential alternative product due to their abundant resources and similar operating mechanisms as lithium ion batteries. However, the sodium ion has a larger atomic diameter than the lithium ion, and it cannot form binary intercalated graphite in a carbonate electrolyte system, and thus it is not easy to form intercalated graphite in SIBs. Other low cost, larger interlayer spacing anode materials need to be explored.
Biomass hard carbon has a low cost, a wide source, an environmentally friendly and highly disordered structure, and a unique structure such as mesopores, porosities and the like, so that sodium ions are easily accommodated, and a higher sodium storage capacity is caused, and the advantages make hard carbon attracting great attention in SIBs. However, biomass hard carbon itself contains a large amount of impurity elements such as sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), silicon (Si) and the like due to factors of growth environment, and meanwhile, the contents of the impurity elements are different due to factors of regional environment, individual difference and the like, and the biomass hard carbon made from different batches has different structures, components and electrochemical properties, so that the biomass hard carbon material is difficult to industrialize and apply, and measures are needed to normalize the components of the biomass hard carbon. Up to now, there are few reports considering the differentiation of the components of biomass hard carbon in different batches.
Disclosure of Invention
The application aims to provide a biomass hard carbon material, and a preparation method and application thereof. The biomass hard carbon material prepared by the preparation method provided by the application contains fewer impurities, and can realize excellent electrochemical performance.
In order to achieve the above purpose, the present application adopts the following technical scheme: the preparation method of the biomass hard carbon material comprises the following steps:
sintering the biomass raw material to obtain a sintered material, and then ball-milling the sintered material to obtain a ball-milled product;
adding an acid washing solution into a ball-milling product, heating, stirring, washing, immersing the washed material into an alkaline washing solution, stirring at normal temperature, and washing to obtain a washing product;
adding a chelating agent into the washing product, heating and stirring, carrying out suction filtration, washing and drying to obtain a chelating product;
and mixing the chelate product with the modified material by a wet method, drying and sintering to obtain the biomass hard carbon material.
As a preferred embodiment of the method for preparing a biomass hard carbon material according to the present application, the biomass raw material includes at least one of coconut shells, litchi wood, bamboo chips, cotton, and rice hulls.
As a preferred embodiment of the preparation method of the biomass hard carbon material, the mass ratio of the chelate product to the modified material is (1-5): 1.
as a preferred embodiment of the method for preparing a biomass hard carbon material according to the present application, the modified material includes at least one of phenolic resin and soluble starch.
As a preferred embodiment of the preparation method of the biomass hard carbon material, the acid washing solution is a solution with pH of less than 7, and the concentration of the acid washing solution is 0.5-3 mol/L. More preferably, the pickling solution comprises at least one of sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid.
As a preferred embodiment of the preparation method of the biomass hard carbon material, the alkaline washing solution is a solution with pH of more than 7, and the concentration of the alkaline washing solution is 2-5 mol/L. More preferably, the alkaline cleaning solution comprises at least one of potassium hydroxide and sodium hydroxide.
As a preferred embodiment of the method for preparing biomass hard carbon material of the present application, the mass ratio of the chelating agent to the washing product is 1: (5-40).
As a preferred embodiment of the method for preparing a biomass hard carbon material according to the present application, the chelating agent is at least one of ethylenediamine tetraacetic acid (EDTA) and disodium ethylenediamine tetraacetic acid solution (EDTA-2 Na).
As a preferred embodiment of the method for producing a biomass hard carbon material of the present application, the concentration of the chelating agent is 0.02 to 0.1mol/L.
As a preferred implementation mode of the preparation method of the biomass hard carbon material, the temperature of heating and stirring the ball-milling product after pickling is 60-90 ℃, the time is 2-5 h, and the stirring speed is 300-600 rpm.
As a preferred embodiment of the method for producing a biomass hard carbon material according to the present application, the stirring time at normal temperature is 2 to 5 hours, and the stirring speed is 300 to 600rpm.
As a preferred embodiment of the preparation method of the biomass hard carbon material, the temperature of heating and stirring the washing product after adding the chelating agent is 80-120 ℃, the treatment time is 1-6 h, and the stirring speed is 300-600 rpm.
As a preferred implementation mode of the preparation method of the biomass hard carbon material, the drying temperature is 80-90 ℃, and the drying time is 8-12 h.
As a preferred embodiment of the preparation method of the biomass hard carbon material, the washing conditions are that water is used as a solvent to wash to be neutral.
As a preferred implementation mode of the preparation method of the biomass hard carbon material, the condition of sintering the biomass raw material is that under the protection of inert atmosphere, the sintering temperature is 400-800 ℃, the heating rate is 5-10 ℃/min, and the sintering time is 4-8 h; the inert atmosphere includes nitrogen, argon, and the like.
As a preferred embodiment of the preparation method of the biomass hard carbon material, the ball milling speed is 300-600 rpm, and the ball milling time is 1-3 h.
As a preferred embodiment of the preparation method of the biomass hard carbon material, the Dv50 particle size of the ball milling product is 10-15 microns.
As a preferred embodiment of the method for preparing a biomass hard carbon material according to the present application, the wet mixed solvent includes at least one of absolute ethanol and deionized water.
As a preferable implementation mode of the preparation method of the biomass hard carbon material, the drying temperature is 60-80 ℃ and the drying time is 6-10 h.
As a preferred implementation mode of the preparation method of the biomass hard carbon material, the condition of sintering after mixing and drying the chelate product and the modified material is that the sintering temperature is 1200-1600 ℃ under the protection of inert atmosphere, the heating rate is 0.5-4 ℃/min, and the sintering time is 2-6 h.
More preferably, the inert atmosphere comprises nitrogen, argon, or the like.
The application also claims a biomass hard carbon material prepared by the preparation method.
The application also claims an application of the biomass hard carbon material in preparing sodium ion batteries.
The application takes coconut shells and the like as biomass raw materials, and considers different impurity types. First, since biomass raw materials contain a large amount of organic carbon such as lignin, cellulose and hemicellulose, unstable organic carbon can be converted into inorganic carbon through a high-temperature sintering process, which can promote rearrangement of structure and discharge most of tar. Secondly, impurities on the surface of the biomass material and metal elements in the particles are removed through acid washing and alkali washing, and residual metal elements, particularly Na, K, ca, mg and other elements, are further removed through interaction with a chelating agent, so that most of impurities can be removed through the combined action of the three elements. And finally, repairing and closing the carbon structure by adding the modified material and carbonizing at high temperature, so that the porosity of the prepared biomass hard carbon material is effectively reduced, and the hard carbon material with excellent performance is obtained. The application adopts hot acid washing to accelerate the reaction rate, and adopts normal temperature alkali washing because the material after primary sintering still maintains the characteristics of cellulose, if the material is washed by hot alkali, the cellulose and the hot alkali react to cause chain breakage and decomposition, thereby reducing the yield. The application adopts the advantages that the treatment is carried out in a specific sequence of acid washing, alkali washing and carbonization: the acid washing and alkali washing can remove part of impurities, and also can destroy a carbon structure, oxygen-containing functional groups are introduced, so that the porosity and defect degree are increased, structural repair and closed pore can be promoted after high-temperature carbonization, and the porosity is reduced.
Compared with the prior art, the application has the following beneficial effects:
(1) The application adopts a treatment method of a specific sequence of sintering, secondary impurity removal and three-high-temperature carbonization to cooperatively remove most of impurity elements, reduce the porosity and realize the normalization of biomass material components in different batches, thereby improving the electrochemical performance of hard carbon.
(2) The preparation method of the biomass hard carbon material can be used for normalizing biomass materials in various batches, and has wide applicability. In addition, normalization has practical significance for improving the electrochemical performance of hard carbon, and is expected to be used for industrialization.
Drawings
Fig. 1 is an SEM image of a biomass hard carbon material prepared in example 2 of the present application.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the examples and comparative examples, the experimental methods used were conventional methods, and the materials, reagents and the like used were commercially available, unless otherwise specified.
Example 1 Biomass hard carbon material and preparation method thereof
Putting litchi wood into a box-type furnace, and adding the litchi wood into N 2 Under the protection of atmosphere, the treatment temperature is 400 ℃, the heating rate is 5 ℃/min, the heat treatment is carried out for 8 hours to obtain a sintering material, and then the sintering material is ball-milled for 3 hours at the rotating speed of 300rpm to obtain a ball-milled product with the Dv50 particle size of 10-15 microns;
immersing ball-milled product into 0.5mol/L H 2 SO 4 Heating and stirring the solution, adjusting the rotating speed to 300rpm, setting the heating temperature to 90 ℃, heating and stirring for 5 hours, washing and filtering the solution after the process is finished, ending the filtering after the pH value of the filtrate reaches 7, immersing the obtained material into 2mol/LKOH solution, stirring at normal temperature, adjusting the rotating speed to 300rpm, stirring for 5 hours, washing and filtering the solution after the process is finished, ending the filtering until the pH value of the filtrate reaches 7, and obtaining a washing product;
adding 0.02mol/L EDTA-2Na solution into the washed product, heating and stirring for 6 hours under the conditions of 300rpm and 80 ℃ of heating temperature, washing and suction-filtering the washed product until the pH value of the filtrate reaches 7, ending suction-filtering, and drying the filtrate in an 80 ℃ oven for 12 hours to obtain a chelate product; wherein the mass ratio of EDTA-2Na solution to washing product is 1:5, a step of;
dispersing the chelate product in phenolic resin ethanol solution (chelate product and phenol)The mass ratio of the aldehyde resin is 5: 1) Heating and stirring until ethanol is evaporated to dryness, then placing the mixed materials into a high-temperature furnace, and adding the materials into N 2 And (3) performing co-sintering under the protection of atmosphere, wherein the treatment temperature is 1200 ℃, the heating rate is 0.5 ℃/min, and carbonizing for 6 hours to obtain the biomass hard carbon material.
Example 2 Biomass hard carbon material of the application and preparation method thereof
Putting coconut shells into a box-type furnace, and adding the coconut shells into N 2 Under the protection of atmosphere, the treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat treatment is carried out for 6 hours to obtain a sintering material, and then the sintering material is ball-milled for 1 hour at the rotating speed of 520rpm to obtain a ball-milled product with the Dv50 particle size of 10-15 microns;
immersing ball-milled product into 0.5mol/L H 2 SO 4 Heating and stirring the solution, adjusting the rotating speed to 500rpm, setting the heating temperature to 80 ℃, heating and stirring for 3 hours, washing and filtering the solution after the process is finished, ending the filtering after the pH value of the filtrate reaches 7, immersing the obtained material into 3mol/LKOH solution, stirring at normal temperature, adjusting the rotating speed to 500rpm, stirring for 4 hours, washing and filtering the solution after the process is finished, ending the filtering until the pH value of the filtrate reaches 7, and obtaining a washing product;
adding 0.04mol/L EDTA-2Na solution into the washed product, heating and stirring for 2 hours under the conditions of 500rpm and 110 ℃ of heating temperature, washing and suction-filtering the washed product until the pH value of the filtrate reaches 7, ending suction-filtering, and drying the filtrate in an oven at 80 ℃ for 8 hours to obtain a chelate product; wherein the mass ratio of EDTA-2Na solution to washing product is 1:20, a step of;
dispersing the chelate product in phenolic resin ethanol solution (the mass ratio of the chelate product to the phenolic resin is 3:1), heating and stirring until ethanol is evaporated to dryness, then placing the mixed material into a high-temperature furnace, and adding the mixture into N 2 And (3) performing co-sintering under the protection of atmosphere, wherein the treatment temperature is 1500 ℃, the heating rate is 1 ℃/min, and carbonizing for 4 hours to obtain the biomass hard carbon material.
Example 3 Biomass hard carbon material of the application and preparation method thereof
Placing bamboo scraps into a box-type furnace, and placingN 2 Under the protection of atmosphere, the treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat treatment is carried out for 4 hours to obtain a sintering material, and then the sintering material is ball-milled for 1 hour at the rotating speed of 600rpm to obtain a ball-milled product with the Dv50 particle size of 10-15 microns;
immersing the ball-milled product into 3mol/L H 2 SO 4 Heating and stirring the solution, adjusting the rotating speed to 600rpm, setting the heating temperature to 60 ℃, heating and stirring for 2 hours, washing and filtering the solution after the process is finished, ending the filtering after the pH value of the filtrate reaches 7, immersing the obtained material into 5mol/LKOH solution, stirring at normal temperature, adjusting the rotating speed to 600rpm, stirring for 2 hours, washing and filtering the solution after the process is finished, ending the filtering until the pH value of the filtrate reaches 7, and obtaining a washing product;
adding 0.1mol/L EDTA solution into the washed product, heating and stirring for 1h under the conditions of 600rpm and 120 ℃ of heating temperature, washing and suction-filtering the washed product until the pH value of the filtrate reaches 7, ending suction-filtering, and drying the filtrate in an oven at 80 ℃ for 8h to obtain a chelate product; wherein the mass ratio of EDTA solution to washing product is 1:40, a step of performing a;
dispersing the chelate product in phenolic resin ethanol solution (the mass ratio of the chelate product to the phenolic resin is 1:1), heating and stirring until ethanol is evaporated to dryness, then placing the mixed material into a high-temperature furnace, and adding the mixture into N 2 And (3) performing co-sintering under the protection of atmosphere, wherein the treatment temperature is 1600 ℃, the heating rate is 4 ℃/min, and carbonizing for 2 hours to obtain the biomass hard carbon material.
Example 4 Biomass hard carbon material of the application and preparation method thereof
Putting coconut shells into a box-type furnace, and adding the coconut shells into N 2 Under the protection of atmosphere, the treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat treatment is carried out for 6 hours to obtain a sintering material, and then the sintering material is ball-milled for 1 hour at the rotating speed of 520rpm to obtain a ball-milled product with the Dv50 particle size of 12 micrometers;
immersing ball-milled product into 0.5mol/L H 2 SO 4 Heating and stirring the solution, adjusting the rotating speed to 500rpm, setting the heating temperature to 80 ℃, heating and stirring for 3 hours, and feeding the solution after the process is finishedWashing with water, filtering until the pH value of the filtrate reaches 7, immersing the obtained material in 3mol/LKOH solution, stirring at normal temperature, adjusting the rotating speed to 500rpm, stirring for 5h, washing with water, filtering until the pH value of the filtrate reaches 7, and filtering to obtain a washing product;
adding 0.06mol/L EDTA-2Na solution into the washed product, heating and stirring for 2 hours under the conditions of 500rpm and 110 ℃ of heating temperature, washing and suction-filtering the washed product until the pH value of the filtrate reaches 7, ending suction-filtering, and drying the filtrate in an oven at 80 ℃ for 8 hours to obtain a chelate product; wherein the mass ratio of EDTA-2Na solution to washing product is 1:20, a step of;
dispersing the chelate product in phenolic resin ethanol solution (the mass ratio of the chelate product to the phenolic resin is 3:1), heating and stirring until ethanol is evaporated to dryness, then placing the mixed material into a high-temperature furnace, and adding the mixture into N 2 And (3) performing co-sintering under the protection of atmosphere, wherein the treatment temperature is 1500 ℃, the heating rate is 1 ℃/min, and carbonizing for 4 hours to obtain the biomass hard carbon material.
Example 5 Biomass hard carbon material of the application and preparation method thereof
Putting coconut shells into a box-type furnace, and adding the coconut shells into N 2 Under the protection of atmosphere, the treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat treatment is carried out for 6 hours to obtain a sintering material, and then the sintering material is ball-milled for 1 hour at the rotating speed of 520rpm to obtain a ball-milled product with the Dv50 particle size of 12 micrometers;
immersing ball-milled product into 0.5mol/L H 2 SO 4 Heating and stirring the solution, adjusting the rotating speed to 500rpm, setting the heating temperature to 80 ℃, heating and stirring for 3 hours, washing and filtering the solution after the process is finished, ending the filtering after the pH value of the filtrate reaches 7, immersing the obtained material into 3mol/LKOH solution, stirring at normal temperature, adjusting the rotating speed to 500rpm, stirring for 5 hours, washing and filtering the solution after the process is finished, ending the filtering until the pH value of the filtrate reaches 7, and obtaining a washing product;
adding 0.08mol/L EDTA-2Na solution into the washed product, heating and stirring for 2 hours under the conditions of 500rpm and 110 ℃ of heating temperature, washing and suction-filtering the washed product until the pH value of the filtrate reaches 7, ending suction-filtering, and drying the filtrate in an oven at 80 ℃ for 8 hours to obtain a chelate product; wherein the mass ratio of EDTA-2Na solution to washing product is 1:20, a step of;
dispersing the chelate product in phenolic resin ethanol solution (the mass ratio of the chelate product to the phenolic resin is 3:1), heating and stirring until ethanol is evaporated to dryness, then placing the mixed material into a high-temperature furnace, and adding the mixture into N 2 And (3) performing co-sintering under the protection of atmosphere, wherein the treatment temperature is 1500 ℃, the heating rate is 1 ℃/min, and carbonizing for 4 hours to obtain the biomass hard carbon material.
Comparative example 1
The comparative example differs from example 2 only in that no acid washing, alkali washing, or chelating agent treatment was performed.
The preparation method is described in example 2.
Comparative example 2
The difference between this comparative example and example 2 is only that EDTA-2Na solution was added at a concentration of 0.01mol/L.
The preparation method is described in example 2.
Comparative example 3
The only difference between this comparative example and example 2 is that no EDTA-2Na solution was added.
The preparation method is described in example 2.
Comparative example 4
The comparative example differs from example 2 only in that no pickling operation was performed.
The preparation method comprises the following steps: putting coconut shells into a box-type furnace, and adding the coconut shells into N 2 Under the protection of atmosphere, the treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat treatment is carried out for 6 hours to obtain a sintering material, and then the sintering material is ball-milled for 1 hour at the rotating speed of 520rpm to obtain a ball-milled product with the Dv50 particle size of 10-15 microns;
immersing the ball-milling product into a 3mol/LKOH solution, stirring at normal temperature, adjusting the rotating speed to 500rpm, stirring for 4 hours, washing the ball-milling product with water after the process is finished, and carrying out suction filtration until the pH value of the filtrate reaches 7, and finishing suction filtration to obtain a washing product;
adding 0.04mol/L EDTA-2Na solution into the washed product, heating and stirring for 2 hours under the conditions of 500rpm and 110 ℃ of heating temperature, washing and suction-filtering the washed product until the pH value of the filtrate reaches 7, ending suction-filtering, and drying the filtrate in an oven at 80 ℃ for 8 hours to obtain a chelate product;
dispersing the chelate product in phenolic resin ethanol solution (the mass ratio of the chelate product to the phenolic resin is 3:1), heating and stirring until ethanol is evaporated to dryness, then placing the mixed material into a high-temperature furnace, and adding the mixture into N 2 And (3) performing co-sintering under the protection of atmosphere, wherein the treatment temperature is 1500 ℃, the heating rate is 1 ℃/min, and carbonizing for 4 hours to obtain the biomass hard carbon material.
Comparative example 5
The only difference of this comparative example compared to example 2 is that no modifying material was added.
The preparation method is described in example 2.
Comparative example 6
The only difference in this comparative example compared to example 2 is that the mass ratio of chelate product to modifying material is 6:1.
The preparation method is described in example 2.
Comparative example 7
The preparation method comprises the following steps:
putting coconut shells into a box-type furnace, and adding the coconut shells into N 2 Under the protection of atmosphere, the treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat treatment is carried out for 6 hours to obtain a sintering material, and then the sintering material is ball-milled for 1 hour at the rotating speed of 520rpm to obtain a ball-milled product with the Dv50 particle size of 10-15 microns;
dispersing ball-milled products in phenolic resin ethanol solution (the mass ratio of the ball-milled products to the phenolic resin is 3:1), heating and stirring until ethanol is evaporated to dryness, then placing the mixed materials into a high-temperature furnace, and adding the materials into N 2 Co-sintering under the protection of atmosphere, wherein the treatment temperature is 1500 ℃, the heating rate is 1 ℃/min, and carbonizing for 4 hours to obtain a washing product 1;
immersing the washed product 1 into 0.5mol/L H 2 SO 4 Heating and stirring the solution, adjusting the rotating speed to 500rpm, setting the heating temperature to 80 ℃, and heating and stirringStirring for 3h, after the process is finished, washing and suction filtering the mixture until the pH value of the filtrate reaches 7, after the suction filtering is finished, immersing the obtained material into a 3mol/LKOH solution, stirring at normal temperature, adjusting the rotating speed to 500rpm, stirring for 4h, after the process is finished, washing and suction filtering the mixture until the pH value of the filtrate reaches 7, and after the suction filtering is finished, obtaining a chelate product 1;
adding 0.04mol/L EDTA-2Na solution into the chelate product 1, heating and stirring for 2 hours under the conditions of 500rpm and 110 ℃ of heating temperature, washing and suction filtering the chelate product until the pH value of the filtrate reaches 7, ending suction filtering, and drying the filtrate in an oven at 80 ℃ for 8 hours to obtain a biomass hard carbon material; wherein the mass ratio of EDTA-2Na solution to chelating product 1 is 1:20.
the comparative example differs from example 2 only in that the ball-milled product subjected to high-temperature sintering was subjected to the modified substance treatment first, followed by the acid washing and alkali washing steps.
Test example 1
1. Impurity content determination
The biomass hard carbon materials prepared in examples 1 to 5, comparative examples 1 to 5 and comparative example 7 were subjected to impurity content measurement by using an ICP-AES device. The experimental data are shown in table 1. As can be seen from Table 1, the impurity levels of the products prepared in the examples were significantly lower than those of comparative examples 1 to 4, especially example 2.
Table 1 impurity content of each sample
2. Electrochemical performance test
The electrochemical performance of the biomass hard carbon materials prepared in examples 1 to 5 and comparative examples 1 to 7 was tested by using a blue-ray test system and other equipment. The experimental results are shown in table 2.
Table 2 electrochemical performance data for each sample
From the data in table 2, it can be known that the biomass hard carbon materials prepared in examples 1 to 5 of the application have better electrochemical performance, and the highest charge-discharge efficiency can reach 88.5%.
In comparative example 1, the prepared biomass hard carbon material has poor electrochemical properties by only performing high-temperature sintering treatment; the chelating agent added in comparative examples 2 to 3 was too low in concentration or no chelating agent was added, and the produced hard carbon material had electrochemical properties inferior to those of examples; in comparative example 4, no acid washing operation was performed, and the first charge specific capacity and the first discharge specific capacity of the prepared biomass hard carbon material were lower than those of the examples; in the comparative example 5, no modified material is added, the mass ratio of the chelate product to the modified material in the comparative example 6 is not suitable, and the prepared hard carbon material has electrochemical properties which are inferior to those of the examples; the order of acid washing, alkali washing and modified substance treatment in comparative example 7 was different, resulting in the produced biomass hard carbon material having poor electrochemical properties.
The experiment shows that the interaction among the steps in the preparation method of the biomass hard carbon material can effectively remove the impurity content in the prepared biomass hard carbon material, reduce the porosity and normalize biomass material components of different batches, thereby improving the electrochemical performance of the hard carbon material.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The preparation method of the biomass hard carbon material is characterized by comprising the following steps of:
sintering the biomass raw material to obtain a sintered material, and then ball-milling the sintered material to obtain a ball-milled product;
adding an acid washing solution into a ball-milling product, heating, stirring, washing, immersing the washed material into an alkaline washing solution, stirring at normal temperature, and washing to obtain a washing product;
adding a chelating agent into the washing product, heating and stirring, carrying out suction filtration, washing and drying to obtain a chelating product;
and mixing the chelate product with the modified material by a wet method, drying and sintering to obtain the biomass hard carbon material.
2. The method of claim 1, comprising at least one of the following (1) to (3):
(1) The biomass raw material comprises at least one of coconut shells, litchi wood, bamboo scraps, cotton and rice hulls;
(2) The mass ratio of the chelate product to the modified material is (1-5): 1, a step of;
(3) The modified material comprises at least one of phenolic resin and soluble starch.
3. The method of claim 1, comprising at least one of the following (1) to (2):
(1) The acid washing solution is a solution with pH of less than 7, and the concentration of the acid washing solution is 0.5-3 mol/L;
(2) The alkaline washing solution is a solution with pH of more than 7, and the concentration of the alkaline washing solution is 2-5 mol/L.
4. A production method according to claim 3, comprising at least one of the following (1) to (2):
(1) The acid washing solution comprises at least one of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid;
(2) The alkaline washing solution comprises at least one of potassium hydroxide and sodium hydroxide.
5. The method of claim 1, comprising at least one of the following (1) to (5):
(1) The mass ratio of the chelating agent to the washing product is 1: (5-40);
(2) The chelating agent is at least one of ethylenediamine tetraacetic acid and disodium ethylenediamine tetraacetate solution;
(3) The concentration of the chelating agent is 0.02-0.1 mol/L;
(4) The temperature of heating and stirring the ball-milling product after pickling is 60-90 ℃, the time is 2-5 h, and the stirring speed is 300-600 rpm;
(5) The stirring time at normal temperature is 2-5 h, and the stirring speed is 300-600 rpm.
6. The method of claim 1, comprising at least one of the following (1) to (3):
(1) The temperature of heating and stirring the washing product after adding the chelating agent is 80-120 ℃, the treatment time is 1-6 h, and the stirring speed is 300-600 rpm;
(2) The temperature of the drying is 80-90 ℃, and the drying time is 8-12 hours;
(3) The washing conditions are that water is used as solvent to wash to neutrality.
7. The method of claim 1, comprising at least one of the following (1) to (3):
(1) The condition of sintering the biomass raw material is that under the protection of inert atmosphere, the sintering temperature is 400-800 ℃, the heating rate is 5-10 ℃/min, and the sintering time is 4-8 h;
(2) The ball milling speed is 300-600 rpm, and the ball milling time is 1-3 h;
(3) The Dv50 particle size of the ball milling product is 10-15 microns.
8. The method of claim 1, comprising at least one of the following (1) to (3):
(1) The wet mixed solvent comprises at least one of absolute ethyl alcohol and deionized water;
(2) The drying temperature is 60-80 ℃ and the drying time is 6-10 hours;
(3) The conditions of the mixing and drying of the chelate product and the modified material and the sintering are that the sintering temperature is 1200-1600 ℃ and the heating rate is 0.5-4 ℃/min under the protection of inert atmosphere, and the sintering time is 2-6 h.
9. A biomass hard carbon material produced by the production method according to any one of claims 1 to 8.
10. Use of the biomass hard carbon material according to claim 9 for the preparation of sodium ion batteries.
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