CN116354332A - Production method of hard carbon negative electrode material of sodium ion battery - Google Patents
Production method of hard carbon negative electrode material of sodium ion battery Download PDFInfo
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- CN116354332A CN116354332A CN202310296062.0A CN202310296062A CN116354332A CN 116354332 A CN116354332 A CN 116354332A CN 202310296062 A CN202310296062 A CN 202310296062A CN 116354332 A CN116354332 A CN 116354332A
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 22
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000010902 straw Substances 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 21
- 238000001994 activation Methods 0.000 claims description 17
- 241000196324 Embryophyta Species 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 241000209140 Triticum Species 0.000 claims description 7
- 235000021307 Triticum Nutrition 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 240000007594 Oryza sativa Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical group [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 3
- 238000004146 energy storage Methods 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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 relates to the field of carbon material electrodes, in particular to a method for producing hard carbon negative electrode materials of sodium ion batteries, wherein the used raw materials are plant straws and plant chaffs; the method comprises the following steps: s1: washing raw materials with deionized water, drying, and cutting into 2cm sections; s2: layering the product obtained in the step S1; s3: heating the layered product to 300-500 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature; s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished; s5: and (5) placing the product in a tube furnace for secondary carbonization. According to the invention, impurities contained in raw materials are further removed through twice carbonization, so that the raw materials can be fully carbonized, the time for carbonization each time can be shortened, the integral carbonization time is reduced to about half of the original carbonization time, the product performance is improved, and the production time is reduced.
Description
Technical Field
The invention relates to the field of carbon material electrodes, in particular to a method for producing a hard carbon negative electrode material of a sodium ion battery.
Background
Lithium ion batteries have been widely used in energy storage systems due to their high power density and long cycle life, and are dominant in the field of electric vehicles and portable electronic products. Sodium metal has similar physical and chemical properties to lithium metal, sodium resources are widely distributed and low in price, and the advantages make the sodium ion battery very suitable for large-scale energy storage. The electrode material of the sodium ion battery is a key part of the battery, and determines the specific energy, the service life and the like of the sodium ion battery. At present, many positive electrode materials for sodium ion batteries have been developed, but developing a negative electrode material suitable for practical use of sodium ion batteries still faces many challenges.
The currently commercialized anode materials are mainly carbon materials, and development of new energy materials and energy storage devices with low cost, renewable and environmental friendliness has become a hot spot of current research. Therefore, the search for low-cost and excellent-performance carbon materials has become an important research direction in the art. Biomass waste (such as bamboo, bagasse, wheat straw, wood, derivatives thereof and the like) has the characteristics of wide sources, sustainable regeneration, low pollution and low price, and the preparation of the carbon material by using the biomass waste as a raw material can save the cost and can also relieve the problem of environmental pollution caused by the mass incineration of the waste. In addition, the biomass material often forms special texture structures and texture features in the growth process, the microstructure of the biomass material can be maintained after carbonization, trace impurity elements such as potassium, silicon and the like can activate a carbon skeleton in the heat treatment process so as to enrich the pore structure of the material, and the biomass material is beneficial to improving the electrochemical performance of the electrode material in the charging and discharging processes of a sodium ion battery.
At present, the Chinese patent publication No. CN107337205B discloses a method for converting waste corn stalks into a sodium ion battery electrode material, which has the advantages of simple preparation method, low raw material cost, good repeatability and capability of obtaining a high-performance sodium ion battery for storing energy while protecting the environment. The carbon material prepared by the method has more defects and maintains the porous characteristic, and the characteristic is beneficial to improving the sodium storage capacity of the assembled sodium ion battery and enhancing the cycle stability and the multiplying power performance of the battery.
Besides the above patent, many methods for preparing sodium ion electrode materials by other biomass wastes are derived, and the methods often remove impurities incompletely in the actual preparation process, so that the effect of the finally obtained electrode materials is not ideal, and the preparation scheme at the present stage needs to consume a large amount of carbonization time, so that the whole time consumption is long, and the preparation yield is low.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for producing a hard carbon negative electrode material of a sodium ion battery, which can effectively solve the problem that impurities in the prior art are not thoroughly removed.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the invention provides a method for producing a hard carbon negative electrode material of a sodium ion battery, wherein the used raw materials are plant straws and plant chaffs; the method comprises the following steps:
s1: washing raw materials with deionized water, drying, and cutting into 2cm sections;
s2: layering the product obtained in the step S1;
s3: heating the layered product to 300-500 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature;
s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished;
s5: placing the product into a tube furnace for secondary carbonization, wherein the carbonization temperature is 600-800 ℃, the carbonization time is 2-3h, and then naturally cooling to room temperature;
s6: and (3) grinding the product in a ball mill to obtain a powdery negative electrode material, mixing 80% of the product, 10% of acetylene black and 10% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on the surface of a current collector copper foil, and slicing the slurry after vacuum drying to obtain the sodium ion negative electrode sheet.
Further, the raw materials comprise one or more of bamboo, wheat straw, rice straw, wheat chaff and rice chaff.
In step S2, the layering mode is upper and lower layering, the layer distance is more than or equal to 50mm, and the thickness of each layer is less than or equal to 12mm.
In step S1, the raw materials are refined before cleaning, the mass ratio of deionized water to the product is 20:1, the time is 10-30min, and the cleaning process is repeated for 3-5 times.
Further, in the step S4, the concentration of KOH adopted in the activation process is 10-25%, the reaction temperature of condensation reflux is 40-80 ℃, and the reaction time is 2-10h.
Further, the concentration of KOH used in the activation process is preferably 18%, the reaction temperature of the condensed reflux is preferably 65 ℃, and the reaction time is preferably 4 hours.
Further, in step S6, the particle size of the ball-milled product is 2-50um.
Further, a secondary activation step is added between the steps S5 and S6, and the product is subjected to microwave treatment for 10-15S under the power of 1000-2000W.
Compared with the prior art, the method has the advantages that impurities contained in the raw materials are further removed through twice carbonization, so that the raw materials can be fully carbonized, the time for each carbonization can be shortened, the integral carbonization time is reduced to about half of the original carbonization time, the product performance is improved, the production time is reduced, and the production efficiency is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is an XRD pattern of a negative electrode material obtained in accordance with an embodiment of the present invention;
fig. 2 is a first charge-discharge electrogram of the battery prepared in the second and third embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. 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 invention is further described below with reference to examples.
Example 1
The method for producing the hard carbon cathode material of the sodium ion battery uses plant straws and plant chaffs as raw materials; the method comprises the following steps:
s1: washing raw materials with deionized water, drying, and cutting into 2cm sections;
s2: layering the product obtained in the step S1; the stacking thickness of the products is reduced in a layering manner, so that the products can be fully carbonized in a short time, the effect of the final products is improved, and the preparation efficiency is improved;
s3: heating the layered product to 300 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature;
s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished;
s5: placing the product into a tube furnace for secondary carbonization, wherein the carbonization temperature is 600 ℃, the carbonization time is 3 hours, and then naturally cooling to room temperature;
s6: and (3) grinding the product in a ball mill to obtain a powdery negative electrode material, mixing 80% of the product, 10% of acetylene black and 10% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on the surface of a current collector copper foil, and slicing the slurry after vacuum drying to obtain the sodium ion negative electrode sheet.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative plate into the CR2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1moL/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Further, the raw materials comprise one or more of bamboo, wheat straw, rice straw, wheat chaff and rice chaff.
In step S2, the layering mode is upper and lower layering, the layer distance is more than or equal to 50mm, and the thickness of each layer is less than or equal to 12mm.
In step S1, the raw materials are refined before cleaning, the mass ratio of deionized water to the product is 20:1, the time is 10-30min, and the cleaning process is repeated for 3-5 times.
Further, in the step S4, the concentration of KOH adopted in the activation process is 10-25%, the reaction temperature of condensation reflux is 40-80 ℃, and the reaction time is 2-10h.
Further, the concentration of KOH used in the activation process is preferably 18%, the reaction temperature of the condensed reflux is preferably 65 ℃, and the reaction time is preferably 4 hours.
Further, in step S6, the particle size of the ball-milled product is 2-50um.
According to the embodiment, impurities contained in raw materials are further removed through twice carbonization, so that the raw materials can be fully carbonized, meanwhile, the time for each carbonization can be shortened, the whole carbonization time is reduced to about half of that of the original carbonization time, the production time consumption is reduced while the product performance is improved, and the production efficiency is improved.
Example two
The method for producing the hard carbon cathode material of the sodium ion battery uses plant straws and plant chaffs as raw materials; the method comprises the following steps:
s1: washing raw materials with deionized water, drying, and cutting into 2cm sections;
s2: layering the product obtained in the step S1; the stacking thickness of the products is reduced in a layering manner, so that the products can be fully carbonized in a short time, the effect of the final products is improved, and the preparation efficiency is improved;
s3: heating the layered product to 300 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature;
s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished;
s5: placing the product into a tube furnace for secondary carbonization, wherein the carbonization temperature is 600 ℃, the carbonization time is 3 hours, and then naturally cooling to room temperature;
s6: and (3) grinding the product in a ball mill to obtain a powdery negative electrode material, mixing 80% of the product, 10% of acetylene black and 10% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on the surface of a current collector copper foil, and slicing the slurry after vacuum drying to obtain the sodium ion negative electrode sheet.
A secondary activation step is added between the steps S5 and S6, and the product is subjected to microwave treatment for 15S under the power of 1200W.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative plate into the CR2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1moL/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Example III
The method for producing the hard carbon cathode material of the sodium ion battery uses plant straws and plant chaffs as raw materials; the method comprises the following steps:
s1: washing raw materials with deionized water, drying, and cutting into 2cm sections;
s2: layering the product obtained in the step S1; the stacking thickness of the products is reduced in a layering manner, so that the products can be fully carbonized in a short time, the effect of the final products is improved, and the preparation efficiency is improved;
s3: heating the layered product to 400 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature;
s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished;
s5: placing the product in a tube furnace for secondary carbonization, wherein the carbonization temperature is 700 ℃, the carbonization time is 2 hours, and then naturally cooling to room temperature;
s6: and (3) grinding the product in a ball mill to obtain a powdery negative electrode material, mixing 80% of the product, 10% of acetylene black and 10% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on the surface of a current collector copper foil, and slicing the slurry after vacuum drying to obtain the sodium ion negative electrode sheet.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative plate into the CR2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1moL/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Referring to fig. 2, the capacity of the second embodiment is slightly larger than that of the third embodiment, and it can be determined that the product after the secondary activation has a better effect. The third embodiment is a preferable scheme, and the product prepared by the parameters of the embodiment has more excellent performance.
Example IV
The method for producing the hard carbon cathode material of the sodium ion battery uses plant straws and plant chaffs as raw materials; the method comprises the following steps:
s1: washing raw materials with deionized water, drying, and cutting into 2cm sections;
s2: layering the product obtained in the step S1; the stacking thickness of the products is reduced in a layering manner, so that the products can be fully carbonized in a short time, the effect of the final products is improved, and the preparation efficiency is improved;
s3: heating the layered product to 500 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature;
s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished;
s5: placing the product into a tube furnace for secondary carbonization, wherein the carbonization temperature is 800 ℃, the carbonization time is 2 hours, and then naturally cooling to room temperature;
s6: and (3) grinding the product in a ball mill to obtain a powdery negative electrode material, mixing 80% of the product, 10% of acetylene black and 10% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on the surface of a current collector copper foil, and slicing the slurry after vacuum drying to obtain the sodium ion negative electrode sheet.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative plate into the CR2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1moL/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Example five
The method for producing the hard carbon cathode material of the sodium ion battery uses plant straws and plant chaffs as raw materials; the method comprises the following steps:
s1: washing raw materials with deionized water, drying, and cutting into 2cm sections;
s2: layering the product obtained in the step S1; the stacking thickness of the products is reduced in a layering manner, so that the products can be fully carbonized in a short time, the effect of the final products is improved, and the preparation efficiency is improved;
s3: heating the layered product to 300 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature;
s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished;
s5: placing the product into a tube furnace for secondary carbonization, wherein the carbonization temperature is 800 ℃, the carbonization time is 2 hours, and then naturally cooling to room temperature;
s6: and (3) grinding the product in a ball mill to obtain a powdery negative electrode material, mixing 80% of the product, 10% of acetylene black and 10% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on the surface of a current collector copper foil, and slicing the slurry after vacuum drying to obtain the sodium ion negative electrode sheet.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative plate into the CR2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1moL/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
The following are data of initial coulombic efficiency, initial charge-discharge specific capacity, and capacity retention after 100 cycles of the batteries prepared in each example:
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; these modifications or substitutions do not depart from the essence of the corresponding technical solutions from the protection scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The method for producing the hard carbon cathode material of the sodium ion battery is characterized in that the used raw materials are plant straws and plant chaffs; the method comprises the following steps:
s1: washing raw materials with deionized water, drying, and cutting into 2cm sections;
s2: layering the product obtained in the step S1;
s3: heating the layered product to 300-500 ℃ in a tube furnace at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours for carbonization, and naturally cooling to room temperature;
s4: activating the obtained product by using KOH solution, and fully cleaning and drying the product after the activation is finished;
s5: placing the product into a tube furnace for secondary carbonization, wherein the carbonization temperature is 600-800 ℃, the carbonization time is 2-3h, and then naturally cooling to room temperature;
s6: and (3) grinding the product in a ball mill to obtain a powdery negative electrode material, mixing 80% of the product, 10% of acetylene black and 10% of polyvinylidene fluoride in N-methyl pyrrolidone to prepare slurry, uniformly coating the slurry on the surface of a current collector copper foil, and slicing the dried slurry after vacuum drying to obtain the sodium ion negative electrode sheet.
2. The method for producing a hard carbon negative electrode material for a sodium ion battery according to claim 1, wherein the raw material comprises one or more of bamboo, wheat straw, rice straw, wheat chaff, and rice chaff.
3. The method for producing the hard carbon negative electrode material of the sodium ion battery according to claim 1, wherein in the step S2, the layering mode is upper and lower layering, the layer distance is more than or equal to 50mm, and the thickness of each layer is less than or equal to 12mm.
4. The method for producing the hard carbon negative electrode material of the sodium ion battery according to claim 2, wherein in the step S1, the raw materials are subjected to refining treatment before cleaning, the mass ratio of deionized water to the product is 20:1 during cleaning, the time is 10-30min, and the cleaning process is repeated for 3-5 times.
5. The method for producing hard carbon negative electrode material of sodium ion battery according to claim 1, wherein in step S4, the concentration of KOH used in the activation process is 10% -25%, the reaction temperature of condensation reflux is 40-80 ℃, and the reaction time is 2-10h.
6. The method for producing hard carbon negative electrode material of sodium ion battery according to claim 5, wherein the concentration of KOH used in the activation process is preferably 18%, the reaction temperature of condensation reflux is preferably 65 ℃, and the reaction time is preferably 4 hours.
7. The method for producing hard carbon negative electrode material of sodium ion battery according to claim 1, wherein in step S6, the particle size of the ball-milled product is 2-50um.
8. The method for producing hard carbon negative electrode material of sodium ion battery according to claim 1, wherein a secondary activation step is added between the steps S5 and S6, and the product is subjected to microwave treatment at a power of 1000-2000W for 10-15S.
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