CN110797533A - Lignin hard carbon microsphere, hydrothermal preparation method and application of lignin hard carbon microsphere in alkali metal ion battery cathode - Google Patents
Lignin hard carbon microsphere, hydrothermal preparation method and application of lignin hard carbon microsphere in alkali metal ion battery cathode Download PDFInfo
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Abstract
The invention relates to a lignin hard carbon microsphere, a hydrothermal preparation method and application thereof to an alkali metal ion battery cathode; the lignin carbon microspheres are prepared by taking lignin as a precursor and adopting a hydrothermal method. Firstly, dissolving lignin in water under full stirring to obtain a lignin solution; directly carrying out hydrothermal reaction on the lignin solution or adding acid and alkali to adjust the pH value of the lignin solution and then carrying out hydrothermal reaction to obtain a lignin hydrothermal microsphere precursor; and (3) after drying, putting the lignin microspheres in a tubular furnace, and carrying out high-temperature carbonization under the protection of inert gas to obtain the lignin carbon microspheres. The lignin carbon microsphere has high sphericity, less adhesion, high structure stability, high dispersivity and capacity of maintaining high dispersivity. The invention researches the low-cost process synthesis of the industrial waste lignin hydrothermal ball forming, successfully applies the industrial waste lignin water to the cathode material of the alkali metal ion battery, and shows high capacity, good rate charge-discharge performance and cycling stability.
Description
Technical Field
The invention belongs to the technical field of alkali metal (Li/Na/K) ion battery cathode materials, and particularly relates to a preparation method of a low-cost lignin carbon microsphere with a hard carbon structure and high sphericity and application of the lignin carbon microsphere in an alkali metal (Li/Na/K) ion battery cathode.
Background
In the past decades, social development has been heavily dependent on fossil energy, and thus the environment is seriously polluted, such as greenhouse effect, haze and the like. Scientists in various countries in the world are constantly developing green energy sources (solar energy, wind energy, tidal energy and the like) to replace fossil energy sources so as to reduce the environmental burden and meet the requirement of social development on energy. But the use of these new energy sources is limited because of its regionality and intermittency. These reasons have led to the research and development of electrical energy storage, and therefore secondary alkali metal ion batteries that can be charged and discharged have attracted much attention. For example, lithium ion batteries have the advantages of high energy density, long cycle life, small self-discharge, good rate capability, etc., and are widely used in portable electronic devices such as mobile phones, notebook computers, digital cameras, and electric tools, and also in main power sources or auxiliary power sources in the fields of hybrid electric vehicles, pure electric vehicles, rail transit, engineering machinery, etc., and these developments have greatly promoted the development and application of negative electrode materials with fast charge performance and new technology systems. And other alkali metal ion batteries, for example, sodium ion batteries have an energy storage principle similar to that of lithium ion batteries, and although have electrochemical performance slightly lower than that of lithium ion batteries, sodium resources have the characteristics of wide distribution, low price and the like, so that the alkali metal ion batteries have great development potential in the fields of electric automobiles, energy storage batteries and the like.
Along with the large-scale popularization of lithium ion batteries in the field of electric automobiles, the defects of short endurance mileage, low charging speed, insufficient cycle life, poor high-temperature and low-temperature performance and the like of the conventional lithium ion batteries are gradually exposed, and the urgent requirements of people on the development of a new electrode material system are initiated. For example, a fast-charging lithium ion battery system develops an electrode material system such as lithium iron phosphate and a ternary positive electrode, and the research and development of a hard carbon negative electrode material with large interlayer spacing and small crystallite size are more and more intensive except that graphite is continuously optimized as a negative electrode material. Meanwhile, since the radius of sodium ions is about 1.5 times that of lithium ions, the graphite structure having a small interlayer spacing (about 0.336nm) is not suitable for intercalation and deintercalation of sodium ions, while the hard carbon material having a large interlayer spacing (. gtoreq.0.37 nm) is more suitable for storage of sodium ions.
The hard carbon precursors mainly comprise fossil fuels, high polymer materials and biomasses. The biomass precursor has the advantages of wide source, various structures, reproducibility, low cost, environmental friendliness and the like, and is expected to become a key negative electrode material for the industrialization of the alkali metal ion battery. Tingzhou Yang et al Advanced Materials,2016,28(3): 539-545. Nitrogen-enriched bean dregs are used as raw Materials to prepare nitrogen-doped carbon sheets, and the specific capacity after 50 weeks of circulation is kept at 247.5 mAh/g. Chinese patent CN 108059144A discloses a preparation method of bagasse hard carbon, which takes bagasse as a raw material, and prepares the hard carbon through mechanical ball milling and high-temperature treatment; when used as the cathode of a sodium ion battery and a potassium ion battery, the lithium ion battery shows excellent electrochemical performance. Chinese patent CN 106299365A discloses a preparation method of a hard carbon negative electrode material for a sodium ion battery based on biomass such as pinecone, walnut shell, rice hull and the like, which comprises the steps of crushing and presintering biomass raw materials, calcining and cooling the biomass raw materials to prepare an intermediate, treating the intermediate with alkali liquor, then treating the intermediate with acid liquor, and finally performing microwave activation treatment to prepare the hard carbon negative electrode material suitable for the sodium ion battery. The preparation method of the cathode composite material for the hard carbon/graphite sodium ion battery based on the mangosteen shell biomass shell disclosed in the Chinese patent CN 107068997 comprises the steps of adding carbon-containing biomass shell powder into an alkaline solution, sealing the solution for hydrothermal treatment, mixing the solution with graphite powder after acid washing and water washing, ball milling and refining, carbonizing at a high temperature, acid washing, drying, and grinding to obtain the hard carbon/graphene composite material which can be used for the sodium ion battery. However, in the above methods, the hard carbon cathode is prepared by performing the processing steps of pretreatment, carbonization and the like on the whole biomass precursor, and the components of lignin, cellulose and hemicellulose of the hard carbon cathode are not finely divided, which is not favorable for uniform regulation and control of the hard carbon structure and stability of electrochemical performance, so that a process technology for preparing the hard carbon by determining the biomass components as the precursor needs to be developed.
The lignin is biomass with second content to cellulose in nature, and is a cheap, green and renewable biomass material. Lignin is composed of three basic building blocks: p-hydroxyphenylpropane unit (H), guaiacyl propane unit (G), syringyl propane unit (S). The three lignin basic structural units are mainly connected by C-O-C and C-C, and the connecting part can be generated between hydroxyl groups on a benzene ring, or between three carbon atoms of the structural units, and can also be generated between side chains of the benzene ring to form a complex three-dimensional network macromolecular structure. When the lignin is directly subjected to carbonization heat treatment to prepare the carbon material as a precursor, dehydration, thermal cracking and polycondensation aromatization processes are mainly performed, the prepared carbon material is low in yield, large in specific surface area and developed in pores, and the prepared negative electrode material is small in capacity and low in first charge-discharge efficiency. When the lignin precursor is subjected to hydrothermal carbonization treatment under high temperature and high pressure, the lignin hydrothermal microspheres can be formed because the lignin precursor is subjected to processes of cracking, condensation aromatization and hydrothermal self-assembly of the phenylalkyl and peripheral side chains and functional groups in the hydrothermal carbonization stage in advance. When the lignin hydrothermal microspheres are subjected to carbonization heat treatment, the carbonization yield is obviously higher than that of direct carbonization of lignin precursors, and the lignin carbon microspheres with small specific surface area, high density and good conductivity can be prepared.
Compared with the traditional carbon material, the carbon microsphere has incomparable advantages of high filling density, good fluidity, high mechanical strength, large specific surface area and other carbon materials due to the unique spherical structure, and is applied to the fields of electrode materials, catalyst carriers, adsorbents, drug delivery and the like. The spherical carbon material is used as an electrode material of the alkali metal ion battery, has high electrode density, small specific surface area, good ductility and isotropy, and is beneficial to obtaining high first efficiency, high capacity, high rate performance and long cycle life.
Disclosure of Invention
The invention aims to provide a simple method for preparing lignin carbon microspheres with hard carbon structures. The invention takes lignin as a precursor and adopts a hydrothermal method to prepare the lignin carbon microspheres. The preparation method of the lignin carbon microspheres provided by the invention comprises the steps of firstly dissolving lignin in water under full stirring to obtain a lignin solution; directly carrying out hydrothermal reaction on the lignin solution or adding acid and alkali to adjust the pH value of the lignin solution and then carrying out hydrothermal reaction to obtain a lignin hydrothermal microsphere precursor; and (3) after drying, putting the lignin microspheres in a tubular furnace, and carrying out high-temperature carbonization under the protection of inert gas to obtain the lignin carbon microspheres. The lignin carbon microsphere has high sphericity, less adhesion, high structure stability, high dispersivity and capacity of maintaining high dispersivity. The invention researches the low-cost process synthesis of the industrial waste lignin hydrothermal ball forming, successfully applies the industrial waste lignin water to the cathode material of the alkali metal ion battery, and shows high capacity, good rate charge-discharge performance and cycling stability.
The invention relates to a specific technical scheme as follows:
a lignin hard carbon microsphere, wherein the lignin hard carbon microsphere is spherical, and the graphite-like microcrystalline interlayer spacing (d) of the lignin hard carbon microsphere002) 0.36-0.40 nm;
preferably, the specific surface area of the lignin hard carbon microspheres is 0.5-300 m2The pore volume is 0.01-0.25 cm 3/g.
Preferably, the particle size distribution of the lignin hard carbon microspheres is 1-15 μm.
The preparation method of the lignin hard carbon microspheres at least comprises the following steps:
(1) dissolving a lignin precursor into deionized water, and stirring at room temperature until the lignin precursor is completely dissolved to obtain a lignin solution;
(2) directly carrying out hydrothermal reaction on the lignin aqueous solution, or adding acid or alkali substances to obtain a neutral solution (pH is approximately equal to 7), an acidic solution (pH is less than 7) or an alkaline solution (pH is greater than 7) respectively;
(3) taking the lignin solution obtained in the step (2) as a reaction solution, and carrying out hydrothermal carbonization treatment by adopting a hydrothermal reaction to obtain a lignin hydrothermal product;
(4) separating and drying the lignin hydrothermal product obtained in the step (3) to obtain lignin carbon microspheres;
(5) and (4) carbonizing the lignin microspheres obtained in the step (4) at high temperature under the protection of inert gas to obtain the lignin hard carbon microspheres.
Preferably, the lignin precursor in step (1) is sodium lignosulfonate, ammonium lignosulfonate, calcium lignosulfonate, lignocellulose, or the like.
Preferably, the acid in step (2) is an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or boric acid, etc.; organic acids such as formic acid, acetic acid, propionic acid or butyric acid, etc.
Preferably, the base in step (2) is an inorganic base such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, anhydrous sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate, and the like.
Preferably, the solid content of the solution in the step (2) is 1 to 30 weight percent.
Preferably, the hydrothermal reaction in the step (3) is carried out under the conditions of 150-350 ℃, the hydrothermal treatment time is 3-60 h, and the filling degree of the reaction kettle is 20-75%.
Preferably, the separation method in step (4) is one of filtration, centrifugation, spray drying and the like.
Preferably, the inert gas in step (5) is one or more of nitrogen, argon, hydrogen and carbon monoxide.
Preferably, the high-temperature carbonization temperature in the step (5) is 900-1800 ℃ and the time is 1-5 h.
The lignin hard carbon microspheres are used for the cathode of the alkali metal ion battery; the alkali metal ion battery is a negative electrode material of a lithium ion battery, a sodium ion battery and a potassium ion battery.
The invention also relates to a negative electrode material of the alkali metal battery, which contains the lignin hard carbon microspheres.
Preferably, the alkali metal battery is a lithium ion battery, a sodium ion battery or a potassium ion battery.
The technical scheme of the application has at least the following beneficial effects:
the preparation process has the advantages of simple flow, rich raw material sources, high preparation efficiency, good sphericity of the product and controllable particle size.
The lignin hard carbon microspheres prepared by the invention can be directly carbonized without preoxidation treatment, and the particles are not bonded with each other and have good dispersibility; and is beneficial to coating and film forming in the electrode preparation process and improving the surface flatness of the electrode.
The lignin hard carbon microspheres prepared by the invention have large interlayer spacing, provide more alkali metal ion storage space when being applied as a negative electrode material of an alkali metal (Li/Na/K) ion battery, and have high capacity and rate capability;
the lignin hard carbon microsphere prepared by the invention has low specific surface area and structural stability, and the spherical microcrystalline structure of the lignin hard carbon microsphere is beneficial to the insertion and extraction of sodium ions, lithium ions or potassium ions from all directions, so that the lignin hard carbon microsphere has more stable cycle performance.
Drawings
Fig. 1 is a scanning electron micrograph of the hydrothermal lignin carbon microspheres prepared in example 1.
Fig. 2 is a scanning electron micrograph of the lignin hard carbon microspheres prepared in example 2.
Fig. 3 is a scanning electron micrograph of the lignin hard carbon microspheres prepared in example 3.
Fig. 4 is a scanning electron micrograph of the lignin hard carbon microspheres prepared in example 4.
Fig. 5 is a first three-time charge and discharge curve of the lithium storage of the lignin hard carbon microsphere negative electrode prepared in example 3.
Fig. 6 is the first three charge-discharge curves of the lignin hard carbon microsphere negative electrode sodium storage prepared in example 9.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1: 2g of sodium lignosulfonate powder was added to 60mL of deionized water and stirred until completely dissolved to give a neutral lignin solution with a solids content of about 3%. Transferring the prepared lignin solution into a reaction kettle with the volume of 100mL, and sealing. And (3) heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 12 hours, and naturally cooling to room temperature. Taking out the hydrothermal reaction product, and centrifuging the hydrothermal reaction product to obtain a bottom precipitate; and continuously drying in a blast oven at 80 ℃ to obtain the lignin hydrothermal microspheres. The scanning electron micrograph thereof is shown in FIG. 1. As can be seen from FIG. 1, the prepared spherical lignin particles have smooth surfaces and particle diameters of 2-3 μm. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 900 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 900 ℃.
Example 2: 2g of sodium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the sodium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 2mol/L sodium hydroxide solution was added to obtain an alkaline solution with a solid content of 3%. Transferring the prepared alkaline lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And (3) heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 12 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal gel microspheres; the scanning electron micrograph is shown in figure 2, the particles are spherical, the primary particle diameter is less than 1 μm, and a small amount of fusion and agglomeration phenomena exist. Putting the lignin hydrothermal gel microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 900 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 900 ℃.
Example 3: 2g of sodium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the sodium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 1mol/L hydrochloric acid solution was added to obtain an acidic solution having a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 60 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal microsphere. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 900 ℃ under the protection of nitrogen gas to obtain lignin hard carbon microspheres carbonized at 900 ℃; the scanning electron micrograph thereof is shown in FIG. 3. As can be seen from FIG. 3, the lignin hard carbon microspheres have high sphericity, particle size of 2-10 μm and good dispersibility.
Example 4: the preparation conditions of the hydrothermal lignin microspheres are the same as those of example 3; putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min, and carbonizing for 3 hours at the high temperature of 1100 ℃ under the protection of nitrogen gas to obtain lignin hard carbon microspheres carbonized at 1100 ℃; the scanning electron micrograph thereof is shown in FIG. 4. As can be seen from FIG. 4, the samples prepared under the process conditions had high sphericity, uniform particle size distribution and good dispersibility.
Example 5: the preparation conditions of the hydrothermal lignin microspheres are the same as those of example 3; putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1300 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 1300 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1300 ℃.
Example 6: the preparation conditions of the hydrothermal lignin microspheres are the same as those of example 3; putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1500 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 1500 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1500 ℃.
Example 7: the preparation conditions of the hydrothermal lignin microspheres are the same as those of example 3; putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1800 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 1800 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1800 ℃.
Example 8: 2g of sodium lignosulfonate powder is added into 20mL of deionized water, and the mixture is stirred until the sodium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 1mol/L hydrochloric acid solution was added to obtain an acidic solution having a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 150 ℃, preserving the temperature for 3 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal microsphere. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 900 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 900 ℃.
Example 9: 2g of ammonium lignosulfonate powder is added into 40mL of deionized water, and the mixture is stirred until the ammonium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 1mol/L hydrochloric acid solution was added to obtain an acidic solution having a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 60 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal microsphere. Placing the lignin hydrothermal microspheres in a corundum crucible, placing the corundum crucible in a high-temperature tube furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min, and carbonizing for 3 hours at the high temperature of 1100 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1100 DEG C
Example 10: 2g of calcium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the calcium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 1mol/L hydrochloric acid solution was added to obtain an acidic solution having a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 30 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at 60 ℃ to obtain the lignin hydrothermal microsphere. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1300 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 900 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1300 ℃.
Example 11: 2g of ammonium lignosulfonate powder was added to 75mL of deionized water and stirred until completely dissolved to obtain a lignin solution. Then 20mL of 1mol/L hydrochloric acid solution was added to obtain an acidic solution having a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 200 ℃, preserving the temperature for 30 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal microsphere. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1500 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 1500 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1500 ℃.
Example 12: 2g of ammonium lignosulfonate powder was added to 75mL of deionized water and stirred until completely dissolved to obtain a lignin solution. Then 20mL of 1mol/L hydrochloric acid solution was added to obtain an acidic solution having a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 350 ℃, preserving the temperature for 20 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal microsphere. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1800 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 1800 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1800 ℃.
Example 13: 2g of ammonium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the ammonium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 1mol/L boric acid solution was added to obtain an acidic solution with a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 60 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at 60 ℃ to obtain the lignin hydrothermal microsphere. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 900 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 900 ℃.
Example 14: 2g of ammonium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the ammonium lignosulfonate powder is completely dissolved to obtain a lignin solution. 20mL of 1mol/L acetic acid solution was added to obtain an acidic solution having a solid content of 3%. Transferring the prepared lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 60 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal microsphere. Putting the lignin hydrothermal microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1100 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at the high temperature of 1100 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1100 ℃.
Example 15: 2g of sodium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the sodium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 2mol/L potassium hydroxide solution was added to obtain an alkaline solution with a solid content of 3%. And transferring the prepared alkaline lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 12 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal gel microspheres. Putting the lignin hydrothermal gel microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1300 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 1300 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1300 ℃.
Example 16: 2g of sodium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the sodium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 2mol/L potassium bicarbonate solution was added to obtain an alkaline solution with a solid content of 3%. Transferring the prepared alkaline lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 30 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 60 ℃ to obtain the lignin hydrothermal gel microspheres; the particle size is less than 1 μm. Putting the lignin hydrothermal gel microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 900 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 900 ℃.
Example 17: 2g of sodium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the sodium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 2mol/L sodium carbonate solution was added to obtain an alkaline solution with a solid content of 3%. Transferring the prepared alkaline lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and sealing. And gradually heating the temperature of the reaction kettle to 250 ℃, preserving the temperature for 60 hours, and naturally cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 80 ℃ to obtain the lignin hydrothermal gel microspheres. Putting the lignin hydrothermal gel microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1100 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at the high temperature of 1100 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1100 ℃.
Example 18: 2g of sodium lignosulfonate powder is added into 60mL of deionized water, and the mixture is stirred until the sodium lignosulfonate powder is completely dissolved to obtain a lignin solution. Then 20mL of 2mol/L sodium bicarbonate solution was added to obtain an alkaline solution with a solid content of 3%. Transferring the prepared alkaline lignin solution into a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing. And then placing the hydrothermal reaction kettle into an oven, setting the temperature of the oven to be 250 ℃, setting the temperature of the oven to be 20 ℃ after reacting for 12 hours, and slowly cooling to room temperature. Taking out the solution, centrifuging the solution, taking the sediment at the bottom, and drying the sediment in a blast oven at the temperature of 60 ℃ to obtain the lignin hydrothermal gel microspheres; the particle size is less than 1 μm. Putting the lignin hydrothermal gel microspheres into a corundum crucible, putting the corundum crucible into a high-temperature tube furnace, heating to 1300 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours at 1300 ℃ under the protection of nitrogen gas to obtain the lignin hard carbon microspheres carbonized at 1300 ℃.
Comparative example 1: in patent CN102956876B, glucose is used as a precursor, and in an air flow of Ar-8% H2(H2 accounts for 8% of the volume of the Ar-H2), the temperature is raised to 750 ℃, and the temperature is kept for 15H, and after natural cooling, the thin pyrolytic hard carbon material is obtained. Specific surface area thereofProduct 623m2/g, graphite-like crystallite interlamellar spacing (d)002) 0.37 nm; sodium carboxymethylcellulose (CMC) is used as a binder, and the proportion of the thin pyrolytic hard carbon to the CMC is 9: 1, manufacturing an electrode plate, and assembling a button cell by using metal lithium as a counter electrode. The electrolyte of the battery is as follows: 1.0mol/L LiPF6(EC: DMC is 1:1, V/V), assembled in an argon-protected glove box, and charged and discharged with constant current at a current density of 37mA/g, with a charging voltage range of 0-3.0V.
Comparative example 2: in patent CN106099109B, medium temperature coal tar pitch is used as a raw material, dissolved in n-methyl pyrrolidone (NMP), and then mixed with a sodium chloride template according to a certain ratio, and NMP is evaporated in an oil bath at 200 ℃. And carbonizing the obtained mixture, heating to 750 ℃ at the speed of 5 ℃/min in a tube furnace under the protection of inert gas, maintaining for 2 hours, cooling, taking out, and washing with water to obtain the pitch-based hard carbon nanosheet. The 002 layer spacing of the hard carbon nano-sheet can reach 0.342 nm.
Preparing a negative electrode material from a hard carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, and assembling the sodium-ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-3V, and the charging and discharging rate of the asphalt-based hard carbon nanosheet is 0.1Ag-1Under the condition of the first reversible capacity of 168.3mAh g-1。
The application of the lithium ion battery is as follows:
examples 1 to 7 and comparative example 1 are applied to a lithium ion battery negative electrode material, and the preparation process of the lithium ion battery negative electrode is as follows: mixing a negative active material, conductive carbon black (VXC72) and polyvinylidene fluoride in a mass ratio of 87:5:8 to form slurry, and adding a proper amount of NMP to adjust the viscosity of the slurry to a proper range. The stirring speed was adjusted to 6000 rpm, and after stirring the slurry for 30min, the slurry was coated on a copper foil. And drying the coated pole piece in a vacuum oven at 120 ℃ for 12h, and cutting the piece to obtain the lignin hard carbon microsphere electrode piece. The lignin hard carbon microsphere electrode plate is used as a working electrode, a metal lithium plate is used as a counter electrode, and the electrolyte is LiPF with the concentration of 1.2mol/L6(EC: DMC: EMC ═ 1:1:1, v/v), polypropylene (PP) septum was used as the septum, and the resulting mixture was placed in an argon glove box (H)2O<1ppm，O2<1ppm) and constant current charging and discharging are carried out by adopting a current density of 20mA/g, and the charging voltage range is 0-3.0V. Fig. 5 shows the first three charge and discharge curves of the lignin hard carbon microsphere negative electrode lithium storage prepared in example 3.
Sodium ion battery applications:
examples 8 to 18 and comparative example 2 are applied to a sodium ion battery negative electrode material, and the preparation process of the sodium ion battery negative electrode is as follows: mixing a negative active material, conductive carbon black (VXC72) and polyvinylidene fluoride in a mass ratio of 87:5:8 to form slurry, and adding a proper amount of NMP to adjust the viscosity of the slurry to a proper range. The stirring speed was adjusted to 6000 rpm, and after stirring the slurry for 30min, the slurry was coated on a copper foil. And drying the coated pole piece in a vacuum oven at 120 ℃ for 12h, and cutting the piece to obtain the lignin hard carbon microsphere electrode piece. The lignin hard carbon microsphere electrode slice is used as a working electrode, a metal sodium slice is used as a counter electrode, and the electrolyte is 1mol/L NaClO4And (EC: DEC ═ 1:1, V/V), the diaphragm is a glass fiber diaphragm (GF/F, D ═ 125mm, Whatman), the CR-2430 button sodium battery is assembled in an argon glove box, constant current charging and discharging are carried out by adopting a current density of 20mA/g, and the charging voltage range is 0-3.0V. Fig. 6 shows the first three charge-discharge curves of the lignin hard carbon microsphere negative electrode sodium storage prepared in example 9.
Description of the attached tables
TABLE 1 comparison of structures and first charge and discharge performances of lignin hard carbon microspheres obtained in the examples of the invention and comparative example carbon materials
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. The lignin hard carbon microsphere is characterized in that the lignin hard carbon microsphere is spherical, and the graphite-like microcrystalline interlayer spacing of the lignin hard carbon microsphere is 0.36-0.40 nm.
2. The lignin hard charcoal microsphere according to claim 1, wherein the specific surface area of the lignin hard charcoal microsphere is 0.5-300 m2A pore volume of 0.01 to 0.25 cm/g3/g。
3. The lignin hard charcoal microsphere according to claim 1, wherein the particle size of the lignin hard charcoal microsphere is 1-15 μm.
4. The hydrothermal preparation method of lignin hard carbon microspheres of claim 1, which is characterized by comprising the following steps:
(1) dissolving lignin in deionized water, and fully stirring at room temperature until the lignin is completely dissolved to obtain a lignin solution;
(2) directly carrying out hydrothermal reaction on the lignin aqueous solution; or adding acid or alkali substances, and then carrying out hydrothermal reaction to obtain a lignin hydrothermal microsphere precursor;
(3) and (3) carrying out high-temperature carbonization on the lignin microsphere precursor obtained in the step (2) under the protection of inert atmosphere to obtain the lignin hard carbon microsphere.
5. The method of claim 4, wherein: the lignin in the step (1) is sodium lignosulfonate, ammonium lignosulfonate, calcium lignosulfonate or lignocellulose.
6. The method of claim 4, wherein: the acid used in the step (2) is inorganic acid of hydrochloric acid, sulfuric acid, nitric acid or boric acid; or an organic acid of formic acid, acetic acid, propionic acid or butyric acid.
7. The method of claim 4, wherein: the alkali used in the step (2) is inorganic alkali of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, anhydrous sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate.
8. The process according to claim 4, wherein: the hydrothermal reaction in the step (3) is carried out under the conditions of 150-350 ℃, the hydrothermal treatment time is 3-60 h, and the filling degree of the reaction kettle is 20-75%.
9. The preparation method of claim 4, wherein the high-temperature carbonization temperature in the step (3) is 900-1800 ℃ and the time is 1-5 h.
10. The lignin hard carbon microspheres of claim 1 are used for the negative electrode of an alkali metal ion battery; the alkali metal ion battery is a negative electrode material of a lithium ion battery, a sodium ion battery and a potassium ion battery.
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| SE2250425A1 (en) * | 2022-04-04 | 2023-10-05 | Stora Enso Oyj | Method for producing carbon from lignin |
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