CN116265391A - Vinasse biomass hard carbon material and preparation method and application thereof - Google Patents
Vinasse biomass hard carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116265391A CN116265391A CN202111557569.4A CN202111557569A CN116265391A CN 116265391 A CN116265391 A CN 116265391A CN 202111557569 A CN202111557569 A CN 202111557569A CN 116265391 A CN116265391 A CN 116265391A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- biomass
- carbon material
- vinasse
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a vinasse biomass hard carbon material and a preparation method thereof, wherein vinasse biomass is used as a raw material, a hard carbon precursor is obtained through hydrothermal reaction in an alkaline aqueous solution, and then the hard carbon material is obtained through high-temperature carbonization in an inert environment at 1000-1600 ℃. The hard carbon material has excellent electrochemical performance, and is an ideal negative electrode material of a sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of recycling of biomass waste, relates to a battery electrode material, and particularly relates to a hard carbon material prepared from vinasse biomass, which is suitable for a sodium ion battery anode material.
Background
The distillers 'grains biomass, such as distillers' grains, vinegar residue, soy sauce residue, etc., is the residue produced in brewing wine, vinegar and soy sauce production, and is used as feed for cultivation. The total of various vinasse biomass such as vinasse, vinegar residue and the like produced in China every year is approximately 5000 ten thousand tons, and the vinasse biomass is a very rich biomass raw material, and is scientifically and reasonably utilized, so that the environment can be protected, the added value of the vinasse biomass can be improved, and the waste utilization can be realized.
Hard carbon is carbon which is difficult to graphitize at 2500 ℃ or higher, and is one of amorphous carbon. The low cost and excellent electrochemical performance are of great interest in the field of secondary battery energy storage.
With the large-scale application of lithium ion batteries, the disadvantage of lithium resource shortage has been developed. Sodium resources are abundant, the cost is low, and the lithium ion battery has similar physical and chemical properties to lithium, so that the sodium ion battery is expected to replace the lithium ion battery to become the first choice of a large-scale energy storage power station. And the hard carbon has the characteristic of high reversible specific capacity as a negative electrode material of the sodium ion battery, so that the hard carbon is widely paid attention to by people.
At present, various biomasses such as rice hulls, shaddock peels, banana peels, corncobs and straws are used as raw materials to prepare hard carbon materials, and the hard carbon materials are used as negative electrode materials of sodium ion batteries, so that good electrochemical performance is shown.
CN 111564630a discloses a hard carbon material and a preparation method thereof, wherein after hesperidin is recovered by hydrothermal reaction of orange peel, a carbon precursor is obtained, pre-carbonization treatment is carried out at 200-300 ℃, then high-temperature pyrolysis treatment is carried out under protective atmosphere, and the product is pickled to obtain the hard carbon material.
However, the currently reported preparation method of the hard carbon material has the problems of complicated general synthesis process, high production cost, difficult collection of biomass raw materials, high impurity content, low carbonization yield and the like, and limits the further development and commercialization process of the hard carbon material.
Therefore, the selection of proper biomass raw materials and the adoption of a simple and environment-friendly preparation process to obtain the hard carbon material with high yield and excellent electrochemical performance are particularly urgent.
Disclosure of Invention
The invention aims to provide a vinasse biomass hard carbon material and a preparation method thereof, which are used for preparing the hard carbon material by adopting a green and environment-friendly process method with simple process and are used as a sodium ion battery anode material with excellent electrochemical performance.
The vinasse biomass hard carbon material is prepared by taking vinasse biomass as a raw material, performing hydrothermal reaction in an alkaline aqueous solution to obtain a hard carbon precursor, and carbonizing at a high temperature in an inert environment at 1000-1600 ℃.
The specific surface area of the hard carbon material obtained by the invention is 3-25 m 2 Per gram, the true density is 1.15-1.65 g/cm 3 002 crystal face layer spacing d 002 The value is between 0.375 and 0.390 nm.
Further, the distillers ' grains biomass is residue produced in the process of brewing various products by using grains through fermentation, including but not limited to one or more of beer distillers ' grains, yellow wine distillers ' grains, vinegar residue and soy sauce residue.
Specifically, the invention also provides a preparation method of the vinasse biomass hard carbon material, which adopts dry vinasse biomass as a raw material, performs closed hydrothermal reaction in an alkaline aqueous solution at 150-200 ℃, washes and dries a reaction product to obtain a hard carbon precursor, and heats the reaction product to 1000-1600 ℃ in an inert environment for high-temperature carbonization to prepare the hard carbon material.
Further, the vinasse biomass is dried for 10 to 20 hours at the temperature of between 90 and 120 ℃ to obtain the vinasse biomass raw material.
Further, it is preferable to pulverize the dried distillers' grains biomass raw material into powder having a particle diameter of 100 to 500. Mu.m.
Further, the concentration of the alkaline aqueous solution is 3 to 10wt.%, wherein the base may be sodium hydroxide or potassium hydroxide.
Further, it is preferable to add a spent biomass to the alkaline aqueous solution so that the concentration thereof is 5 to 100mg/mL.
Further, the hydrothermal reaction time is 10-20 h.
Further, it is preferable to grind the product after the hydrothermal reaction to obtain a hard carbon precursor having a particle diameter of 2 to 45. Mu.m.
Further, the hard carbon precursor is heated to 1000-1600 ℃ in an inert environment at a heating rate of 0.5-5 ℃/min for high-temperature carbonization treatment.
Further, the high-temperature carbonization treatment time is 1-10 hours.
Further, the inert environment is introduced with nitrogen or argon.
Furthermore, the invention also provides application of the vinasse biomass hard carbon material as a sodium ion battery anode material.
Still further, the present invention also provides a negative electrode material for sodium ion batteries comprising the distillers' grains biomass hard carbon material as an active material.
The invention adopts the vinasse biomass as the raw material, prepares the hard carbon material with high purity and low ash content at low cost, and improves the economic added value of the biomass while protecting the environment.
The preparation method disclosed by the invention is simple in process, environment-friendly in raw materials, suitable for mass production, and excellent in electrochemical performance, and is an ideal sodium ion battery anode material.
Drawings
Fig. 1 is a transmission electron micrograph of the hard carbon material prepared in example 1.
Fig. 2 is a scanning electron micrograph of the hard carbon material prepared in example 1.
Fig. 3 is a charge-discharge graph of the hard carbon material prepared in example 1.
FIG. 4 is a graph showing the cycle performance of the hard carbon material prepared in example 1.
Fig. 5 is a charge-discharge graph of the hard carbon material prepared in the comparative example.
FIG. 6 is a graph of the cycle performance of the hard carbon material prepared in the comparative example.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are presented only to more clearly illustrate the technical aspects of the present invention so that those skilled in the art can better understand and utilize the present invention without limiting the scope of the present invention.
The experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention, the names and abbreviations thereof are all conventional in the art, and are clearly understood and defined in the relevant fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names, and perform the operations according to the conventional conditions or the conditions suggested by the manufacturer.
The various raw materials or reagents used in the examples and comparative examples of the present invention are not particularly limited in source, and are conventional products commercially available. The preparation may also be carried out according to conventional methods known to the person skilled in the art.
Example 1.
Drying beer lees at 100 ℃ for 15 hours, naturally cooling to room temperature, and crushing to obtain powder raw materials with the grain diameter of 100-300 mu m.
The powder raw materials are added into 5wt.% potassium hydroxide aqueous solution to make the concentration of the powder raw materials be 5mg/mL, and the mixture is heated to 180 ℃ for hydrothermal reaction for 12 hours after sealing, and the mixture is stirred at a stirring speed of 500rpm in the reaction process.
And after the reaction is finished, taking out a reaction product, washing, drying and further grinding to obtain a hard carbon precursor with the particle size of 2-45 mu m.
Under the protection of nitrogen atmosphere, the hard carbon precursor is heated to 1400 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 3 hours for high-temperature carbonization treatment, and the hard carbon material is obtained after cooling to room temperature.
The hard carbon material prepared in this example was tested with a full-automatic specific surface area and porosity analyzer, and the specific surface area was 10m 2 /g。
The actual density of the hard carbon material of this example was 1.47g/cm as measured by the pycnometer method 3 。
As can be seen from the transmission electron micrograph of fig. 1, the interlayer spacing of the hard carbon material is large, 0.379nm, and is suitable as a negative electrode material of a sodium ion battery.
FIG. 2 is a scanning electron micrograph of the hard carbon material prepared in this example, showing that the hard carbon material has a particle size of 5 to 10. Mu.m.
The hard carbon material prepared by the method is evenly mixed with the binder polyvinylidene fluoride (PVDF) and the conductive agent Super-P according to the mass ratio of 8:1:1, then N-methyl pyrrolidone (NMP) is added as a dispersing agent, the mixture is stirred to prepare slurry, the slurry is evenly coated on copper foil, the copper foil is dried at 100 ℃ for 12 hours, pressed into tablets, and the round electrode plates are cut.
The metal sodium sheet is used as a counter electrode, and 1mol/L NaClO is used 4 Or NaPF 6 The EC/DMC (1:1) solution of (a) was used as an electrolyte, a polypropylene film was used as a separator, and a CR2032 type coin cell was assembled in a glove box filled with argon.
The charge and discharge test of the battery was performed on a LanD CT2001A battery test system (Wuhan city blue electric Co., ltd.) to test the specific capacity, cycle performance and rate performance of the battery.
Fig. 3 shows a graph of the first charge and discharge of the hard carbon material prepared in this example at a current density of 0.1C, and it can be seen from the graph that the reversible specific capacity of the material is as high as 289mAh/g.
Fig. 4 further provides a cycle performance graph for the present example to produce a hard carbon material. It can be seen from the graph that after 150 cycles at a current density of 0.5C, the specific capacity of the hard carbon material is still as high as 101mAh/g, and good cycle stability is shown.
Comparative example 1.
Drying beer lees at 100 ℃ for 15 hours, naturally cooling to room temperature, and crushing to obtain powder raw materials with the grain diameter of 100-300 mu m.
The powder raw materials are added into water to make the concentration of the powder raw materials be 5mg/mL, and the mixture is heated to 180 ℃ for hydrothermal reaction for 12 hours after sealing, and the mixture is stirred at a stirring speed of 500rpm in the reaction process.
And after the reaction is finished, taking out a reaction product, washing, drying and further grinding to obtain a hard carbon precursor with the particle size of 2-45 mu m.
Under the protection of nitrogen atmosphere, the hard carbon precursor is heated to 1400 ℃ at the heating rate of 2 ℃/min, and is subjected to high-temperature carbonization treatment after heat preservation for 3 hours, and is cooled to room temperature.
Adding the high-temperature carbonized material into 10wt.% potassium hydroxide aqueous solution, stirring for 12h, washing and drying to obtain the hard carbon material.
Fig. 5 and 6 show the charge-discharge curve and cycle performance of the present comparative example for preparing a hard carbon material, respectively. As can be seen from the graph, the reversible specific capacity of the hard carbon material under the current density of 0.1C is 260mAh/g, the specific capacity after the hard carbon material is cycled for 150 times at 0.5C is only 83mAh/g, and compared with the hard carbon material of the embodiment 1, the reversible specific capacity of the hard carbon material is lower, and the cycle performance is poorer.
Example 2.
Drying yellow wine lees at 110 ℃ for 12 hours, naturally cooling to room temperature, and crushing to obtain powder raw materials with the particle size of 100-300 mu m.
The powder raw materials are added into 10wt.% sodium hydroxide aqueous solution to make the concentration of the powder raw materials be 15mg/mL, and the mixture is heated to 200 ℃ for hydrothermal reaction for 15h after sealing, and the mixture is stirred at a stirring speed of 600rpm in the reaction process.
And after the reaction is finished, taking out a reaction product, washing, drying and further grinding to obtain a hard carbon precursor with the particle size of 2-45 mu m.
Under the protection of argon atmosphere, the hard carbon precursor is heated to 1300 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 5 hours for high-temperature carbonization treatment, and the hard carbon material is obtained after cooling to room temperature.
The hard carbon material prepared in this example was tested with a full-automatic specific surface area and porosity analyzer, and had a specific surface area of 9m 2 /g。
The actual density of the hard carbon material of this example was 1.45g/cm as measured by the pycnometer method 3 。
Example 3.
Drying the vinegar residue at 120 ℃ for 10 hours, naturally cooling to room temperature, and crushing to obtain the powder raw material with the grain diameter of 100-500 mu m.
The powder raw materials are added into 8wt.% sodium hydroxide aqueous solution to make the concentration of the powder raw materials be 30mg/mL, and the mixture is heated to 190 ℃ after sealing for hydrothermal reaction for 10 hours, and the mixture is stirred at a stirring speed of 600rpm in the reaction process.
And after the reaction is finished, taking out a reaction product, washing, drying and further grinding to obtain a hard carbon precursor with the particle size of 2-45 mu m.
Under the protection of nitrogen atmosphere, the hard carbon precursor is heated to 1200 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 6 hours for high-temperature carbonization treatment, and the hard carbon material is obtained after cooling to room temperature.
The hard carbon material prepared in this example was tested with a full-automatic specific surface area and porosity analyzer, and the specific surface area was 16m 2 /g。
The actual density of the hard carbon material of this example was 1.29g/cm as measured by the pycnometer method 3 。
Example 4.
Drying the soy sauce lees at 120 ℃ for 10 hours, naturally cooling to room temperature, and crushing to obtain the powder raw material with the grain diameter of 100-500 mu m.
The powder raw materials are added into 4wt.% potassium hydroxide aqueous solution to ensure that the concentration of the powder raw materials is 60mg/mL, the mixture is sealed and then heated to 160 ℃ for hydrothermal reaction for 18 hours, and the mixture is stirred at a stirring speed of 700rpm in the reaction process.
And after the reaction is finished, taking out a reaction product, washing, drying and further grinding to obtain a hard carbon precursor with the particle size of 2-45 mu m.
Under the protection of argon atmosphere, the hard carbon precursor is heated to 1000 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 6 hours for high-temperature carbonization treatment, and the hard carbon material is obtained after cooling to room temperature.
The hard carbon material prepared in this example was tested with a full-automatic specific surface area and porosity analyzer, and the specific surface area was 21m 2 /g。
Example 5.
Drying vinasse at 120 ℃ for 12 hours, naturally cooling to room temperature, and crushing to obtain powder raw materials with the particle size of 100-500 mu m.
The powder raw materials are added into 3wt.% sodium hydroxide aqueous solution to make the concentration of the powder raw materials be 50mg/mL, and the mixture is heated to 150 ℃ for hydrothermal reaction for 20h after being sealed, and the mixture is stirred at a stirring speed of 800rpm in the reaction process.
And after the reaction is finished, taking out a reaction product, washing, drying and further grinding to obtain a hard carbon precursor with the particle size of 2-45 mu m.
Under the protection of nitrogen atmosphere, the hard carbon precursor is heated to 1500 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 6 hours for high-temperature carbonization treatment, and the hard carbon material is obtained after cooling to room temperature.
The actual density of the hard carbon material of this example was 1.57g/cm as measured by the pycnometer method 3 。
The above embodiments of the invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Claims (10)
1. A hard carbon material is prepared from the vinasse biomass through hydrothermal reaction in alkaline aqueous solution to obtain hard carbon precursor, and high-temp carbonizing at 1000-1600 deg.C in inertial environment.
2. The distillers' grains biomass hard carbon material according to claim 1, wherein the specific surface area of the hard carbon material is 3-25 m 2 Per gram, the true density is 1.15-1.65 g/cm 3 002 crystal face layer spacing d 002 The value is between 0.375 and 0.390 nm.
3. The distillers biomass hard carbon material according to claim 1, wherein the distillers biomass is one or more of brewer's grain, yellow wine grain, vinegar grain, soy sauce grain.
4. The method for preparing the vinasse biomass hard carbon material according to claim 1, wherein dry vinasse biomass is used as a raw material, sealed hydrothermal reaction is carried out at 150-200 ℃ in alkaline aqueous solution, a reaction product is washed and dried to obtain a hard carbon precursor, and the hard carbon precursor is heated to 1000-1600 ℃ in an inert environment for high-temperature carbonization, so that the hard carbon material is prepared.
5. The method for producing a hard carbon material of a spent grain biomass as claimed in claim 4, wherein the spent grain biomass is dried at 90 to 120 ℃ for 10 to 20 hours and pulverized into powder having a particle size of 100 to 500. Mu.m.
6. The method for producing a hard carbon material of a vinasse biomass as claimed in claim 4, wherein the alkaline aqueous solution is an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of 3 to 10wt.%, and the vinasse biomass is added thereto so as to have a concentration of 5 to 100mg/mL.
7. The method for producing a biomass hard carbon material in the form of distillers grains according to claim 4, wherein the hydrothermal reaction time is 10 to 20 hours.
8. The method for producing a biomass hard carbon material in the form of grains according to claim 4, wherein the hard carbon precursor is carbonized in an inert atmosphere at a high temperature of 1000 to 1600 ℃ for 1 to 10 hours at a heating rate of 0.5 to 5 ℃/min.
9. The use of the vinasse biomass hard carbon material of claim 1 as a negative electrode material of a sodium ion battery.
10. A negative electrode material of a sodium ion battery, comprising the vinasse biomass hard carbon material as a negative electrode active material of the sodium ion battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111557569.4A CN116265391A (en) | 2021-12-19 | 2021-12-19 | Vinasse biomass hard carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111557569.4A CN116265391A (en) | 2021-12-19 | 2021-12-19 | Vinasse biomass hard carbon material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116265391A true CN116265391A (en) | 2023-06-20 |
Family
ID=86744001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111557569.4A Pending CN116265391A (en) | 2021-12-19 | 2021-12-19 | Vinasse biomass hard carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116265391A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117735525A (en) * | 2024-02-19 | 2024-03-22 | 山东埃尔派粉体科技股份有限公司 | Biomass hard carbon material, and two-stage carbonization preparation method and application thereof |
| CN117735525B (en) * | 2024-02-19 | 2024-05-14 | 山东埃尔派粉体科技股份有限公司 | Biomass hard carbon material, and two-stage carbonization preparation method and application thereof |
-
2021
- 2021-12-19 CN CN202111557569.4A patent/CN116265391A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117735525A (en) * | 2024-02-19 | 2024-03-22 | 山东埃尔派粉体科技股份有限公司 | Biomass hard carbon material, and two-stage carbonization preparation method and application thereof |
| CN117735525B (en) * | 2024-02-19 | 2024-05-14 | 山东埃尔派粉体科技股份有限公司 | Biomass hard carbon material, and two-stage carbonization preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107275606B (en) | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof | |
| CN102969489B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material | |
| CN113651307A (en) | Sodium ion battery carbon negative electrode material prepared based on waste wood chips and preparation method thereof | |
| CN108059144B (en) | Hard carbon prepared from biomass waste bagasse, and preparation method and application thereof | |
| CN104269555B (en) | A kind of lithium ion power and energy-storage battery soft carbon negative material, preparation method and its usage | |
| CN109461902B (en) | Preparation method and application of iron diselenide/honeycomb carbon composite material | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN115744872B (en) | Asphalt-based soft carbon composite cellulose hard carbon negative electrode material and preparation method thereof | |
| CN108715447A (en) | A kind of camphor tree Quito mesoporous activated carbon and preparation method thereof and the application in electrochemical energy storage | |
| CN114242968A (en) | Carbon-coated sodium iron fluorophosphate material and preparation method and application thereof | |
| CN109768218A (en) | A kind of hard carbon lithium ion battery negative material of N doping and preparation method thereof and anode plate for lithium ionic cell and lithium ion battery | |
| CN112499631A (en) | Fe3C/C composite material and application thereof | |
| CN112125294A (en) | Coal-based silicon-carbon composite negative electrode material and preparation method thereof | |
| CN112174119B (en) | Method for preparing graphene foam from antibiotic fungi residues | |
| CN107445210B (en) | High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1) | |
| CN112811409A (en) | Method for preparing hard carbon negative electrode material and high-specific-capacity lithium ion battery by using salix purpurea as carbon source | |
| CN107959024A (en) | A kind of sodium-ion battery anode sheet Sb2Se3Nanocrystalline preparation method | |
| CN108682832B (en) | Composite negative electrode material for lithium battery and preparation method thereof | |
| CN104701531B (en) | In-situ carbon-coating hexagon K0.7[Fe0.5Mn0.5]O2 nano material as well as preparation method and application thereof | |
| CN106848249A (en) | SiO2The preparation method of@C nucleocapsid complex lithium ion battery cathode materials | |
| CN108155022B (en) | Preparation method of lithium ion capacitor using microcrystalline graphite material | |
| CN115832294A (en) | Method for preparing biomass-based hard carbon composite negative electrode through magnetron sputtering | |
| CN106067548B (en) | A kind of SnO2/ iron tungstate lithium/carbon composite nano-material and preparation method thereof | |
| CN116265391A (en) | Vinasse biomass hard carbon material and preparation method and application thereof | |
| CN110518194B (en) | Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |