CN116081599A - Preparation method and application of hard carbon anode material - Google Patents
Preparation method and application of hard carbon anode material Download PDFInfo
- Publication number
- CN116081599A CN116081599A CN202211700152.3A CN202211700152A CN116081599A CN 116081599 A CN116081599 A CN 116081599A CN 202211700152 A CN202211700152 A CN 202211700152A CN 116081599 A CN116081599 A CN 116081599A
- Authority
- CN
- China
- Prior art keywords
- lignin
- hard carbon
- temperature
- drying
- based hard
- 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
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 54
- 239000010405 anode material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920005610 lignin Polymers 0.000 claims abstract description 87
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005187 foaming Methods 0.000 claims abstract description 10
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- -1 preferably Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000007773 negative electrode material Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002296 pyrolytic carbon Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010866 blackwater Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method and application of a hard carbon anode material, wherein the preparation method of the hard carbon material comprises the following steps: extracting lignin from papermaking black liquor, converting the lignin into lignin-based resin by a certain method, washing, drying and then standby. Mixing lignin-based resin, surfactant and foaming agent, and stirring at high speed with a stirrer. And continuously stirring at 60 ℃, gradually dripping a plasticizer, starting foaming of the system, and drying after the system is basically plasticized to obtain the lignin-based hard carbon foam with hard texture. And (5) placing the sample into a furnace for carbonization to obtain lignin-based hard carbon. And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon material. The lignin-based hard carbon provided by the invention has the advantages of simple preparation process, excellent low-temperature performance, good quick charge performance and good cycle performance when being used as a negative electrode material of a lithium ion battery.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage components, and particularly relates to a preparation method and application of a hard carbon anode material
Technical Field
Along with the development of new energy automobile industry and energy storage field, the lithium ion battery industry has generated higher requirements on the birth of lithium ion batteries, and the traditional graphite negative electrode material has poor charge and discharge performance and slow charge speed in a low-temperature environment, so that related requirements are difficult to meet.
Because of the larger interlayer spacing and the abundant microporous structure of the surface, the hard carbon negative electrode material has more excellent low-temperature performance and excellent quick charge capability than the graphite negative electrode material, and is valued by the industry.
The hard carbon has rich raw material sources including fossil fuels, high polymer materials and biomasses, wherein the biomasses have the advantages of wide sources, various structures, reproducibility, low cost, environmental friendliness and the like, and become an important research direction in the field of lithium ion battery anode materials.
Lignin is the second most abundant organic matter in the world, and lignin produced by industrial production is 1.3-1.5 hundred million tons each year in the world currently, wherein about 5000 ten thousand tons of lignin is produced in papermaking black water only by papermaking each year, and most of lignin is discharged into a natural water system or is burnt after simple treatment due to lack of utilization means, so that the environment is seriously damaged, and resource waste is caused.
The lignin has a complex structure and rich aromatic structure, is a hard carbon precursor material with huge potential, and the lignin sulfonate in CN110797533A is used as a precursor to prepare hard carbon microspheres, and in CN111170298B, alkali lignin or lignin sulfonate is used as a raw material to prepare lignin-based hard carbon, but the lignin-based hard carbon material prepared by the method has overlarge specific surface area (even can reach 100 m) 2 Over/g), first inefficiency (all about 80-85%, and low compaction density (0.7-1.0 g/cm) 2 In range), and the like. The large-scale application of the lignin-based hard carbon material is severely restricted.
Disclosure of Invention
The invention relates to a preparation method and application of a hard carbon anode material, wherein the preparation method of the hard carbon anode material comprises the following steps:
(1) The black liquor is evaporated and concentrated to make its solid content reach about 50%.
(2) Heating the concentrated papermaking black liquor to 50-70 ℃, adding inorganic acid into the papermaking black liquor, adjusting the pH value to a great amount of precipitation, filtering, drying and crushing after the precipitation is finished, thus obtaining the alkali lignin.
(3) Adding lignin and glucose into a reaction kettle provided with a stirrer, adding sulfuric acid solution with a certain concentration, uniformly stirring to uniformly distribute the lignin and the glucose in a water phase, and adjusting the acidity of the solution. Heating the reaction kettle, performing constant temperature treatment for a period of time, filtering and separating to obtain black powdery lignin-based resin, and cleaning and drying for later use.
(4) Mixing lignin-based resin, surfactant and foaming agent, and stirring at high speed with a stirrer. And continuing stirring at a certain temperature, gradually dripping a plasticizer, starting foaming of the system, and drying after the system is basically plasticized to obtain the lignin-based hard carbon foam with hard texture.
(5) And (3) soaking the obtained sample in acetone to remove residual micromolecular impurities in the sample, adding fresh acetone, and drying in an oven to obtain the sample.
(6) And (3) placing the sample into a furnace for calcination, raising the temperature to 400-600 ℃ at a speed of 2 ℃/min, keeping the temperature for 4-8 hours, raising the temperature to 1200-1600 ℃ at a speed of 5 ℃/min, and keeping the temperature for 2-12 hours to obtain the lignin-based hard carbon.
(7) And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon anode material.
According to the invention, the surface layer structure of the lignin-based hard carbon is changed by adding the foaming agent into the lignin-based resin, so that the abundant micropore structure is changed into larger mesopores, the specific surface area of the lignin-based hard carbon is reduced, and meanwhile, the pore volume is not changed greatly, so that the good lithium storage capacity of the lignin-based hard carbon is maintained.
In the step (1), the papermaking black liquor is treated by adopting an indirect evaporation method, and the direct evaporation of the excessive solid content can cause the subsequent treatment difficulty.
In step (2), the mineral acid may be H 2 SO 4 、HCl、HNO 3 One or more of inorganic acids such as HF.
In step (3), the acidity of the solution is required to be ph=0-2.
In the step (3), the heating temperature is 180-230 ℃, and the constant temperature treatment time is 8-16h.
In the step (4), the surfactant is an organic solvent, preferably, the surfactant is polyoxyethylene sorbitan monooleate.
In the step (4), the foaming agent is alkane or fluorocarbon, preferably n-pentane, and the lignin-based resin and the foaming agent are mixed in a ratio of 100:5-10:3.
In the step (6), the material is carbonized in nitrogen atmosphere or/and argon atmosphere to obtain lignin-based hard carbon.
Drawings
The negative electrode material and advantageous effects thereof according to the present invention will be described in detail with reference to the accompanying drawings and detailed description.
FIG. 1 is a flow chart of the preparation of examples 1-4 of the present invention.
FIG. 2 is an electron micrograph of a hard carbon material prepared using the present method
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The black liquor is evaporated and concentrated to make its solid content reach about 50%. Heating the concentrated papermaking black liquor to 50-70 ℃, adding H into the papermaking black liquor 2 SO 4 And adjusting the pH value until a large amount of sediment is generated, filtering, drying and crushing after the sediment is finished, so as to obtain the alkali lignin.
Adding 10:1 alkali lignin and glucose into a reaction kettle provided with a stirrer, adding sulfuric acid solution with a certain concentration, uniformly stirring to uniformly distribute the alkali lignin and the glucose in a water phase, and adjusting the acidity of the solution to PH=0.5. Heating the reaction kettle to 190 ℃, keeping the temperature for 10 hours, filtering and separating to obtain black powdery lignin-based resin, and washing and drying the lignin-based resin for later use.
Mixing lignin-based resin, polyoxyethylene sorbitan monooleate and n-pentane at a ratio of 100:20:5, and stirring at high speed with a stirrer. And continuously stirring at 60 ℃, gradually dripping a plasticizer, starting foaming of the system, and drying after the system is basically plasticized to obtain the lignin-based hard carbon foam with hard texture.
And (3) immersing the obtained sample in acetone for 24 hours to remove residual micromolecular impurities in the sample, adding fresh acetone, and treating in a 60 ℃ oven for 24 hours to obtain the sample.
And (3) placing the sample into a furnace for calcination, raising the temperature to 400 ℃ at a speed of 2 ℃/min, keeping the temperature for 4 hours, raising the temperature to 1200 ℃ at a speed of 5 ℃/min, and keeping the temperature for 6 hours to obtain the lignin-based hard carbon with low specific surface area.
And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon anode material.
Example 2
The black liquor is evaporated and concentrated to make its solid content reach about 50%. Heating the concentrated papermaking black liquor to 50-70 ℃, adding HCl into the papermaking black liquor, adjusting the pH value to generate a large amount of precipitation, filtering, drying and crushing after the precipitation is finished, thus obtaining the alkali lignin.
Adding 100:5 alkali lignin and glucose into a reaction kettle provided with a stirrer, adding sulfuric acid solution with a certain concentration, uniformly stirring to uniformly distribute the alkali lignin and the glucose in a water phase, and adjusting the acidity of the solution to PH=0.5. Heating the reaction kettle to 210 ℃, keeping the temperature for 12 hours, filtering and separating to obtain black powdery lignin-based resin, and cleaning and drying for later use.
Mixing lignin-based resin, polyoxyethylene sorbitan monooleate and n-pentane at a ratio of 10:2:1, and stirring at high speed with a stirrer. And continuously stirring at 60 ℃, gradually dripping a plasticizer, starting foaming of the system, and drying after the system is basically plasticized to obtain the lignin-based hard carbon foam with hard texture.
And (3) immersing the obtained sample in acetone for 24 hours to remove residual micromolecular impurities in the sample, adding fresh acetone, and treating in a 60 ℃ oven for 24 hours to obtain the sample.
And (3) placing the sample into a furnace for calcination, raising the temperature to 600 ℃ at a speed of 2 ℃/min, keeping the temperature for 8 hours, raising the temperature to 1600 ℃ at a speed of 5 ℃/min, and keeping the temperature for 12 hours to obtain the lignin-based hard carbon with low specific surface area.
And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon anode material.
Example 3
The black liquor is evaporated and concentrated to make its solid content reach about 50%. Heating the concentrated papermaking black liquor to 60 ℃, and adding HNO into the papermaking black liquor 3 And adjusting the pH value until a large amount of sediment is generated, filtering, drying and crushing after the sediment is finished, so as to obtain the alkali lignin.
Adding 5:1 alkali lignin and glucose into a reaction kettle provided with a stirrer, adding sulfuric acid solution with a certain concentration, uniformly stirring to uniformly distribute the alkali lignin and the glucose in a water phase, and adjusting the acidity of the solution to PH=0.5. Heating the reaction kettle to 230 ℃, keeping the temperature for 8 hours, filtering and separating to obtain black powdery lignin-based resin, and cleaning and drying for later use.
Mixing lignin-based resin, polyoxyethylene sorbitan monooleate and n-pentane at a ratio of 10:2:2, and stirring at high speed with a stirrer. And continuously stirring at 70 ℃, gradually dripping a plasticizer, starting foaming of the system, and drying after the system is basically plasticized to obtain the lignin-based hard carbon foam with hard texture.
And (3) immersing the obtained sample in acetone for 24 hours to remove residual micromolecular impurities in the sample, adding fresh acetone, and treating in a 60 ℃ oven for 16 hours to obtain the sample.
And (3) placing the sample into a furnace for calcination, raising the temperature to 600 ℃ at a speed of 2 ℃/min, keeping the temperature for 6 hours, raising the temperature to 1500 ℃ at a speed of 5 ℃/min, and keeping the temperature for 10 hours to obtain the lignin-based hard carbon.
And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon anode material.
Example 4
The black liquor is evaporated and concentrated to make its solid content reach about 50%. Heating the concentrated papermaking black liquor to 50 ℃, adding HF into the papermaking black liquor, adjusting the pH value to generate a large amount of precipitates, filtering, drying and crushing after the precipitation is finished, thus obtaining the alkali lignin.
Adding 10:3 alkali lignin and glucose into a reaction kettle provided with a stirrer, adding sulfuric acid solution with a certain concentration, uniformly stirring to uniformly distribute the alkali lignin and the glucose in a water phase, and adjusting the acidity of the solution to PH=0.5. Heating the reaction kettle to 200 ℃, keeping the temperature for 8 hours, filtering and separating to obtain black powdery lignin-based resin, and cleaning and drying for later use.
Mixing lignin-based resin, polyoxyethylene sorbitan monooleate and n-pentane at a ratio of 10:2:3, and stirring at high speed with a stirrer. And continuously stirring at 60 ℃, gradually dripping a plasticizer, starting foaming of the system, and drying after the system is basically plasticized to obtain the lignin-based hard carbon foam with hard texture.
And (3) immersing the obtained sample in acetone for 24 hours to remove residual micromolecular impurities in the sample, adding fresh acetone, and treating in a baking oven at 70 ℃ for 24 hours to obtain the sample.
And (3) placing the sample into a furnace for calcination, raising the temperature to 500 ℃ at a speed of 2 ℃/min, keeping the temperature for 8 hours, raising the temperature to 1400 ℃ at a speed of 5 ℃/min, and keeping the temperature for 8 hours to obtain the lignin-based hard carbon.
And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon anode material.
Comparative example
The papermaking black liquor is evaporated and concentrated to make the solid content reach about 50%. Heating the concentrated papermaking black liquor to 50-70 ℃, adding H into the papermaking black liquor 2 SO 4 And adjusting the pH value until a large amount of sediment is generated, filtering, drying and crushing after the sediment is finished, so as to obtain the alkali lignin.
And (3) immersing the obtained sample in acetone for 24 hours to remove residual micromolecular impurities in the sample, adding fresh acetone, and treating in a 60 ℃ oven for 24 hours to obtain the sample.
And (3) placing the sample into a furnace for calcination, raising the temperature to 400 ℃ at a speed of 2 ℃/min, keeping the temperature for 4 hours, raising the temperature to 1200 ℃ at a speed of 5 ℃/min, and keeping the temperature for 6 hours to obtain the lignin-based hard carbon with low specific surface area.
And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon anode material.
Specifically, compared with the comparative examples, examples 1 to 4 were greatly improved in both of the first charge and discharge efficiency, the low-temperature performance and the fast charge performance, and by changing the surface morphology of the anode material, the specific surface area was reduced, the total surface energy was reduced, the system was more stable, the first coulombic efficiency of the battery was improved, the specific surface area of the pyrolytic carbon after the foaming treatment was first reduced and then increased, the average pore diameter was first increased and then reduced, and when the n-pentane amount was 20%, the specific surface area of the pyrolytic carbon was reduced to 1.52m 2 And/g. The method is mainly characterized in that bubbles volatilized from n-pentane in the foaming process press the surface of a sample, and then the sample structure is compressed through high-temperature heat treatment, so that the specific surface area of pyrolytic carbon is reduced, and the average pore diameter is increased. However, when the amount of n-pentane is too large, the viscosity of the lignin-based resin solution is too high, but the resistance to dispersion of bubbles is increased, and the dispersion is not easy, so that the specific surface area of pyrolytic carbon is increased again. In addition, as micropores spread on the surface of the hard carbon become mesopores after foaming, a channel for lithium ion diffusion is maintained, the extra lithium intercalation capacity corresponding to a disordered structure area is reduced, the discharge capacity of the carbon material is reduced, but only the discharge capacity of a high potential area is reduced; the discharge capacity corresponding to the low potential region of ordered interlayer intercalation of lithium of graphite is instead increased and the voltage hysteresis phenomenon is suppressed.
Table 1 shows the performance comparison of the negative electrode materials of the lithium ion batteries of examples 1-4 and comparative example
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Specific surface area (μm) | 10.83 | 6.32 | 1.52 | 3.94 | 124.43 |
| Capacity (mAh/g) | 382.4 | 380.7 | 413.1 | 403.3 | 420.9 |
| First charge efficiency (%) | 86 | 87 | 89 | 87 | 67 |
| Charging and discharging efficiency at-40 ℃ (%) | 59.3 | 63.6 | 68.9 | 64.2 | 62.8 |
| 10C rate cycle 1000 weeks charge capacity retention (%) | 87 | 86 | 91 | 87 | 80 |
Claims (8)
1. The preparation method and application of the hard carbon anode material are characterized by comprising the following steps:
(1) The black liquor is evaporated and concentrated to make its solid content reach about 50%.
(2) Heating the concentrated papermaking black liquor to 50-70 ℃, adding inorganic acid into the papermaking black liquor, adjusting the pH value to 3-5, precipitating lignin, filtering, drying and crushing after the precipitation is completed, thus obtaining alkali lignin.
(3) Adding lignin and glucose into a reaction kettle provided with a stirrer, adding sulfuric acid solution with a certain concentration, uniformly stirring to uniformly distribute the lignin and the glucose in a water phase, and adjusting the acidity of the solution. Heating the reaction kettle, performing constant temperature treatment for a period of time, filtering and separating to obtain black powdery lignin-based resin, and cleaning and drying for later use.
(4) Mixing lignin-based resin, surfactant and foaming agent, and stirring at high speed with a stirrer. And then heating to 50-70 ℃ and continuously stirring, gradually dripping a plasticizer, starting foaming of the system, and drying after the system is basically plasticized to obtain the lignin-based hard carbon foam with hard texture.
(5) And (3) soaking the obtained sample in acetone for 16-32h to remove residual micromolecular impurities in the sample, adding fresh acetone, and drying in an oven at 50-70 ℃ for 16-32h to obtain the sample.
(6) And (3) placing the sample into a furnace for calcination, raising the temperature to 400-600 ℃ at a speed of 2 ℃/min, keeping the temperature for 4-8 hours, raising the temperature to 1200-1600 ℃ at a speed of 5 ℃/min, and keeping the temperature for 2-12 hours to obtain the lignin-based hard carbon.
(7) And crushing the lignin-based hard carbon to obtain the lignin-based hard carbon anode material.
2. The method according to claim (1), characterized in that: in the step (1), the papermaking black liquor is treated by adopting an indirect evaporation method, and the direct evaporation of the excessive solid content can cause the subsequent treatment difficulty.
3. The method according to claim (1), characterized in that: in step (2), the mineral acid may be H 2 SO 4 、HCl、HNO 3 One or more of inorganic acids such as HF.
4. The method according to claim (1), characterized in that: in step (3), the acidity of the solution is required to be ph=0-2.
5. The method according to claim (1), characterized in that: in the step (3), the heating temperature is 180-230 ℃, and the constant temperature treatment time is 8-16h.
6. The method according to claim (1), characterized in that: in the step (4), the surfactant is an organic solvent, preferably, the surfactant is polyoxyethylene sorbitan monooleate.
7. The method according to claim (1), characterized in that: in the step (4), the foaming agent is alkane or fluorocarbon, preferably n-pentane, and the lignin-based resin and the foaming agent are mixed in a ratio of 100:5-10:3.
8. The method according to claim (1), characterized in that: in the step (6), the material is carbonized in nitrogen atmosphere or/and argon atmosphere to obtain lignin-based hard carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211700152.3A CN116081599A (en) | 2022-12-28 | 2022-12-28 | Preparation method and application of hard carbon anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211700152.3A CN116081599A (en) | 2022-12-28 | 2022-12-28 | Preparation method and application of hard carbon anode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116081599A true CN116081599A (en) | 2023-05-09 |
Family
ID=86186201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211700152.3A Pending CN116081599A (en) | 2022-12-28 | 2022-12-28 | Preparation method and application of hard carbon anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116081599A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116621157A (en) * | 2023-07-20 | 2023-08-22 | 河北科技大学 | Preparation method of hard carbon material, hard carbon material and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6099990A (en) * | 1998-03-26 | 2000-08-08 | Motorola, Inc. | Carbon electrode material for electrochemical cells and method of making same |
| CN103253651A (en) * | 2013-05-23 | 2013-08-21 | 广西大学 | Lignin-based porous carbon material and preparation method thereof |
| CN105061778A (en) * | 2015-08-11 | 2015-11-18 | 湖州长盛化工有限公司 | Preparation technology of lignin resin |
| CN112408359A (en) * | 2020-11-18 | 2021-02-26 | 上海汉禾生物新材料科技有限公司 | Method for preparing battery negative electrode material by using enzymatic hydrolysis lignin-based epoxy resin |
| CN115180611A (en) * | 2022-07-07 | 2022-10-14 | 广东工业大学 | Lignin-based carbon foam and preparation method and application thereof |
| CN115332521A (en) * | 2022-09-21 | 2022-11-11 | 中南大学 | Lignin-based hard carbon composite active material, preparation thereof and application thereof in sodium-ion battery |
-
2022
- 2022-12-28 CN CN202211700152.3A patent/CN116081599A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6099990A (en) * | 1998-03-26 | 2000-08-08 | Motorola, Inc. | Carbon electrode material for electrochemical cells and method of making same |
| CN103253651A (en) * | 2013-05-23 | 2013-08-21 | 广西大学 | Lignin-based porous carbon material and preparation method thereof |
| CN105061778A (en) * | 2015-08-11 | 2015-11-18 | 湖州长盛化工有限公司 | Preparation technology of lignin resin |
| CN112408359A (en) * | 2020-11-18 | 2021-02-26 | 上海汉禾生物新材料科技有限公司 | Method for preparing battery negative electrode material by using enzymatic hydrolysis lignin-based epoxy resin |
| CN115180611A (en) * | 2022-07-07 | 2022-10-14 | 广东工业大学 | Lignin-based carbon foam and preparation method and application thereof |
| CN115332521A (en) * | 2022-09-21 | 2022-11-11 | 中南大学 | Lignin-based hard carbon composite active material, preparation thereof and application thereof in sodium-ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116621157A (en) * | 2023-07-20 | 2023-08-22 | 河北科技大学 | Preparation method of hard carbon material, hard carbon material and application |
| CN116621157B (en) * | 2023-07-20 | 2023-09-29 | 河北科技大学 | Preparation method of hard carbon material, hard carbon material and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020103635A1 (en) | Lignin porous carbon nano sheet, preparation method therefor, and application thereof in super capacitor electrode material | |
| CN112225194B (en) | Hard carbon material and preparation method and application thereof | |
| CN113800496A (en) | Hard carbon material and preparation method and application thereof | |
| CN113735095A (en) | Porous hard carbon material and preparation method and application thereof | |
| WO2015106720A1 (en) | Method for producing super activated charcoal from biomass power plant ash | |
| CN112758911B (en) | Hard carbon material, preparation method and application thereof, and lithium ion battery | |
| CN107140633A (en) | A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived | |
| CN116715239A (en) | Coal-based porous sodium ion battery hard carbon negative electrode material and preparation method thereof | |
| CN116081599A (en) | Preparation method and application of hard carbon anode material | |
| CN116314773A (en) | Pre-oxidized asphalt-based sodium ion battery anode material, preparation method thereof and obtained product | |
| CN116534837A (en) | Mechanical surface modified biomass hard carbon material and preparation method and application thereof | |
| CN109231205B (en) | Sulfonate surfactant modified activated carbon for supercapacitor and preparation method thereof | |
| CN112320784B (en) | Sulfur-doped iron-nitrogen-carbon supercapacitor electrode material and preparation method and application thereof | |
| CN112174119B (en) | Method for preparing graphene foam from antibiotic fungi residues | |
| CN113371709A (en) | Preparation method of rice hull-based high-specific-surface-area biochar material | |
| CN114516627B (en) | Preparation method of soft and hard carbon composite nano material | |
| CN116936800A (en) | Asphalt-based hard carbon negative electrode material and preparation method and application thereof | |
| CN115579470B (en) | Modified asphalt coated microcrystalline graphite negative electrode material and preparation method thereof | |
| CN117003235A (en) | Method for regenerating graphite in waste battery | |
| CN114314556B (en) | Resin-based carbon negative electrode material, preparation method and application thereof, and battery containing resin-based carbon negative electrode material | |
| CN115411244A (en) | Nitrogen-doped porous hard carbon negative electrode material and preparation method and application thereof | |
| CN113955747A (en) | Preparation method of graphene-coated natural graphite negative electrode material | |
| CN114291808A (en) | Graded ordered porous carbon nanosheet material and preparation method and application thereof | |
| CN109546148B (en) | Method for preparing porous irregular spherical biological carbon lithium sulfur battery positive electrode material from chestnut peels | |
| CN111924842A (en) | Lotus stalk-based electrode material and preparation method 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 |