CN117466284B - Surface modified hard carbon negative electrode material of sodium ion battery and preparation method thereof - Google Patents
Surface modified hard carbon negative electrode material of sodium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN117466284B CN117466284B CN202311825147.XA CN202311825147A CN117466284B CN 117466284 B CN117466284 B CN 117466284B CN 202311825147 A CN202311825147 A CN 202311825147A CN 117466284 B CN117466284 B CN 117466284B
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- acid
- sodium ion
- asphalt
- ion battery
- 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.)
- Active
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010426 asphalt Substances 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 45
- 230000004927 fusion Effects 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000002028 Biomass Substances 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 102220043159 rs587780996 Human genes 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a surface modified hard carbon anode material of a sodium ion battery and a preparation method thereof, and relates to the technical field of sodium ion batteries. After biomass hard carbon source is crushed, acid steam is introduced into the carbon source to regulate and control pores, and the biomass hard carbon source is dried after being washed to pH value=6-7; fusing the dried material with asphalt to obtain a fused material; the fusion material is then put under N 2 And (3) carrying out polycondensation reaction on asphalt on the surface of the hard carbon under the protection to realize closed cell modification, and carbonizing the closed cell modified material to obtain the hard carbon negative electrode material of the sodium ion battery. According to the invention, through pore regulation and closed pore modification, the first efficiency, capacity density and cycle performance of the biomass hard carbon anode and the energy storage device are improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a hard carbon negative electrode material for a sodium ion battery and a preparation technology thereof.
Background
In recent years, low-cost sodium ion batteries are rapidly developed and applied in various fields such as energy storage devices, communication base stations and low-speed electric vehicles. As a negative electrode material, the hard carbon has the advantages of low voltage platform, good cycle performance, rich sources and the like, and is greatly focused by researchers and industry. Among the raw material sources of many hard carbons, biomass raw materials have the advantages of stable sources, low price and the like.
However, due to the fact that the surface of the traditional biomass hard carbon material contains a large number of defects and oxygen-containing functional groups, the controllability of internal pores is poor, a large number of holes are formed by heat treatment, and the like, the traditional biomass sodium ion battery hard carbon negative electrode material and the sodium ion battery have a series of problems of gas production, low reversible capacity, low first efficiency and the like, and the large-scale application of the biomass hard carbon and the sodium ion battery is restricted.
Therefore, developing a hard carbon material with high sodium storage performance, high first efficiency and low gas production based on a biomass carbon source has important significance for promoting the industrialization of sodium ion batteries.
Disclosure of Invention
The invention aims to provide a surface modified sodium ion battery hard carbon negative electrode material and a preparation method thereof, and the primary efficiency, capacity density and cycle performance of a biomass hard carbon negative electrode and an energy storage device are improved through pore regulation and closed pore modification.
In order to solve the technical problems, according to one aspect of the present invention, there is provided a method for preparing a surface-modified hard carbon anode material for a sodium ion battery, comprising the steps of:
firstly, crushing a biomass hard carbon source;
wherein, the biomass hard carbon can be selected from coconut shell carbon, bamboo carbon or starch carbon;
step two, preparing acid steam, and introducing the acid steam into the crushed carbon source in the step one to regulate and control pores;
step three, washing the material with the pore regulated in the step two to a pH value of=6-7, and then drying; the pH after washing is preferably 6, 6.2, 6.5, 6.7 or 7.
Step four, fusing the dried material in the step three with asphalt with a softening point of 120-280 ℃ to obtain a fused material; the fusion material is then put under N 2 And carrying out polycondensation reaction on the asphalt on the surface of the hard carbon under the protection to realize closed pore modification.
Higher softening point asphalts, such as 120 asphalt, 150 asphalt, 180 asphalt, 220 asphalt, 250 asphalt, 280 asphalt, have higher condensation degree of polycyclic aromatic hydrocarbon, more ordered structure, and high carbon structure order degree and high capacity formed in carbonization process.
And fifthly, carbonizing the closed-pore modified material to obtain the hard carbon anode material of the sodium ion battery.
Further, in the first step, the particle size of the crushed carbon source ranges from d50=4 to 12um.
Further, in the second step, the acid solution is heated to obtain the acid steam, the mass concentration range of the acid solution is 30-60%, and the temperature of the acid steam is 60-110 ℃.
Further, in the second step, the acid solution is selected from one or a combination of more of nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid.
In the mixed acid, the respective acid solutions may be mixed at any ratio, or may be mixed at a specific ratio so that the overall concentration of the acid solutions can be controlled within a range of 30 to 60%.
In the third step, the material with the pores regulated is washed with water and then dried until the volatile content is less than or equal to 1 percent.
In the fourth step, the dried material and asphalt are fused in a fusion machine, the fusion speed revolution is 500 revolutions per minute, and the fusion time is 4 minutes, so that the fusion material is obtained.
Further, in the fourth step, the softening point of the asphalt is 220 ℃.
Further, in step four, the fusion material is at N 2 Heating to 250 ℃ under protection, and keeping the temperature for 3 hours to enable the asphalt to be subjected to polycondensation on the surface of the hard carbon.
Further, in the fifth step, the carbonization reaction temperature is 1000-1200 ℃.
According to another aspect of the present invention, there is provided a surface-modified sodium ion battery hard carbon anode material obtained by the above preparation method.
The invention adopts one-step acid washing and activation to shorten the preparation process, reduce the preparation cost and improve the preparation yield. The pore depth can be effectively controlled by adopting acid water vapor with different concentrations and types, and simultaneously the ash content of a biomass carbon source is effectively controlled, so that a foundation is laid for obtaining ideal sodium storage capacity. Asphalt is uniformly dispersed on the surface of hard carbon through a fusion machine to perform solid-phase-like reaction, so that the asphalt content of coating polycondensation is reduced, the coating integrity is effectively improved, the thickness of a coating layer is reduced, and the first efficiency of the negative electrode of the sodium ion battery is obviously improved.
According to the preparation method provided by the invention, the capacity of the obtained hard carbon anode reaches 368.5mAh/g at most through pore regulation and surface modification technology, the first efficiency is improved to 91%, and the capacity retention rate of the system rapid charge-discharge cycle of 0.3C charge/0.3C discharge can reach 94% for 50 times.
Drawings
FIG. 1 is a pore distribution diagram of example 20;
FIG. 2 is a graph of the first charge and discharge curve of example 20;
FIG. 3 is a graph showing the charge and discharge rate of 0.3C/charge and discharge rate of 0.1C in example 20;
fig. 4 is a transmission electron microscope image of example 20 and comparative example 2.
Detailed Description
Example 1
The coconut shell charcoal was crushed to a suitable particle size in the range d50=6±0.5um. Acid steam is prepared by heating hydrochloric acid with the mass concentration of 30% to 60 ℃, and the acid steam is introduced into a crushed carbon source to regulate and control pores.
The carbon source after the acid steam treatment was water washed to ph=6.50 and dried to a volatile of less than 1%.
And (3) high-speed fusion of the prepared material and asphalt with the softening point of 220 ℃ in a fusion machine to obtain a fusion material, wherein the amount of the asphalt is controlled to be 0.5% of carbon residue, the fusion speed is 500 revolutions per minute, and the fusion time is 4 minutes. Fusion material at N 2 Heating to 250 ℃ under protection, and keeping the temperature for 3 hours to enable the asphalt to carry out polycondensation reaction on the surface of the hard carbon so as to realize closed pore modification.
Carbonizing the powder coated by the polycondensed asphalt at the carbonization temperature of 1000 ℃ to obtain the hard carbon negative electrode material of the sodium ion battery.
Example 2-example 21 was prepared in the same manner as in example 1, except that the following materials, parameters and reaction conditions were varied: (1) the type, concentration and temperature of acid solution for preparing acid steam, (2) the type of coating and the amount of asphalt for controlling carbon residue value, and (3) carbonization temperature. Table 1 shows the preparation conditions of examples 1 to 21.
Wherein examples 1-4 used a single acid solution to produce acid vapors. Example 5-example 21 acid vapors were prepared using a mixed acid solution, and example 20 is used as an illustration.
Example 20
The coconut shell charcoal was crushed to a suitable particle size in the range d50=6±0.5um. The method comprises the steps of preparing acid steam by heating mixed acid with the mass concentration of 40% (the mass ratio of concentrated nitric acid to concentrated hydrochloric acid to concentrated sulfuric acid is 1:7:2), adding distilled water to adjust to the specified concentration) to 60 ℃, and introducing the acid steam into crushed carbon sources to regulate and control pores.
The carbon source after the acid steam treatment was water washed to ph=6.5 and dried to a volatile of less than 1%.
And (3) high-speed fusion of the prepared material and asphalt with the softening point of 220 ℃ in a fusion machine to obtain a fusion material, wherein the amount of the asphalt is controlled to be 0.5% of carbon residue, the fusion speed is 500 revolutions per minute, and the fusion time is 4 minutes. Fusion material at N 2 Heating to 250 ℃ under protection, and keeping the temperature for 3 hours to enable the asphalt to carry out polycondensation reaction on the surface of the hard carbon so as to realize closed pore modification.
Carbonizing the powder coated by the polycondensed asphalt at the carbonization temperature of 1000 ℃ to obtain the hard carbon negative electrode material of the sodium ion battery.
Comparative example 1
S1, crushing a coconut shell carbon source to a particle size range D50=6+/-0.5 um;
s2, passing the crushed material S1 through hydrochloric acid: nitric acid: sulfuric acid = 1:7:2 (mass ratio) of mixed acid washing;
s3, washing the material prepared in the step S2 with water until the pH value is=6.5, and drying until the volatile component is lower than 1%;
s4, mixing the powder of S3 with N 2 Carbonizing under the protection of the hard carbon anode material, wherein the carbonization temperature range is 1000 ℃, and the hard carbon anode material of the sodium ion battery is prepared.
Comparative example 2
S1, crushing a coconut shell carbon source to a particle size range D50=6+/-0.5 um;
s2, preparing high-temperature high-pressure acid steam by heating mixed acid (the mass ratio is 1:7:2) of hydrochloric acid, nitric acid and sulfuric acid with the concentration of 40 percent and adding distilled water to adjust to the specified concentration) to 60 ℃;
s3, introducing the steam prepared in the step S2 into the crushed carbon source prepared in the step S1 to regulate and control pores;
s4, washing the material prepared in the step S3 with water until the pH value is=6.5, and drying until the volatile component is lower than 1%;
s5, putting the powder prepared in the S3 in N 2 Carbonizing under protection at 1000 ℃ to obtain the hard carbon anode material of the sodium ion battery.
Table 1 main preparation conditions of each of examples and comparative examples
| Numbering device | Acid solution species | Mass ratio of mixed acid | Concentration of acid solution (%) | Acid solution temperature (. Degree. C.) | Coating type | Cladding mode | Carbon residue value (%) | Carbonization temperature (. Degree. C.) |
| Example 1 | Hydrochloric acid | / | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 2 | Nitric acid | / | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 3 | Sulfuric acid | / | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 4 | Hydrofluoric acid | / | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 5 | Nitric acid, hydrochloric acid | 1:1 | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 6 | Hydrochloric acid, sulfuric acid | 1:1 | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 7 | Sulfuric acid, hydrofluoric acid | 1:1 | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 8 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 9 | Hydrochloric acid, sulfuric acid, hydrofluoric acid | 1:7:2 | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 10 | Nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid | 1:7:2 | 30 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 11 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 75 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 12 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 75 | Phenolic resin | Fusion machine | 0.5 | 1000 |
| Example 13 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 75 | 150 asphalt | Fusion machine | 0.5 | 1000 |
| Example 14 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 60 | 75 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 15 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 110 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 16 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 60 | 220 asphalt | Liquid phase concentration | 0.5 | 1000 |
| Example 17 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 60 | 220 asphalt | Solid phase mixing | 0.5 | 1000 |
| Example 18 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 60 | 220 asphalt | Fusion machine | 1.5 | 1000 |
| Example 19 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 60 | 220 asphalt | Fusion machine | 5 | 1000 |
| Example 20 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 60 | 220 asphalt | Fusion machine | 0.5 | 1000 |
| Example 21 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 60 | 220 asphalt | Fusion machine | 0.5 | 1200 |
| Comparative example 1 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | / | / | / | / | / | 1000 |
| Comparative example 2 | Nitric acid, hydrochloric acid and sulfuric acid | 1:7:2 | 40 | 60 | / | / | / | 1000 |
The above-mentioned examples 1 to 21 and comparative examples 1 and 2 were tested for their properties and the results are shown in Table 2.
(1) Sodium ion negative electrode and battery test conditions: taking the materials prepared in the comparative examples and the examples as negative electrode materials, mixing the materials with a conductive agent (Super-P) and a binder sodium carboxymethylcellulose (CMC) according to the mass ratio of 95:2.5:2.5, adding a proper amount of deionized water as a solvent to prepare slurry, coating the slurry on an aluminum foil, and preparing a negative electrode plate through vacuum drying and rolling; adopting a metal sodium sheet as a counter electrode, adopting a 1mol/L NaClO4 bi-component mixed solvent to mix electrolyte according to the ratio of DEC to EC=1:1 (v/v), adopting glass fiber (Whatman GF/D) as a diaphragm, and assembling the CR2032 button cell in a glove box filled with inert gas; the charge and discharge test of the button cell is carried out on a cell test system of blue electric power electronic Co., ltd. In Wuhan, under the condition of normal temperature, 0.05C constant current discharge and 0.1C constant current charge, and the charge and discharge voltage is limited to 0.0-2.0V.
(2) The cycle performance was tested and calculated using the following method:
the cell was charged with 0.1C/discharged with 0.1C, and the discharge capacity was recorded as C 1 Then the charge and discharge cycles are carried out for 50 times by a system of 0.3C charge/0.3C discharge, and the 50 th discharge capacity is marked as C 50 The cycle performance is marked by CL,。
TABLE 2 characterization of physical and electrochemical Properties of the materials of the examples and comparative examples
| Numbering device | Specific surface area (m) 2 /g） | Ash (%) | Aperture (nm) | Pore volume (10) -3 cm 3 /g） | First-time capacity (mAh/g) | First time efficiency (%) | Cycle performance (CL) 50 %） |
| Example 1 | 20.5 | 0.4 | 12.8 | 56 | 344.7 | 90.5 | 73.2 |
| Example 2 | 30.7 | 0.4 | 8.4 | 80 | 348.9 | 89.6 | 69.0 |
| Example 3 | 25.0 | 0.5 | 9.5 | 70 | 330.7 | 89.2 | 68.2 |
| Example 4 | 30.2 | 0.3 | 10.7 | 78 | 345.2 | 88.9 | 71.4 |
| Example 5 | 28.8 | 0.4 | 9.2 | 75 | 347.8 | 90.3 | 84.8 |
| Example 6 | 25.5 | 0.3 | 9.8 | 72 | 339.7 | 90.7 | 89.3 |
| Example 7 | 29.3 | 0.2 | 9.0 | 77 | 345.9 | 92.1 | 88.6 |
| Example 8 | 40.9 | 0.2 | 8.4 | 95 | 352.9 | 90.8 | 78.4 |
| Example 9 | 30.5 | 0.2 | 9.5 | 85 | 350.8 | 93.4 | 82.4 |
| Example 10 | 42.8 | 0.1 | 8.0 | 100 | 362.4 | 91.0 | 87.5 |
| Example 11 | 43.1 | 0.1 | 8.5 | 98 | 362.3 | 90.5 | 89.7 |
| Example 12 | 41.8 | 0.1 | 8.2 | 94 | 348.9 | 90.8 | 93.2 |
| Example 13 | 38.8 | 0.2 | 8.6 | 95 | 355.2 | 88.7 | 90.4 |
| Example 14 | 45.9 | 0.1 | 8.7 | 102 | 360.8 | 91.0 | 86.3 |
| Example 15 | 42.8 | 0.2 | 7.8 | 98 | 367.8 | 91.1 | 78.2 |
| Example 16 | 40.0 | 0.1 | 8.2 | 95 | 365.8 | 91.7 | 90.4 |
| Example 17 | 34.8 | 0.1 | 9.0 | 87 | 360.2 | 89.2 | 67.8 |
| Example 18 | 32.0 | 0.1 | 8.0 | 80 | 362.3 | 91.3 | 92.7 |
| Example 19 | 21.8 | 0.2 | 9.5 | 55 | 360.8 | 91.7 | 94.3 |
| Example 20 | 42.7 | 0.1 | 8.6 | 96 | 368.5 | 91.2 | 93.2 |
| Example 21 | 33.4 | 0.1 | 8.4 | 86 | 330.5 | 88.7 | 90.1 |
| Comparative example 1 | 238.4 | 0.5 | 15.6 | 750 | 318.4 | 86.0 | 53.3 |
| Comparative example 2 | 197.2 | 0.2 | 10.8 | 600 | 320.7 | 87.4 | 90.2 |
By comparing example 20 with examples 1-10, the mixed acid employed in example 20 can reduce ash more than other single or mixed acid schemes can under the premise of controlling the type of acid used as much as possible, and higher capacity is obtained; by comparing example 20 with examples 8, 14, the concentration of the mixed acid can control ash at lower concentration, thereby increasing capacity; by comparing example 20 with examples 11 and 15, the desired ash and porosity control effect can be achieved by controlling the temperature of the acid vapor to 60 ℃; comparison of example 20 with examples 11 and 12 shows that the first efficiency is higher with bitumen having a softening point of 220 ℃ than with other bitumen or resins; comparison of example 20 with examples 16 and 17 shows that the processing by the fusion method has higher capacity and first efficiency than the liquid phase mixing or solid phase mixing method; comparison of example 20 with examples 18 and 19 shows that carbon residue value controlled at 0.5% has higher capacity; comparison of example 20 and example 21 shows that higher capacity and initial effect can be achieved by controlling the carbonization temperature to 1000 ℃ than 1200 ℃; the activated carbon negative electrode prepared according to the optimized scheme in example 20 has higher capacity, initial efficiency, cycle and other comprehensive properties. Comparison of the examples with the comparative examples shows that the surface coating has a higher capacity and first efficiency than the uncoated version.
Claims (6)
1. The preparation method of the surface modified sodium ion battery hard carbon anode material is characterized by comprising the following steps of:
firstly, crushing a biomass hard carbon source;
step two, preparing acid steam, and introducing the acid steam into the crushed carbon source in the step one to regulate and control pores; heating an acid solution to obtain the acid steam, wherein the mass concentration range of the acid solution is 30-60%, and the temperature of the acid steam is 60-110 ℃; the acid solution is selected from one or a combination of more of nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid;
step three, the material with the pores regulated in the step two is washed with water until the pH value is=6-7, and then dried until the volatile matter is less than or equal to 1%;
step four, fusing the dried material in the step three with asphalt with a softening point of 120-280 ℃ to obtain a fused material; the fusion material is then put under N 2 Carrying out polycondensation reaction on the asphalt on the surface of hard carbon under the protection to realize closed pore modification;
and fifthly, carbonizing the closed-pore modified material to obtain the hard carbon negative electrode material of the sodium ion battery, wherein the carbonization reaction temperature is 1000-1200 ℃.
2. The method for preparing the surface modified sodium ion battery hard carbon negative electrode material according to claim 1, wherein the method comprises the following steps: in the first step, the particle size range of the crushed carbon source is d50=4-12 um.
3. The method for preparing the surface modified sodium ion battery hard carbon negative electrode material according to claim 1 or 2, wherein the method comprises the following steps: in the fourth step, the dried material and asphalt are fused in a fusion machine, the fusion speed revolution is 500 revolutions per minute, and the fusion time is 4 minutes, so that the fusion material is obtained.
4. The method for preparing a surface-modified sodium ion battery hard carbon negative electrode material according to claim 3, wherein the method comprises the following steps: in the fourth step, the softening point of the asphalt is 220 ℃.
5. The surface-modified sodium ion battery hard carbon negative electrode material of claim 4The preparation method is characterized in that: in step four, the fusion material is in N 2 Heating to 250 ℃ under protection, and keeping the temperature for 3 hours to enable the asphalt to be subjected to polycondensation on the surface of the hard carbon.
6. The surface-modified sodium ion battery hard carbon anode material obtained by the preparation method of any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311825147.XA CN117466284B (en) | 2023-12-28 | 2023-12-28 | Surface modified hard carbon negative electrode material of sodium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311825147.XA CN117466284B (en) | 2023-12-28 | 2023-12-28 | Surface modified hard carbon negative electrode material of sodium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117466284A CN117466284A (en) | 2024-01-30 |
| CN117466284B true CN117466284B (en) | 2024-03-15 |
Family
ID=89624207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311825147.XA Active CN117466284B (en) | 2023-12-28 | 2023-12-28 | Surface modified hard carbon negative electrode material of sodium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117466284B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367517A (en) * | 2008-09-24 | 2009-02-18 | 青岛恒胜石墨有限公司 | Method for preparing high pure graphite with steam heating |
| CN107500263A (en) * | 2017-08-03 | 2017-12-22 | 南京师范大学 | A kind of rice husk derives preparation method and its resulting materials and the application of hard carbon |
| CN113363448A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Soft carbon composite graphite negative electrode material and preparation method thereof |
| CN114477130A (en) * | 2021-12-31 | 2022-05-13 | 深圳市翔丰华科技股份有限公司 | Method for preparing hard carbon negative electrode material for sodium ion battery by adopting porous material |
| CN114516627A (en) * | 2021-12-24 | 2022-05-20 | 宁波中车新能源科技有限公司 | Preparation method of soft and hard carbon composite nano material |
| CN115626630A (en) * | 2022-11-08 | 2023-01-20 | 湘潭大学 | Biomass carbon negative electrode material for sodium ion battery and preparation method and application thereof |
| CN115911320A (en) * | 2022-11-22 | 2023-04-04 | 中国科学院深圳先进技术研究院 | Composite hard carbon material and preparation method and application thereof |
| CN116332152A (en) * | 2023-01-20 | 2023-06-27 | 桂林电子科技大学 | Bagasse hard carbon-based anode material with sodium ion battery core-shell structure and preparation method thereof |
| CN117080401A (en) * | 2023-09-11 | 2023-11-17 | 晖阳(贵州)新能源材料有限公司 | Antimony alloy doped hard carbon composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI751485B (en) * | 2020-02-04 | 2022-01-01 | 台灣中油股份有限公司 | Method of manufacturing biomass hard carbon for negative electrode of sodium-ion batteries and sodium-ion batteries containing biomass hard carbon thereof |
| WO2023018546A1 (en) * | 2021-08-09 | 2023-02-16 | Phillips 66 Company | Methods for preparing hard carbon by acid oxidation |
-
2023
- 2023-12-28 CN CN202311825147.XA patent/CN117466284B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367517A (en) * | 2008-09-24 | 2009-02-18 | 青岛恒胜石墨有限公司 | Method for preparing high pure graphite with steam heating |
| CN107500263A (en) * | 2017-08-03 | 2017-12-22 | 南京师范大学 | A kind of rice husk derives preparation method and its resulting materials and the application of hard carbon |
| CN113363448A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Soft carbon composite graphite negative electrode material and preparation method thereof |
| CN114516627A (en) * | 2021-12-24 | 2022-05-20 | 宁波中车新能源科技有限公司 | Preparation method of soft and hard carbon composite nano material |
| CN114477130A (en) * | 2021-12-31 | 2022-05-13 | 深圳市翔丰华科技股份有限公司 | Method for preparing hard carbon negative electrode material for sodium ion battery by adopting porous material |
| CN115626630A (en) * | 2022-11-08 | 2023-01-20 | 湘潭大学 | Biomass carbon negative electrode material for sodium ion battery and preparation method and application thereof |
| CN115911320A (en) * | 2022-11-22 | 2023-04-04 | 中国科学院深圳先进技术研究院 | Composite hard carbon material and preparation method and application thereof |
| CN116332152A (en) * | 2023-01-20 | 2023-06-27 | 桂林电子科技大学 | Bagasse hard carbon-based anode material with sodium ion battery core-shell structure and preparation method thereof |
| CN117080401A (en) * | 2023-09-11 | 2023-11-17 | 晖阳(贵州)新能源材料有限公司 | Antimony alloy doped hard carbon composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117466284A (en) | 2024-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109599546B (en) | Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same | |
| JP5509458B2 (en) | Negative electrode material and manufacturing method thereof | |
| EP3790082A1 (en) | Preparation method for long-cycle modified graphite-based composite material and lithium ion battery comprising material | |
| CN108598414B (en) | Amorphous zinc oxide/carbon composite lithium ion battery cathode material and preparation method thereof | |
| CN101162775A (en) | High performance lithium ionic cell cathode material and method for producing the same | |
| CN108063233A (en) | A kind of silicon-carbon cathode material and preparation method thereof | |
| CN112289986B (en) | Preparation method of high-rate quick-charging graphite negative electrode material | |
| CN106450424A (en) | Polymer composite solid electrolyte and preparation method and application thereof | |
| CN111785915B (en) | Low-crystallization-degree coating material and preparation method thereof, negative electrode material and lithium battery negative electrode | |
| Chen et al. | Robust Biomass‐Derived Carbon Frameworks as High‐Performance Anodes in Potassium‐Ion Batteries | |
| CN114852991A (en) | Hard carbon and soft carbon co-modified artificial graphite anode material and preparation method thereof | |
| CN116553524B (en) | Hard carbon negative electrode material of sodium ion battery, and preparation process and application thereof | |
| CN110504450B (en) | Preparation method of heteroatom-doped hierarchical pore carbon material and application of heteroatom-doped hierarchical pore carbon material in lithium battery negative electrode slurry | |
| CN117466284B (en) | Surface modified hard carbon negative electrode material of sodium ion battery and preparation method thereof | |
| CN116154159A (en) | Artificial graphite negative electrode material and preparation method thereof | |
| CN114394592B (en) | Method for modulating sludge-based hierarchical porous phosphorus-containing carbon by microwaves for super capacitor | |
| CN114314556B (en) | Resin-based carbon negative electrode material, preparation method and application thereof, and battery containing resin-based carbon negative electrode material | |
| CN112599754B (en) | Polymer modified composite positive electrode for lithium-sulfur battery and preparation method thereof | |
| CN112366305A (en) | Method for preparing graphite cathode of lithium ion battery | |
| CN109360959B (en) | Carbon selenium material, preparation method thereof and application thereof in energy storage device | |
| CN112510199A (en) | Nitrogen-doped carbon multi-layer coated graphite negative electrode material and preparation method thereof | |
| CN116477615B (en) | High-magnification graphite negative electrode material and preparation method thereof | |
| CN116283363B (en) | High-energy-density quick-charging graphite composite material, preparation method and application | |
| CN114899394B (en) | Modified lithium iron manganese phosphate positive electrode material and preparation method and application thereof | |
| CN117416946A (en) | Resinated lignin-based hard carbon negative electrode material, and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |