CN117334886B - Preparation method and application of polyaniline in-situ coated hard carbon material - Google Patents
Preparation method and application of polyaniline in-situ coated hard carbon material Download PDFInfo
- Publication number
- CN117334886B CN117334886B CN202311627940.9A CN202311627940A CN117334886B CN 117334886 B CN117334886 B CN 117334886B CN 202311627940 A CN202311627940 A CN 202311627940A CN 117334886 B CN117334886 B CN 117334886B
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- polyaniline
- carbon material
- negative electrode
- situ coated
- 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 125
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 79
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 72
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 241000353135 Psenopsis anomala Species 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000001768 carboxy methyl cellulose Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 239000011267 electrode slurry Substances 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 159000000000 sodium salts Chemical class 0.000 description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- 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 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 244000241235 Citrullus lanatus Species 0.000 description 1
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000408747 Lepomis gibbosus Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000020236 pumpkin seed Nutrition 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method and application of polyaniline in-situ coated hard carbon material. The invention utilizes the micropore structure of the shell biomass material, and prepares the hard carbon material which is highly disordered and rich in micropores by controlling the carbonization temperature and carbonization time; meanwhile, by controlling the addition amount of aniline, a polyaniline protective layer which is uniform, compact and suitable in thickness is formed on the surface of the hard carbon material, so that the prepared composite material is good in electrochemical performance and cycle stability.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a preparation method and application of a polyaniline in-situ coated hard carbon material.
Background
Lithium ion batteries are considered to be one of the most promising technologies for electrochemical energy storage. However, the limited lithium resources on earth cannot meet the requirement of continuous development of lithium ion batteries, so that finding new alternative energy technologies is particularly important. Sodium ion batteries are widely studied in the energy storage field because of the abundance of sodium resources in nature and the electrochemical properties of sodium ion batteries similar to those of lithium ion batteries. In recent years, research on the application of hard carbon materials as negative electrode materials in sodium ion batteries has been increasing, and the hard carbon materials are considered as negative electrode materials of sodium ion batteries most likely to realize commercialization.
The complex structure and chemistry of hard carbon materials makes their interfacial properties elusive, which largely determines the thermodynamics and kinetics of hard carbon redox reactions. Because the hard carbon material easily forms an unstable solid electrolyte interface in the charge and discharge process, the thermodynamics and dynamics of the interface are affected, and poor circulation stability is shown. Therefore, it is needed to find a method for forming a protective layer on the surface of the hard carbon material in advance, so as to alleviate the generation of a solid electrolyte interface, reduce the damage of the electrolyte to the hard carbon interface, and simultaneously improve the electrochemical performance of the hard carbon material as much as possible.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to a preparation method of polyaniline in-situ coated hard carbon material, which is used to solve the problem that in the prior art, the hard carbon material easily forms an unstable solid electrolyte interface during charging and discharging, so as to reduce the cycle life of a sodium ion battery; meanwhile, the invention also provides a polyaniline in-situ coated hard carbon composite material; in addition, the invention also provides application of the polyaniline in-situ coated hard carbon composite material.
To achieve the above and other related objects, the present invention provides the following technical solutions:
in a first aspect of the present invention, a preparation method of polyaniline in-situ coated hard carbon material is provided, comprising the following steps:
s1, taking shell biomass materials as raw materials, crushing the raw materials, and carbonizing the crushed raw materials under the protection of inert gas to obtain hard carbon materials;
s2, uniformly dispersing the hard carbon material obtained in the step S1 in deionized water to obtain a first dispersion liquid;
s3, adding aniline in the stirring process of the first dispersion liquid, adding an acidic solution to adjust the pH value, and stirring for a certain time to obtain a second dispersion liquid;
s4, transferring the second dispersion liquid into a reaction kettle for hydrothermal reaction to obtain a hydrothermal product;
and S5, washing the hydrothermal product obtained in the step S4, and then carrying out vacuum drying to obtain the polyaniline in-situ coated hard carbon composite material.
In an embodiment of the present invention, in step S1, the shell biomass material includes a melon seed shell, and the melon seed shell includes at least one of sunflower seed, watermelon seed, pumpkin seed, and melon seed. The invention selects the melon seed shells with abundant raw materials and environmental protection as the raw materials, has low cost and low energy consumption, and the obtained hard carbon material has high cost performance.
The prepared hard carbon material has the characteristics of high disorder and rich micropores, and small specific surface area, and can store more sodium ions when being used as a negative electrode material of a sodium ion battery, so that the energy density of the battery can be greatly improved. Preferably, the carbonization temperature is 1200-1400 ℃, and the carbonization time is 3-5 h. In step S1, the inert gas includes nitrogen, argon or a mixture of nitrogen and argon.
The first dispersion liquid in the step S2 is a dispersion water solution of hard carbon, and aniline is firstly added into the first dispersion liquid in the step S3 to enable the aniline to cover the hard carbon; then adding an acid solution, wherein the aniline monomer can realize polymerization reaction of head-tail coupling (coupling between N atoms and C-4 carbon atoms on an aromatic ring) in an acid solution medium; and the hydrothermal reaction of S4 improves the reaction efficiency, reduces or can realize the in-situ coating of polyaniline without introducing a catalyst, and effectively saves the cost. In particular, due to the characteristic that the hard carbon material is rich in micropores, polyaniline not only can form a uniform and compact protective layer on the surface of the hard carbon, but also can permeate into the micropores of the hard carbon, so that the combination of the polyaniline and a hard carbon matrix is tighter and firmer, the cycling stability of the composite material is better, and the electrochemical activity of the composite material is improved. Meanwhile, compared with a structure without micropores, the structure rich in micropores can increase the area of the polyaniline protective layer, store more sodium ions and greatly improve the energy density of the battery.
In one embodiment of the present invention, in step S3, aniline is added during the stirring of the first dispersion, and then an acidic solution is added to adjust the pH to 3-4. In the polymerization process of aniline, when the acid degree of the solution is too low, aniline can be polymerized in a head-tail mode and a head-head mode, so that a large amount of azo byproducts are obtained; when the acidity of the solution is too high, substitution reaction on the aromatic ring occurs again, so that the conductivity of polyaniline is reduced. Preferably, the hydrochloric acid solution is added in step S3 and the pH is adjusted to 3. In hydrochloric acid solution with proper concentration, aniline monomer is easy to generate polymerization reaction in the stirring process, and the reaction formula is as follows:
the concentration of the hydrochloric acid solution is 2-3 mol/L, and the stirring time is 1-2 h. More preferably, the concentration of the hydrochloric acid solution is 2mol/L. According to the invention, the pH value of the second dispersion liquid is adjusted to 3-4, and then the hydrothermal reaction is carried out, so that aniline is polymerized under a proper acidic condition, the reaction energy is controlled through the hydrothermal reaction, the reaction efficiency is improved, a catalyst is not required to be added, the cost is lower, and the large-scale industrial production is easy to realize.
In one embodiment of the present invention, the mass ratio of aniline added in step S3 to hard carbon material added in step S2 is 0.01-0.1:2; preferably 0.05:2. When the addition amount of aniline is small, the polyaniline layer formed on the surface of the hard carbon is thin, and the polyaniline layer is combined with the hard carbon, is not firm and stable, and is easy to damage in the long-term charge and discharge process. When the addition amount of the aniline is large, a thick polyaniline layer is formed, so that each performance of the composite material is biased towards polyaniline, and the circulation stability of the composite material is poor. Therefore, the invention promotes good combination between polyaniline and hard carbon matrix by controlling the mass ratio of aniline to hard carbon material, and forms a uniform and compact protective layer with moderate thickness, so that the composite material is suitable for storing sufficient sodium ions on one hand and ensures the structural stability in the circulation process on the other hand. Preferably, the aniline addition amount is 10-100 μl, more preferably, the aniline addition amount is 50 μl.
In one embodiment of the present invention, in the step S4, the temperature of the hydrothermal reaction is 80-120 ℃, and the time of the hydrothermal reaction is 24-36 hours. The invention can improve the efficiency of the polymerization reaction to the greatest extent by controlling the temperature and time of the hydrothermal reaction.
In one embodiment of the present invention, in step S5, the hydrothermal product is washed with deionized water and absolute ethanol, and then transferred to a vacuum oven for drying at a drying temperature of 60-100 ℃ for 12-24 hours.
In a second aspect of the present invention, a polyaniline in-situ coated hard carbon composite material is provided, which is prepared by the preparation method of the polyaniline in-situ coated hard carbon material.
In a third aspect of the present invention, there is provided a negative electrode sheet, wherein the negative electrode sheet adopts a polyaniline in-situ coated hard carbon composite material as a negative electrode active material, and the negative electrode sheet is prepared by the following steps:
t1, mixing a polyaniline in-situ coated hard carbon material, a conductive agent and a binder in proportion to prepare negative electrode slurry;
and T2, coating the negative electrode slurry on a current collector, and drying to obtain the negative electrode plate.
In one embodiment of the present invention, in the step T1, the mass ratio of the hard carbon material, the conductive agent and the binder is (7-8): (2-1): 1. Preferably, the mass ratio of the hard carbon material, the conductive agent and the binder is 7:2:1 or 8:1:1.
In an embodiment of the present invention, in step T1, the conductive agent includes conductive carbon black. The binder comprises any one of sodium carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF) and sodium alginate; sodium carboxymethylcellulose (CMC) is preferred. Wherein the solvent used for polyvinylidene fluoride (PVDF) is N-methyl pyrrolidone (NMP); the solvents used for sodium carboxymethylcellulose (CMC) and sodium alginate are water.
In an embodiment of the present invention, in step T2, the current collector is copper foil or aluminum foil; preferably aluminum foil.
In an embodiment of the present invention, in the step T2, the drying temperature is 80 to 120 ℃ and the drying time is 12 to 24 hours.
According to a fourth aspect of the invention, a sodium ion battery is provided, which comprises a negative electrode, a positive electrode, a diaphragm and electrolyte, wherein the negative electrode adopts the negative electrode plate.
In one embodiment of the invention, the electrolyte comprises a sodium salt and a nonaqueous solvent. Wherein the sodium salt is NaClO 4 、NaPF 6 Any one of them; the nonaqueous solvent is any one or combination of Ethylene Carbonate (EC), diethyl carbonate (DEC), propylene Carbonate (PC) and dimethyl carbonate (DMC). In the electrolyte, the concentration of the sodium salt is 0.8-1.5 mol/L.
Preferably, when the sodium salt is NaClO 4 When the solvent is a mixture of EC and DEC with the volume ratio of 1:1, or PC is selected as the nonaqueous solvent; when the sodium salt is NaPF 6 When the nonaqueous solvent is selected from the mixture of EC, DMC and DEC with the volume ratio of 1:1:1, or the nonaqueous solvent is selected from the mixture of EC and PC with the volume ratio of 1:1.
As described above, the preparation method and application of the polyaniline in-situ coated hard carbon material have the following beneficial effects:
1. the invention selects the melon seed shells which are rich in resources, wide in sources and environment-friendly as the raw materials of the hard carbon, has low cost and less energy consumption, and the prepared hard carbon material has the characteristics of high disorder and rich micropores by controlling the carbonization temperature and the carbonization time due to the developed micropore structure of the melon seed shells, and has small specific surface area, and when the melon seed shells are used as the negative electrode material of the sodium ion battery, more sodium ions can be stored, so that the energy density of the battery can be greatly improved.
2. Because the hard carbon material is rich in micropores, polyaniline not only can form a uniform and compact protective layer on the surface of the hard carbon, but also can permeate into micropores of the hard carbon, so that the combination of the polyaniline and a hard carbon matrix is tighter and firmer, the cycling stability of the composite material is better, and the electrochemical activity of the composite material is improved.
3. According to the invention, by controlling the mass ratio of the polyaniline to the hard carbon material, good combination of the polyaniline and the hard carbon material is promoted, and a polyaniline protective layer which is uniform and compact and has proper thickness is formed on the surface of the hard carbon material, so that the composite material is suitable for storing sufficient sodium ions on one hand, and the structural stability in the circulation process is ensured on the other hand.
4. According to the invention, by adjusting the acid and alkali and the water heat energy, under the condition of no need of adding a catalyst, aniline is polymerized in situ on the surface of the hard carbon material to form a uniform and compact protective layer, and the composite material has good conductivity and interface stability.
5. The preparation method has simple operation and short process flow, and is suitable for large-scale industrial production; the prepared composite material has stable protective layer and good conductivity, and can ensure the integrity of an electrode when being applied to a sodium ion battery, and ensure good cycling stability and electrochemical performance of the battery.
Drawings
Fig. 1 is an SEM image of the hard carbon material prepared in inventive example 2.
Fig. 2 is a SEM image of the polyaniline in-situ coated hard carbon composite material prepared in example 2 of the present invention.
FIG. 3 is a SEM image of a polyaniline in-situ coated hard carbon composite material prepared in example 2 of the present invention.
Fig. 4 is a TEM image of the hard carbon material prepared in example 2 of the present invention.
Fig. 5 is a TEM image of the polyaniline in-situ coated hard carbon composite material prepared in example 2 of the present invention.
Fig. 6 is a cycle performance chart of the sodium ion battery prepared in example 2 of the present invention.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
Example 1
A preparation method of polyaniline in-situ coated hard carbon material comprises the following steps:
s1, crushing melon seed shells in a crusher, then moving the crushed melon seed shells into a tube furnace, and heating the melon seed shells to 1200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen gas, and carrying out heat preservation and calcination for 4 hours to obtain a hard carbon material;
s2, transferring 2g of the hard carbon material obtained in the step S1 to a beaker, adding 100mL of deionized water, and stirring and dispersing to obtain a first dispersion liquid;
s3, adding 50 mu L of aniline into the first dispersion liquid in the step S2, and uniformly stirring; adding the mixture into a hydrochloric acid solution with the concentration of 2mol/L, regulating the pH to 3, and stirring for 1h to obtain a second dispersion liquid;
s4, loading the second dispersion liquid obtained in the step S3 into a reaction kettle, then placing the reaction kettle into an oven, and preserving the temperature at 80 ℃ for 24 hours to obtain suspension liquid of polyaniline in-situ coated hard carbon, namely a hydrothermal product;
s5, centrifuging the suspension of the polyaniline in-situ coated hard carbon obtained in the step S4, washing off excessive impurities by using deionized water and absolute ethyl alcohol, and then placing the suspension in a vacuum oven for drying at 80 ℃ for 24 hours to obtain the polyaniline in-situ coated hard carbon composite material.
And uniformly mixing the prepared polyaniline in-situ coated hard carbon composite material serving as a negative electrode active substance with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, adding a water solvent to prepare negative electrode slurry, coating the negative electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at 100 ℃ for 12 hours, and rolling and blanking to obtain the negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO 4 The concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Tested, the initial coulombic efficiency was 84.2% at 27℃and a current density of 30 mA/g; the cell was capable of cycling 500 cycles at a current density of 300 mA/g.
Example 2
A preparation method of polyaniline in-situ coated hard carbon material comprises the following steps:
s1, crushing melon seed shells in a crusher, then moving the crushed melon seed shells into a tube furnace, and heating the melon seed shells to 1300 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen gas, and carrying out heat preservation and calcination for 4 hours to obtain a hard carbon material;
s2, transferring 2g of the hard carbon material obtained in the step S1 to a beaker, adding 100mL of deionized water, and stirring and dispersing to obtain a first dispersion liquid;
s3, adding 50 mu L of aniline into the first dispersion liquid in the step S2, and uniformly stirring; adding the mixture into a hydrochloric acid solution with the concentration of 2mol/L, adjusting the pH to 3, and stirring for 1h to obtain a second dispersion;
s4, loading the second dispersion liquid obtained in the step S3 into a reaction kettle, then placing the reaction kettle into a baking oven, and preserving heat at 100 ℃ for 24 hours to obtain suspension liquid of polyaniline in-situ coated hard carbon, namely a hydrothermal product;
s5, centrifuging the suspension of the polyaniline in-situ coated hard carbon obtained in the step S4, washing off excessive impurities by using deionized water and absolute ethyl alcohol, and then placing the suspension in a vacuum oven for drying at 80 ℃ for 24 hours to obtain the polyaniline in-situ coated hard carbon composite material.
And uniformly mixing the prepared polyaniline in-situ coated hard carbon composite material serving as a negative electrode active substance with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, adding an aqueous solvent to prepare a negative electrode slurry, coating the negative electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at 100 ℃ for 12 hours, and rolling and blanking to obtain the negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO 4 The concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Tested, the initial coulombic efficiency was 91.6% at 27℃and a current density of 30 mA/g; the battery was able to cycle 1000 cycles at a current density of 300 mA/g.
Example 3
A preparation method of polyaniline in-situ coated hard carbon material comprises the following steps:
s1, crushing melon seed shells in a crusher, then moving the crushed melon seed shells into a tube furnace, and heating the melon seed shells to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and carrying out heat preservation and calcination for 4 hours to obtain a hard carbon material;
s2, transferring 2g of the hard carbon material obtained in the step S1 to a beaker, adding 100mL of deionized water, and stirring and dispersing to obtain a first dispersion liquid;
s3, adding 50 mu L of aniline into the first dispersion liquid in the step S2, and uniformly stirring; adding the mixture into a hydrochloric acid solution with the concentration of 2mol/L, adjusting the pH to 3, and stirring for 1h to obtain a second dispersion;
s4, loading the second dispersion liquid obtained in the step S3 into a reaction kettle, then placing the reaction kettle into an oven, and preserving heat at 120 ℃ for 24 hours to obtain suspension liquid of polyaniline in-situ coated hard carbon, namely a hydrothermal product;
s5, centrifuging the suspension of the polyaniline in-situ coated hard carbon obtained in the step S4, washing off excessive impurities by using deionized water and absolute ethyl alcohol, and then placing the suspension in a vacuum oven for drying at 80 ℃ for 24 hours to obtain the polyaniline in-situ coated hard carbon composite material.
And uniformly mixing the prepared polyaniline in-situ coated hard carbon composite material serving as a negative electrode active substance with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, adding an aqueous solvent to prepare a negative electrode slurry, coating the negative electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at 100 ℃ for 12 hours, and rolling and blanking to obtain the negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO 4 The concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Tested, the initial coulombic efficiency was 82.5% at 27℃and a current density of 30 mA/g; the cell was capable of cycling 300 cycles at a current density of 300 mA/g.
Example 4
A preparation method of polyaniline in-situ coated hard carbon material comprises the following steps:
s1, crushing melon seed shells in a crusher, then moving the crushed melon seed shells into a tube furnace, and heating the melon seed shells to 1300 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen gas, and carrying out heat preservation and calcination for 4 hours to obtain a hard carbon material;
s2, transferring 2g of the hard carbon material obtained in the step S1 to a beaker, adding 100mL of deionized water, and stirring and dispersing to obtain a first dispersion liquid;
s3, adding 10 mu L of aniline into the first dispersion liquid in the step S2, and uniformly stirring; adding the mixture into a hydrochloric acid solution with the concentration of 2mol/L, adjusting the pH to 3, and stirring for 1h to obtain a second dispersion;
s4, loading the second dispersion liquid obtained in the step S3 into a reaction kettle, then placing the reaction kettle into a baking oven, and preserving heat at 100 ℃ for 24 hours to obtain suspension liquid of polyaniline in-situ coated hard carbon, namely a hydrothermal product;
s5, centrifuging the suspension of the polyaniline in-situ coated hard carbon obtained in the step S4, washing off excessive impurities by using deionized water and absolute ethyl alcohol, and then placing the suspension in a vacuum oven for drying at 80 ℃ for 24 hours to obtain the polyaniline in-situ coated hard carbon composite material.
And uniformly mixing the prepared polyaniline in-situ coated hard carbon composite material serving as a negative electrode active substance with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, adding an aqueous solvent to prepare a negative electrode slurry, coating the negative electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at 100 ℃ for 12 hours, and rolling and blanking to obtain the negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO 4 The concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Tested, the initial coulombic efficiency was 79.8% at 27℃and a current density of 30 mA/g; the cell was capable of cycling 100 cycles at a current density of 300 mA/g.
Example 5
A preparation method of polyaniline in-situ coated hard carbon material comprises the following steps:
s1, crushing melon seed shells in a crusher, then moving the crushed melon seed shells into a tube furnace, and heating the melon seed shells to 1300 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen gas, and carrying out heat preservation and calcination for 4 hours to obtain a hard carbon material;
s2, transferring 2g of the hard carbon material obtained in the step S1 to a beaker, adding 100mL of deionized water, and stirring and dispersing to obtain a first dispersion liquid;
s3, adding 100 mu L of aniline into the first dispersion liquid in the step S2, and uniformly stirring; adding the mixture into a hydrochloric acid solution with the concentration of 2mol/L, adjusting the pH to 3, and stirring for 1h to obtain a second dispersion;
s4, loading the second dispersion liquid obtained in the step S3 into a reaction kettle, then placing the reaction kettle into a baking oven, and preserving heat at 100 ℃ for 24 hours to obtain suspension liquid of polyaniline in-situ coated hard carbon, namely a hydrothermal product;
s5, centrifuging the suspension of the polyaniline in-situ coated hard carbon obtained in the step S4, washing off excessive impurities by using deionized water and absolute ethyl alcohol, and then placing the suspension in a vacuum oven for drying at 80 ℃ for 24 hours to obtain the polyaniline in-situ coated hard carbon composite material.
And uniformly mixing the prepared polyaniline in-situ coated hard carbon composite material serving as a negative electrode active substance with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, adding an aqueous solvent to prepare a negative electrode slurry, coating the negative electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at 100 ℃ for 12 hours, and rolling and blanking to obtain the negative electrode plate.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO 4 The concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
Tested, the initial coulombic efficiency was 88.4% at 27℃and a current density of 30 mA/g; the cell was capable of cycling 800 cycles at a current density of 300 mA/g.
From the test results of the above 5 examples, it is clear that the composite material prepared in example 2 has the best performance.
Comparing example 2 with examples 1 and 3, it is clear that the carbonization temperature of the raw material in step S1 affects the performance of the hard carbon material, and further affects the electrochemical performance of the polyaniline-coated composite material. The method is characterized in that the carbonization temperature is too low, and organic matters in the raw materials are not thoroughly decomposed, so that micropores are not formed easily, and therefore, the sodium storage of the hard carbon material is insufficient; if the carbonization temperature is too high, the hard carbon material can form a regular graphitized structure, which is unfavorable for sodium storage of the hard carbon. Therefore, the carbonization temperature and the carbonization time need to be controlled, so that the hard carbon material has the characteristics of high disorder and rich micropores, can store more sodium ions, and the most preferred carbonization temperature is 1300 ℃.
Comparing example 2 with examples 4 and 5, it is understood that the addition amount of aniline in step S3 affects the formation of the polyaniline protective layer. When the addition amount of aniline is small, the polyaniline layer formed on the surface of the hard carbon is thin, and the combination with the hard carbon is not firm and stable; when the addition amount of the aniline is large, a thick polyaniline layer is formed, so that each performance of the composite material is biased towards polyaniline, and the circulation stability of the composite material is poor. Therefore, the mass ratio of the aniline to the hard carbon material needs to be controlled, so that good combination between polyaniline and a hard carbon matrix is promoted, the composite material is suitable for storing sufficient sodium ions on one hand, and the structural stability in the circulation process is ensured on the other hand. Most preferably, the aniline is added in an amount of 50 μl per 2g of hard carbon, i.e. the mass ratio of aniline to hard carbon material is 0.05:2.
The hard carbon material and the composite material obtained in example 2 were examined by SEM and TEM, respectively. As can be seen from fig. 1 and 2, the hard carbon materials without and with polyaniline coating have no difference in overall morphology as observed by SEM. As can be seen from fig. 4 and fig. 5, a thin protective film is formed on the surface of the hard carbon material after polyaniline coating by TEM observation, which proves that polyaniline is coated on the hard carbon material in situ. As can be seen from fig. 3, SEM observation proves that the hard carbon material prepared by the method has abundant microporous structure, and increases the surface area, so that the composite material coated with polyaniline can store more sodium ions.
In summary, the invention utilizes the microporous structure of the shell biomass material, and prepares the hard carbon material with high disorder and rich micropores by controlling the carbonization temperature and carbonization time; because the hard carbon material is rich in micropores, polyaniline not only can form a uniform and compact protective layer on the surface of the hard carbon, but also can permeate into the micropores of the hard carbon, so that the polyaniline and a hard carbon matrix are combined more tightly and firmly; meanwhile, the polyaniline protective layer which is uniform, compact and suitable in thickness is formed on the surface of the hard carbon material by controlling the addition amount of the aniline, so that the prepared composite material is good in electrochemical performance and circulation stability. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (7)
1. The preparation method of the polyaniline in-situ coated hard carbon material is characterized by comprising the following steps of:
s1, taking melon seed shells as raw materials, crushing the raw materials, and carbonizing the crushed raw materials under the protection of inert gas to obtain a hard carbon material;
s2, uniformly dispersing the hard carbon material obtained in the step S1 in deionized water to obtain a first dispersion liquid;
s3, adding aniline in the stirring process of the first dispersion liquid, wherein the mass ratio of the added aniline to the added hard carbon material is 0.01-0.1:2, adding an acidic solution to adjust the pH value to 3-4, and stirring for a certain time to enable aniline monomers to realize polymerization of head-tail coupling to obtain a second dispersion liquid;
s4, transferring the second dispersion liquid into a reaction kettle, and performing a hydrothermal reaction at the temperature of 80-120 ℃ for 24-36 hours to obtain a hydrothermal product;
and S5, washing the hydrothermal product obtained in the step S4, and then carrying out vacuum drying to obtain the polyaniline in-situ coated hard carbon composite material.
2. The method for preparing the polyaniline in-situ coated hard carbon material according to claim 1, wherein in the step S1, the carbonization treatment is performed at a temperature of 1200-1400 ℃ for 3-5 hours.
3. The method for preparing polyaniline in-situ coated hard carbon material according to claim 2, wherein in step S1, the inert gas comprises nitrogen, argon or a mixture of nitrogen and argon.
4. The method for preparing the polyaniline in-situ coated hard carbon material according to claim 1, wherein in step S5, deionized water and absolute ethyl alcohol are used to wash the hydrothermal product, and then the hydrothermal product is transferred to a vacuum oven for drying at a drying temperature of 60-100 ℃ for 12-24 hours.
5. The polyaniline in-situ coated hard carbon composite material is characterized by being prepared by the polyaniline in-situ coated hard carbon material preparation method according to any one of claims 1-4.
6. A negative electrode plate, which is characterized in that the negative electrode plate adopts the polyaniline in-situ coated hard carbon composite material as a negative electrode active material.
7. A sodium ion battery comprising a negative electrode, a positive electrode, a separator, and an electrolyte, wherein the negative electrode comprises the negative electrode tab of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311627940.9A CN117334886B (en) | 2023-12-01 | 2023-12-01 | Preparation method and application of polyaniline in-situ coated hard carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311627940.9A CN117334886B (en) | 2023-12-01 | 2023-12-01 | Preparation method and application of polyaniline in-situ coated hard carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117334886A CN117334886A (en) | 2024-01-02 |
| CN117334886B true CN117334886B (en) | 2024-03-19 |
Family
ID=89279631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311627940.9A Active CN117334886B (en) | 2023-12-01 | 2023-12-01 | Preparation method and application of polyaniline in-situ coated hard carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117334886B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020070763A (en) * | 2001-03-02 | 2002-09-11 | 삼성에스디아이 주식회사 | Carbonaceous material and lithium secondary battery comprising the same |
| CN103151179A (en) * | 2013-02-28 | 2013-06-12 | 南京大学 | High-specific-capacitance manganese-dioxide conducting polymer composite electrode material with core-shell structure and manufacturing method thereof |
| CN103539939A (en) * | 2013-09-23 | 2014-01-29 | 哈尔滨工业大学（威海） | Preparation method for polyaniline |
| CN106449148A (en) * | 2016-11-22 | 2017-02-22 | 中国地质大学（北京） | Method for preparing tubular manganese dioxide / poly-aniline / graphene composite material |
| CN114094097A (en) * | 2020-08-24 | 2022-02-25 | 洛阳月星新能源科技有限公司 | Preparation method of long-life high-power graphite composite material |
| CN116715228A (en) * | 2023-07-03 | 2023-09-08 | 桂林理工大学 | Preparation method of sisal fiber carbon anode material with crown-shaped core-shell structure |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9437344B2 (en) * | 2010-07-22 | 2016-09-06 | Nanotek Instruments, Inc. | Graphite or carbon particulates for the lithium ion battery anode |
| US10411254B2 (en) * | 2015-10-15 | 2019-09-10 | Lg Chem, Ltd. | Negative electrode active material and secondary battery including the same |
-
2023
- 2023-12-01 CN CN202311627940.9A patent/CN117334886B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020070763A (en) * | 2001-03-02 | 2002-09-11 | 삼성에스디아이 주식회사 | Carbonaceous material and lithium secondary battery comprising the same |
| CN103151179A (en) * | 2013-02-28 | 2013-06-12 | 南京大学 | High-specific-capacitance manganese-dioxide conducting polymer composite electrode material with core-shell structure and manufacturing method thereof |
| CN103539939A (en) * | 2013-09-23 | 2014-01-29 | 哈尔滨工业大学（威海） | Preparation method for polyaniline |
| CN106449148A (en) * | 2016-11-22 | 2017-02-22 | 中国地质大学（北京） | Method for preparing tubular manganese dioxide / poly-aniline / graphene composite material |
| CN114094097A (en) * | 2020-08-24 | 2022-02-25 | 洛阳月星新能源科技有限公司 | Preparation method of long-life high-power graphite composite material |
| CN116715228A (en) * | 2023-07-03 | 2023-09-08 | 桂林理工大学 | Preparation method of sisal fiber carbon anode material with crown-shaped core-shell structure |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;潘健;"多孔碳材料的合成及在电化学电容器中的应用"(第12期);第三章 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117334886A (en) | 2024-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110835104A (en) | Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery | |
| CN109904387B (en) | Preparation method of high-performance lithium battery positive plate | |
| 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 | |
| CN103000874A (en) | Preparation method of carbon-coated ternary positive electrode material | |
| CN102916178A (en) | Preparation method of carbon cladding modified lithium manganate anode material | |
| CN112038614A (en) | Negative electrode material for sodium ion battery and preparation method thereof | |
| CN111628154A (en) | Lithium battery positive active material, preparation method thereof and lithium battery | |
| CN116654895A (en) | Phosphorus-tin co-doped hard carbon negative electrode material and preparation method thereof | |
| CN109755542B (en) | Sodium-sulfur battery positive electrode material and preparation method thereof | |
| CN110620226A (en) | Preparation method of nitrogen and boron co-doped carbon fiber loaded molybdenum selenide electrode material | |
| CN112174119B (en) | Method for preparing graphene foam from antibiotic fungi residues | |
| CN113193196A (en) | Multifunctional aqueous binder for sodium ion battery and application thereof | |
| CN109449440B (en) | Microporous ultrathin soft carbon nanosheet and preparation method and application thereof | |
| CN117334886B (en) | Preparation method and application of polyaniline in-situ coated hard carbon material | |
| CN115775917A (en) | Preparation method of gel electrolyte applied to secondary sodium ion battery | |
| CN116364886A (en) | Silicon-mesoporous titanium dioxide composite anode material, preparation method and battery | |
| CN116936737A (en) | Sodium ion battery and preparation method and application thereof | |
| CN114751395A (en) | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery | |
| CN114639827A (en) | Preparation method of iron-based fluoride composite positive electrode material | |
| CN114613963A (en) | Negative electrode material, preparation method thereof, negative electrode plate and secondary battery | |
| CN113072056A (en) | Preparation method of metal organic framework derived carbon with high specific surface area | |
| CN112018355A (en) | Preparation method of three-dimensional rod-shaped potassium titanate material | |
| CN110707321A (en) | Copper-coated hollow nickel phosphide material and preparation method and application thereof | |
| CN109686975A (en) | A kind of hard charcoal negative electrode material and preparation method thereof | |
| CN117550587B (en) | 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 |