CN113113599A - Preparation method and application of nitrogen-doped self-supporting nanofiber membrane - Google Patents
Preparation method and application of nitrogen-doped self-supporting nanofiber membrane Download PDFInfo
- Publication number
- CN113113599A CN113113599A CN202110419018.5A CN202110419018A CN113113599A CN 113113599 A CN113113599 A CN 113113599A CN 202110419018 A CN202110419018 A CN 202110419018A CN 113113599 A CN113113599 A CN 113113599A
- Authority
- CN
- China
- Prior art keywords
- nanofiber membrane
- nitrogen
- temperature
- supporting
- solvent
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 239000002121 nanofiber Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 238000009987 spinning Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010030 laminating Methods 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 229910001415 sodium ion Inorganic materials 0.000 claims description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 16
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- 239000003921 oil Substances 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 229920002239 polyacrylonitrile Polymers 0.000 description 15
- 230000008569 process Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 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 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002134 carbon nanofiber Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
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
- H01M4/58—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
-
- 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
- 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)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a preparation method and application of a nitrogen-doped self-supporting nanofiber membrane. The preparation method of the nitrogen-doped self-supporting nanofiber membrane comprises the following steps: s1, accurately weighing the solute and the solvent, and then placing the solute and the solvent in an oil bath kettle at the temperature of 40-80 ℃ to stir for 5-20 hours at constant temperature to prepare spinning solution; s2, preparing the spinning solution prepared in the S1 into a composite nanofiber membrane; placing the composite nanofiber membrane in a drying oven to remove a solvent, cutting the composite nanofiber membrane into a certain size, and laminating the fiber membrane by using a graphite sheet with a smooth surface; s3, placing the fiber membrane obtained in the step S2 in a quartz tube furnace, and preserving heat for 1-2 hours at 260-280 ℃ in an air atmosphere; then preserving heat for 1-3 h at 600-800 ℃ in a nitrogen atmosphere for carbonization treatment; and after the reaction is finished, cooling the mixture along with the furnace to room temperature to obtain the nitrogen-doped self-supporting nanofiber membrane. The nitrogen-doped self-supporting nanofiber membrane prepared by the method has high storage capacity and high electrochemical performance, and can be directly used as an SIB (silicon dioxide solution) cathode material.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a preparation method and application of a nitrogen-doped self-supporting nanofiber membrane.
Background
In view of the high availability and low cost of sodium, Sodium Ion Batteries (SIBs) are of great interest as an alternative energy storage system to Lithium Ion Batteries (LIBs) for portable electronic devices. However, due to the lack of high performance electrode materials, the rate capability of sodium ion batteries is insufficient; the ionic radius of sodium ion is larger than that of lithium ion, and Na is affected+Ion transport and structural stability during cycling lead to short cycle life of sodium ion batteries, which severely hampers the development of SIBs. To meet the demand for high energy density devices, efficient electrode materials with high storage capacity and rapid kinetic processes of SIBs are needed.
Conventional SIB electrodes typically use copper or aluminum as the current collector and an insulating polymer as the binder, and these inert materials (metal substrate, binder and carbon black) significantly reduce the total energy density of the electrode, resulting in the inability of conventional electrodes to meet the demand for high energy density. Carbon material is considered to be one of the most promising anode materials for SIB. Various carbon-based materials, such as amorphous carbon, graphene, graphite, and expanded graphite, which can promote the insertion/extraction of sodium, are considered as anode materials suitable for SIB. However, in the application of these carbon-based materials in SIB, rate capability and long-term cycling performance are still to be improved. At present, most sodium ion negative electrode materials contain metal ions, and although the metal ions can provide the capacity of a sodium battery, the stability is poor, and the recycling is affected. When the metal and the alloy are used as the negative electrode material of the sodium-ion battery, the metal and the alloy can generate huge volume expansion in the charging process, so that the electrode material is rapidly crushed, the stability is poor, and the practical application is the biggest challenge.
Therefore, the SIB cathode material with excellent electrochemical performance still remains a great challenge, and how to prepare the SIB cathode material with high storage capacity and high electrochemical performance is a problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the problems of small storage capacity and poor electrochemical performance of an SIB (silicon dioxide single crystal) cathode material in the prior art, and provides a preparation method and application of a nitrogen-doped self-supporting nanofiber membrane.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped self-supporting nanofiber membrane comprises the following steps:
s1, accurately weighing the solute and the solvent, placing the solute and the solvent in an oil bath kettle at the temperature of 40-80 ℃, stirring for 5-20 hours at constant temperature, and preparing a spinning solution after the solute is completely dissolved; the solute is PAN (polyacrylonitrile), PS (polystyrene) or PVA (polyacrylonitrile), the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass ratio of the solvent to the solute is 4-9: 1;
s2, preparing the spinning solution prepared in the S1 into a composite nanofiber membrane by adopting electrostatic spinning equipment; placing the composite nanofiber membrane in a drying oven at 40-80 ℃ to remove a solvent, cutting the composite nanofiber membrane into a certain size, and laminating the fiber membrane by using a graphite sheet with a smooth surface;
s3, placing the fiber membrane obtained in the step S2 in a quartz tube furnace, and keeping the temperature for 1-2 hours at 260-280 ℃ in an air atmosphere; then preserving heat for 1-3 h at 600-800 ℃ in a nitrogen atmosphere for carbonization treatment; and after the reaction is finished, cooling the mixture along with the furnace to room temperature to obtain the nitrogen-doped self-supporting nanofiber membrane.
Further, before the step S3, carrying out hot stretching on the cut fiber film by using a load-bearing fixture of 10 g-300 g, and laminating the fiber film by using a graphite sheet with a smooth surface after stretching.
In the step S2, parameters of the electrostatic spinning equipment are that the spinning temperature is 35-50 ℃, the humidity is 36%, 18G-25G needles are used, the voltage is 18 Kv-30 Kv, the rotating speed is 150 r/min-300 r/min, the flow speed is 1 ul/min-3 ul/min, and the distance between the needles and a receiving disc is 15 cm-25 cm.
In the step S4, heating to 260-280 ℃ at a heating rate of 1-5 ℃/min in an air atmosphere; heating to 600-800 deg.C at a heating rate of 1-5 deg.C/min in nitrogen atmosphere
The invention also provides a nitrogen-doped self-supporting nanofiber membrane applied to the sodium ion battery electrode material, and the nitrogen-doped self-supporting nanofiber membrane is obtained by adopting the preparation method.
Compared with the prior art, the invention has the following advantages:
1. the invention prepares the nitrogen-doped self-supporting nanofiber membrane (N-CNFs) with a three-dimensional network structure by an electrostatic spinning technology, the nanofiber membrane has better flexibility, the fiber yarns of the nanofiber membrane have higher specific surface area and active sites, electrolyte is more fully infiltrated, and the electrolyte is also Na+More storage/storage positions are provided, the insertion and extraction path of sodium ions in the material can be favorably shortened in the charging and discharging process, the migration rate of charges on the surface and inside of the material is accelerated, and the adsorption sites of the sodium ions are increased, so that the battery capacity is increased.
The three-dimensional network structure of the nanofiber membrane can form a conductive network, the ordered turbine layer structure of the nanofiber membrane is weaker, the interlayer spacing between graphene sheets is large, N provided by PAN (polyacrylonitrile) is doped in the three-dimensional network structure of the fiber membrane, the state of electrons in a carbon material can be changed, the rate capability and the cycle performance of the carbon material are improved, more defects can be created by doping N, more active sites for adsorbing sodium ions and channels for diffusing the active sites are provided, and therefore the nanofiber membrane has high capacity, good rate capability and excellent cycle stability, and the electrochemical performance of the nanofiber membrane is improved.
2. The fiber filaments can be further refined through load heat treatment, more uniform and thinner nano fiber filaments are prepared, the nano fiber filaments have good specific capacity and cycle performance, and the diffusion migration path of sodium ions is effectively shortened. In the carbonization process, the pressure of the graphite plate can prevent the fiber filaments from curling and having rough surfaces in the carbonization process, so that the surfaces are smoother and smoother. Therefore, when the fiber membrane is used in a sodium ion battery, the diffusion migration path of sodium ions in the charge and discharge process can be effectively shortened, and the specific capacity and the cycle performance of the fiber membrane are further improved.
3. According to the invention, PAN is dissolved in DMF and is placed in an oil bath kettle at 40-80 ℃ for constant-temperature stirring, so that the subsequent treatment process is not required, and the solution is simple and easy to obtain. The uniform, stable, continuous and slender fiber yarns are prepared by controlling spinning parameters, and the operation is easy. The boiling point of DMF is 152.8 deg.C, and the DMF has high boiling point and is not easy to volatilize to cause inhalation poisoning.
4. The nanofiber membrane provided by the invention avoids using inactive ingredients such as a binder and a conductive agent, and the binderless nanofiber membrane can be directly used as an electrode of a sodium battery, all materials in the binderless nanofiber membrane can participate in sodium storage, so that the energy density and the conductivity are improved, and the preparation cost of the sodium battery can be saved.
Drawings
Fig. 1 is a schematic view of a jig used for loading the load in examples 2 and 3.
FIG. 2 is a bending test electron photograph of N-CNFs-100 prepared in example 2 of the present invention.
FIG. 3 is an SEM image of the nanofiber membranes prepared in examples 1-3 of the present invention, wherein (a) is example 1, (b) is example 2, and (c) is example 3.
FIG. 4 is an XRD pattern of the N-CNFs-100 electrode prepared in example 2 of the present invention.
FIG. 5 is a Raman diagram of the N-CNFs-100 electrode prepared in example 2 of the present invention.
Fig. 6 is a graph of the cycle performance of the nanofiber membrane electrode prepared in examples 1-3 of the present invention.
FIG. 7 is an EDS diagram of N-CNFs-100 electrodes prepared in example 2 of the present invention.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Preparation of nitrogen-doped self-supporting nanofiber membrane
Example 1
A preparation method of a nitrogen-doped self-supporting nanofiber membrane comprises the following steps:
s1, accurately weighing 8.7 g of DMF and 1.3g of PAN, melting PAN into DMF, placing in an oil bath kettle at 60 ℃, stirring for 10 hours at constant temperature, and obtaining the spinning solution after the PAN is completely dissolved.
S2, selecting a 20 ml syringe to absorb the spinning solution, fixing the spinning solution on an injection flow rate controller, opening an electrostatic spinning device to adjust relevant spinning parameters (the spinning temperature is 45 ℃, the humidity is 36%, a 22G needle head is used, the voltage is 26 Kv, the rotating speed is 200r/min, the flow rate is 2 ul/min, and the distance between the needle head and a receiving disc is 21 cm), and preparing the nanofiber membrane. And (3) placing the nanofiber membrane in a 60 ℃ forced air drying oven to remove the solvent for 6 h, cutting the nanofiber membrane into square sheets of 5 x 9 cm, and laminating the fiber membrane by using graphite sheets with smooth surfaces.
S3, placing the fiber membrane pressed by the graphite sheets in a quartz tube furnace, adopting program temperature control, heating to 150 ℃ at the heating rate of 2 ℃/min in the Air (Air) atmosphere, and preserving heat for 3 h; then the temperature is raised to 230 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 3 h; heating to 280 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1.5 h. Then under nitrogen (N)2) Heating to 350 ℃ at the heating rate of 2 ℃/min in the atmosphere, and keeping the temperature for 30 min; heating to 430 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1 h; and finally, respectively heating to 650 ℃ at the heating rate of 2 ℃/min, preserving the heat for 3 h for carbonization, and cooling to room temperature to obtain N-CNFs-0 which can be directly used as the cathode of the sodium-ion battery.
Example 2
A preparation method of a nitrogen-doped self-supporting nanofiber membrane comprises the following steps:
s1, accurately weighing 8.2 g of DMF and 1.8g of PAN, melting PAN into DMF, placing in an oil bath kettle at 50 ℃, stirring for 10 hours at constant temperature, and obtaining the spinning solution after the PAN is completely dissolved.
S2, selecting a 20 ml syringe to absorb the spinning solution, fixing the spinning solution on an injection flow rate controller, opening an electrostatic spinning device to adjust relevant spinning parameters (the spinning temperature is 45 ℃, the humidity is 36%, a 22G needle head is used, the voltage is 26 Kv, the rotating speed is 200r/min, the flow rate is 2 ul/min, and the distance between the needle head and a receiving disc is 21 cm), and preparing the nanofiber membrane. The nanofiber membrane was placed in a 60 ℃ forced air drying oven to remove the solvent for 6 hours, cut into 5X 9 cm square pieces, subjected to thermal stretching with a jig as shown in FIG. 1 under a load of 100g for 2 hours, and then laminated with a graphite sheet having a smooth surface.
S3, placing the fiber membrane pressed by the graphite sheets in a quartz tube furnace, adopting program temperature control, and heating up at a heating rate of 2 ℃/min in Air (Air) atmosphereKeeping the temperature for 3 h at 150 ℃; then the temperature is raised to 230 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 3 h; heating to 280 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1.5 h. Then under nitrogen (N)2) Heating to 350 ℃ at the heating rate of 2 ℃/min in the atmosphere, and keeping the temperature for 30 min; heating to 430 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1 h; and finally, respectively heating to 650 ℃ at the heating rate of 2 ℃/min, preserving the heat for 3 h for carbonization, and cooling to room temperature to obtain the N-CNFs-100 which can be directly used as the cathode of the sodium-ion battery.
Example 3
A preparation method of a nitrogen-doped self-supporting nanofiber membrane comprises the following steps:
s1, accurately weighing 10g of DMF and 1.6g of PAN, melting the PAN into the DMF, placing the mixture into an oil bath kettle at the temperature of 55 ℃, stirring for 10 hours at constant temperature, and preparing the spinning solution after the PAN is completely dissolved.
S2, selecting a 20 ml syringe to absorb the spinning solution, fixing the spinning solution on an injection flow rate controller, opening an electrostatic spinning device to adjust relevant spinning parameters (the spinning temperature is 45 ℃, the humidity is 36%, a 22G needle head is used, the voltage is 26 Kv, the rotating speed is 200r/min, the flow rate is 2 ul/min, and the distance between the needle head and a receiving disc is 21 cm), and preparing the nanofiber membrane. The nanofiber membrane was placed in a 60 ℃ forced air drying oven to remove the solvent for 10 hours, cut into 5X 9 cm square pieces, subjected to thermal stretching with a load of 200g for 2 hours using a jig as shown in FIG. 1, and then laminated with a graphite sheet having a smooth surface.
S3, placing the fiber membrane pressed by the graphite sheets in a quartz tube furnace, adopting program temperature control, heating to 150 ℃ at the heating rate of 2 ℃/min in the Air (Air) atmosphere, and preserving heat for 3 h; then the temperature is raised to 230 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 3 h; heating to 280 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1 h. Then under nitrogen (N)2) Heating to 350 ℃ at the heating rate of 2 ℃/min in the atmosphere, and keeping the temperature for 30 min; heating to 430 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1 h; and finally, respectively heating to 650 ℃ at the heating rate of 2 ℃/min, preserving the heat for 3 h for carbonization, and cooling to room temperature to obtain the N-CNFs-200 which can be directly used as the cathode of the sodium-ion battery.
Fig. 2 is an electron photograph of the nitrogen-doped self-supporting nanofiber membrane prepared in example 2. As can be seen from fig. 2, the prepared nitrogen-doped self-supported nanofiber membrane has good toughness. The nitrogen-doped self-supporting nanofiber membrane exhibits strong mechanical strength and excellent flexibility, and can be folded and bent without any damage.
Fig. 3 is an SEM image of the nanofiber membranes prepared in examples 1-3. Wherein (a) in FIG. 3 is an SEM image of N-CNFs-0 prepared in example 1, and the nanofiber membrane in example 1 was carbonized at a high temperature without additional load. As can be seen from the figure, the appearance of the fiber is not damaged after carbonization, the phenomenon of fiber breakage does not occur, the obvious contraction phenomenon does not occur, adjacent fiber yarns are overlapped in a crossed mode, the nano fiber yarns with smooth surfaces are provided, and the average diameter distribution is about 200-350 nm. (b) The SEM image of N-CNFs-100 prepared in example 2 is shown in fig. 3 (b), and it can be seen from fig. 3 (b) that the morphology of the fiber is not damaged after carbonization, the fiber is not broken, and no significant shrinkage occurs, the adjacent fiber filaments are stacked in a crossing manner, and the nano fiber filaments with smooth surfaces have an average diameter distribution of about 200 nm, which is significantly reduced compared to the average diameter of the fiber filaments in (a). (c) The SEM image of the N-CNFs-200 prepared in example 4 shows that the average diameter of the fibers in the nanofiber membrane stretched under a load of 200g is about 150 nm, and the filaments are arranged in a certain order. The arrangement of the fiber filaments is more regular and the average diameter is obviously reduced compared with that in (a) and (b).
Secondly, testing the electrochemical performance of the nitrogen-doped self-supporting nanofiber membrane as the cathode of the sodium ion battery
The nanofiber membranes prepared in example 1 and example 2 were directly used as negative electrode materials of sodium ion batteries to test electrochemical performance. A 2032 type button cell was assembled in an argon-filled glove box using fiberglass as the separator and sodium metal as the counter electrode. The electrolyte used was 1M sodium perchlorate (NaClO)4P98.0%, Sigma-Aldrich), dissolved in a mixture of ethylene carbonate (EC, 99%, Sigma-Aldrich) and dimethyl carbonate (DMC, P99%, Sigma-Aldrich) (EC/DMC =1:1 volume ratio). Assembling to form a CR3032 button cell, and performing electrochemistry on the button cellCan be tested.
FIG. 4 is an XRD test performed on N-CNFs-100 prepared in example 2 as an electrode, in which a nitrogen-doped self-supporting carbon nanofiber membrane is directly used in the XRD test without performing particle pulverization, and the test range is set to 10-90 °. As can be seen from FIG. 4, "steamed bun" diffraction peaks appeared both at around 24 ° and 44 °, indicating that N-CNFs-100 has low crystallinity, both of which are composed of amorphous carbon.
FIG. 5 shows the Raman test performed on the N-CNFs-100 prepared in example 2 as an electrode, the N-CNFs-100 being 1300 cm-1、1580 cm-1Vibration peaks appear nearby and respectively correspond to a D peak (representing a defect characteristic peak of a crystal lattice to correspond to disordered carbon) and a G peak (representing an in-plane stretching vibration peak hybridized by a C atom SP2 to correspond to graphite carbon). For Raman spectroscopy, the R value is commonly used to determine the defect level of the sample, R = ID/IGAnd the larger the R value is, the stronger the defect characteristic peak intensity corresponding to the sample is. In fig. 5, R is 2.17, indicating a low-crystallinity carbon having a disordered orientation in the CNFs.
FIG. 6 is a graph of cycling performance of 70 cycles at 50 mA/g current density for the nanofiber membranes prepared in examples 1-3 as electrodes. Table 1 shows cycle performance test data of the nanofiber membranes prepared in examples 1 to 3 as electrodes. As can be seen from FIG. 6 and Table 1, the specific discharge capacity of N-CNFs-100 is significantly higher than that of the N-CNFs-0 electrode and N-CNFs-200 electrode, and higher and more stable cycling performance is exhibited. The initial discharge specific capacity of the N-CNFs-100 is 438 mAh/g, the discharge specific capacity is 193.83 mAh/g after circulation for 3 times, the discharge specific capacity is 196.57 mAh/g after circulation for 20 times, then the capacity begins to slowly rise, and the discharge specific capacity is 212.09 mAh/g after circulation for 70 times.
Compared with N-CNFs-0, the N-CNFs-100 has thinner fiber filaments and higher specific surface area, and can be beneficial to shortening the embedding and separating paths of sodium ions in the material in the charging and discharging process, accelerating the migration rate of charges on the surface and in the material, increasing the adsorption sites of the sodium ions and further increasing the battery capacity. With the increase of the load to 200g, although the fiber filaments are thinner after being stretched, the specific discharge capacity of the N-CNFs-200 electrode in the initial discharge time, the specific discharge capacity in the cycle of 3 times, the cycle of 20 times and the cycle of 70 times are lower than those of the N-CNFs-100, and even lower than that of the N-CNFs-0 without load. The fiber filaments are likely to be broken more easily while the fiber filaments are small due to the increase of the load, so that a large number of broken fiber filaments exist in the N-CNFs-200, the paths of sodium ions inserted into and removed from the material are blocked, and the specific discharge capacity of the intersecting bottom is caused.
TABLE 1 data of cycle performance tests of nanofiber membranes prepared in examples 1-3 as electrodes
| Specific discharge capacity mAh/g | First time | Circulating for 3 times | Circulating for 20 times | Circulating for 70 times | |
| Example 1 | N-CNFs-0 | 323.25 | 164.70 | 164.43 | 170.02 |
| Example 2 | N-CNFs-100 | 438 | 193.83 | 196.57 | 212.09 |
| Example 3 | N-CNFs-200 | 381.33 | 145 | 127 | 151.355 |
FIG. 7 is an X-ray photoelectron spectroscopy analysis of the nitrogen-doped self-supporting nanofiber membrane prepared in example 2 as an electrode, from which FIG. 7 the element C, O and N content can be found. The test result shows that no impurity is introduced in the process of pre-oxidizing and carbonizing the self-supporting N-CNFs, and the content of C, N and O in the self-supporting N-CNFs is 79.72%, 17.32% and 2.95%. It is demonstrated that by using a solute with a high nitrogen content, carbon fibers with a higher N content can be produced. And the increase of the N content also tends to influence the ionic conductivity of the electrode; during the charging and discharging process of large current, the lithium ion battery can exert higher specific capacity.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (5)
1. A preparation method of a nitrogen-doped self-supporting nanofiber membrane is characterized by comprising the following steps:
s1, accurately weighing the solute and the solvent, placing the solute and the solvent in an oil bath kettle at the temperature of 40-80 ℃, stirring for 5-20 hours at constant temperature, and preparing a spinning solution after the solute is completely dissolved; the solute is PAN, PS or PVA, the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass ratio of the solvent to the solute is 4-9: 1;
s2, preparing the spinning solution prepared in the S1 into a composite nanofiber membrane by adopting electrostatic spinning equipment; placing the composite nanofiber membrane in a drying oven at 40-80 ℃ to remove a solvent, cutting the composite nanofiber membrane into a certain size, and laminating the fiber membrane by using a graphite sheet with a smooth surface;
s3, placing the fiber membrane obtained in the step S2 in a quartz tube furnace, and keeping the temperature for 1-2 hours at 260-280 ℃ in an air atmosphere; then preserving heat for 1-3 h at 600-800 ℃ in a nitrogen atmosphere for carbonization treatment; and after the reaction is finished, cooling the mixture along with the furnace to room temperature to obtain the nitrogen-doped self-supporting nanofiber membrane.
2. The method for preparing the nitrogen-doped self-supporting nanofiber membrane as claimed in claim 1, further comprising, before step S3, thermally stretching the cut fiber membrane by using a 10 g-300 g loading jig, and laminating the fiber membrane with a graphite sheet having a smooth surface after stretching.
3. The method for preparing the nitrogen-doped self-supporting nanofiber membrane according to claim 1 or 2, wherein in the step S2, parameters of electrostatic spinning equipment are that the spinning temperature is 35-50 ℃, the humidity is 36%, 18G-25G needle heads are used, the voltage is 18 Kv-30 Kv, the rotating speed is 150 r/min-300 r/min, the flowing speed is 1 ul/min-3 ul/min, and the distance between the needle heads and a receiving disc is 15 cm-25 cm.
4. The method for preparing a nitrogen-doped self-supporting nanofiber membrane according to claim 1, wherein in step S4, the temperature is raised to 260-280 ℃ at a temperature raising rate of 1-5 ℃/min in an air atmosphere; heating to 600-800 ℃ at a heating rate of 1-5 ℃/min in a nitrogen atmosphere.
5. The nitrogen-doped self-supporting nanofiber membrane applied to the sodium ion battery electrode material is characterized by being obtained by the preparation method of any one of claims 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110419018.5A CN113113599B (en) | 2021-04-19 | 2021-04-19 | Preparation method and application of nitrogen-doped self-supporting nanofiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110419018.5A CN113113599B (en) | 2021-04-19 | 2021-04-19 | Preparation method and application of nitrogen-doped self-supporting nanofiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113113599A true CN113113599A (en) | 2021-07-13 |
| CN113113599B CN113113599B (en) | 2022-08-05 |
Family
ID=76718424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110419018.5A Active CN113113599B (en) | 2021-04-19 | 2021-04-19 | Preparation method and application of nitrogen-doped self-supporting nanofiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113113599B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113540407A (en) * | 2021-07-26 | 2021-10-22 | 四川轻化工大学 | Self-supporting Sn/CNFs composite electrode and preparation method thereof |
| WO2023087129A1 (en) * | 2021-11-16 | 2023-05-25 | 宁波杉杉新材料科技有限公司 | Preparation method for carbon electrode material and carbon electrode material |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| WO2010053291A2 (en) * | 2008-11-06 | 2010-05-14 | 전남대학교산학협력단 | Carbon nano fiber having skin-core structure, method of preparing same, and product containing said carbon nano fiber |
| CN102162154A (en) * | 2011-03-10 | 2011-08-24 | 江苏国正新材料科技有限公司 | Method for preparing super-energy battery active electrical carbon hollow fibers |
| US20130280603A1 (en) * | 2012-04-20 | 2013-10-24 | Korea Institute Of Energy Research | Method of manufacturing anode active material, and anode and lithium battery using the anode active material |
| CN103753725A (en) * | 2014-01-06 | 2014-04-30 | 四川大学 | Biaxial tension melt mixer for preparing polymer-based commixture or composite material |
| CN103855361A (en) * | 2014-03-28 | 2014-06-11 | 清华大学 | Method for preparing nitrogen-doped porous carbon nanofiber cloth |
| CN105161722A (en) * | 2015-10-16 | 2015-12-16 | 天津工业大学 | Porous carbon nanofiber membrane for positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN107503000A (en) * | 2017-09-30 | 2017-12-22 | 东华大学 | A kind of method that carbon nano-fiber tow is prepared using electrostatic spinning |
| CN110517900A (en) * | 2019-09-12 | 2019-11-29 | 四川轻化工大学 | Preparation method of nitrogen-doped low-temperature carbon nanofiber electrode material for supercapacitor |
| US20200056303A1 (en) * | 2018-08-17 | 2020-02-20 | Cence Inc. | Novel carbon nanofiber and method of manufacture |
| CN111029170A (en) * | 2019-12-24 | 2020-04-17 | 郑州四维特种材料有限责任公司 | Method for preparing novel flexible energy storage material |
| CN111900411A (en) * | 2020-08-14 | 2020-11-06 | 四川轻化工大学 | Self-supporting silicon-carbon negative electrode material and preparation method thereof |
| CN112342644A (en) * | 2020-11-26 | 2021-02-09 | 湖北亿纬动力有限公司 | Porous carbon fiber and preparation method and application thereof |
-
2021
- 2021-04-19 CN CN202110419018.5A patent/CN113113599B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010053291A2 (en) * | 2008-11-06 | 2010-05-14 | 전남대학교산학협력단 | Carbon nano fiber having skin-core structure, method of preparing same, and product containing said carbon nano fiber |
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN102162154A (en) * | 2011-03-10 | 2011-08-24 | 江苏国正新材料科技有限公司 | Method for preparing super-energy battery active electrical carbon hollow fibers |
| US20130280603A1 (en) * | 2012-04-20 | 2013-10-24 | Korea Institute Of Energy Research | Method of manufacturing anode active material, and anode and lithium battery using the anode active material |
| CN103753725A (en) * | 2014-01-06 | 2014-04-30 | 四川大学 | Biaxial tension melt mixer for preparing polymer-based commixture or composite material |
| CN103855361A (en) * | 2014-03-28 | 2014-06-11 | 清华大学 | Method for preparing nitrogen-doped porous carbon nanofiber cloth |
| CN105161722A (en) * | 2015-10-16 | 2015-12-16 | 天津工业大学 | Porous carbon nanofiber membrane for positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN107503000A (en) * | 2017-09-30 | 2017-12-22 | 东华大学 | A kind of method that carbon nano-fiber tow is prepared using electrostatic spinning |
| US20200056303A1 (en) * | 2018-08-17 | 2020-02-20 | Cence Inc. | Novel carbon nanofiber and method of manufacture |
| CN110517900A (en) * | 2019-09-12 | 2019-11-29 | 四川轻化工大学 | Preparation method of nitrogen-doped low-temperature carbon nanofiber electrode material for supercapacitor |
| CN111029170A (en) * | 2019-12-24 | 2020-04-17 | 郑州四维特种材料有限责任公司 | Method for preparing novel flexible energy storage material |
| CN111900411A (en) * | 2020-08-14 | 2020-11-06 | 四川轻化工大学 | Self-supporting silicon-carbon negative electrode material and preparation method thereof |
| CN112342644A (en) * | 2020-11-26 | 2021-02-09 | 湖北亿纬动力有限公司 | Porous carbon fiber and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUAN JIN等: "Electrochemical Performance of Electrospun carbon nanofibers as free-standing and binder-free anodes for sodium-Ion and Lithium-Ion Batteries", 《ELECTROCHIMICA ACTA》 * |
| 唐雯: "高强度静电纺聚丙烯腈基纳米碳纤维毡的研制", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113540407A (en) * | 2021-07-26 | 2021-10-22 | 四川轻化工大学 | Self-supporting Sn/CNFs composite electrode and preparation method thereof |
| WO2023087129A1 (en) * | 2021-11-16 | 2023-05-25 | 宁波杉杉新材料科技有限公司 | Preparation method for carbon electrode material and carbon electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113113599B (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yue et al. | Cuprite-coated Cu foam skeleton host enabling lateral growth of lithium dendrites for advanced Li metal batteries | |
| Yue et al. | “Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode | |
| CN108923035B (en) | Preparation method of nano silicon-carbon composite negative electrode material for lithium ion battery | |
| CN113113599B (en) | Preparation method and application of nitrogen-doped self-supporting nanofiber membrane | |
| Sun et al. | Ultra-robust polyimide nanofiber separators with shutdown function for advanced lithium-ion batteries | |
| CN111900411B (en) | Self-supporting silicon-carbon negative electrode material and preparation method thereof | |
| CN110416546A (en) | The preparation method and application of three-dimensional self-supporting nitrogen-doped carbon sodium ion negative electrode material | |
| Sun et al. | Favorable lithium deposition behaviors on flexible carbon microtube skeleton enable a high-performance lithium metal anode | |
| CN112670507B (en) | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery | |
| CN114497545A (en) | Hard carbon negative electrode material and preparation method and application thereof | |
| CN113161604A (en) | Preparation method and application of high-strength solid composite electrolyte film | |
| CN113839146B (en) | Lithium ion battery diaphragm coated with negative electrode active material, and preparation method and application thereof | |
| Peng et al. | A poly (ethylene terephthalate) nonwoven sandwiched electrospun polysulfonamide fibrous separator for rechargeable lithium ion batteries | |
| CN114127986B (en) | Negative pole piece, electrochemical device and electronic device | |
| Han et al. | Hierarchical 3D Electrode Design with High Mass Loading Enabling High‐Energy‐Density Flexible Lithium‐Ion Batteries | |
| Tan et al. | Electrospun Polyacrylonitrile/Polyvinylidene Fluoride/Boehmite Separator and Gel Polymer Electrolyte Polyethylene Oxide/Polyvinylidene Fluoride‐hexafluoropropylene/Lithium Bis (trifluoromethanesulfonyl) imide/Boehmite Composite Separator Are Used for Fast Charging | |
| CN113629353A (en) | PET (polyethylene terephthalate) basic weight ion track composite diaphragm for lithium ion battery and preparation method of PET basic weight ion track composite diaphragm | |
| CN117023569B (en) | Graphene electrothermal film and preparation method thereof, negative electrode, lithium metal battery and dendrite removing method thereof | |
| CN108242546B (en) | Amorphous carbon negative electrode material, preparation method thereof and battery | |
| WO2016110112A1 (en) | Lithium ion battery anode material preparation method | |
| WO2018119956A1 (en) | Porous aluminum-foil anode and method for preparing same, and lithium secondary battery | |
| CN113451575A (en) | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery | |
| CN113097482B (en) | Negative electrode material, preparation method thereof and lithium battery with negative electrode material | |
| CN114628776A (en) | Application method of graphene film in sodium-ion battery and preparation method of graphene film | |
| CN114361400A (en) | Preparation method of flexible lithium metal battery negative electrode framework material, product 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 |