CN114975975A - Preparation method of iron-iron oxide/porous carbon nanofiber composite anode material - Google Patents
Preparation method of iron-iron oxide/porous carbon nanofiber composite anode material Download PDFInfo
- Publication number
- CN114975975A CN114975975A CN202210823792.7A CN202210823792A CN114975975A CN 114975975 A CN114975975 A CN 114975975A CN 202210823792 A CN202210823792 A CN 202210823792A CN 114975975 A CN114975975 A CN 114975975A
- Authority
- CN
- China
- Prior art keywords
- iron
- porous carbon
- carbon nanofiber
- temperature
- iron oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 57
- IGHXQFUXKMLEAW-UHFFFAOYSA-N iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Fe+2].[O-2] IGHXQFUXKMLEAW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010405 anode material Substances 0.000 title claims abstract description 16
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 40
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 description 22
- 238000009987 spinning Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000002134 carbon nanofiber Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000003759 ester based solvent Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 229910017108 Fe—Fe Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- UNDOASFVPXTZNA-UHFFFAOYSA-N potassium iron(2+) oxygen(2-) Chemical compound [O-2].[K+].[Fe+2] UNDOASFVPXTZNA-UHFFFAOYSA-N 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 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
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of an iron-iron oxide/porous carbon nanofiber composite negative electrode material, which comprises the steps of preparing the iron-iron oxide/porous carbon nanofiber composite negative electrode material by electrostatic spinning and calcining a product of the electrostatic spinning; the preparation method is simple, easy to repeat and high in controllability, the prepared iron-iron oxide/porous carbon nanofiber composite anode material has good flexibility and bendability, is stable in structure and has good conductivity, and the material has excellent rate capability and long cycle stability when being used as a potassium ion battery anode material.
Description
Technical Field
The invention belongs to the technical field of potassium ion battery cathode materials, and relates to a preparation method of an iron-iron oxide/porous carbon nanofiber composite cathode material.
Background
With the continuous improvement of the social and economic level, electronic equipment is developed vigorously, and the demand for high-energy batteries is increased rapidly. Due to the limitation of lithium resources, high capacity sodium and potassium ion batteries are receiving attention because of their abundant materials and low cost. The reduction potential (-2.93V) of potassium ions is closer to that of lithium ions (-3.04V) than that of sodium ions (-2.71V), and the solvated potassium ions have a smaller radius, and are therefore treated with Na + And K + In place of Li + Expected to show a ratio of Li to Li + Better transmission characteristics. However, potassium ion batteries also have some drawbacks that are difficult to overcome. For example, the radius of potassium ions is much larger than that of lithium ions, so that the potassium ion battery is easy to expand in volume during charging and discharging, and the electrode material structure collapses and the electrode pulverizes. Potassium ions have a standard reduction potential similar to that of lithium ions, and the high potential of oxidation-reduction causes partial decomposition of the electrolyte or side reactions. Therefore, the search for high capacity negative electrode materials with good cycling performance is an urgent direction for the development of potassium ion batteries.
The electrochemical reaction of the transition metal oxide follows a conversion type reaction mechanism, and has higher theoretical capacity due to more electrons participating in redox reaction in the charge and discharge processes due to the self property of the transition metal oxide. Among the different transition metal oxides, Fe 2 O 3 Due to the characteristics of low cost, high natural abundance, no toxicity, stable thermodynamics and the like, the method attracts the attention of researchers. However, Fe 2 O 3 The application of the negative electrode material is limited by the defects of poor cycle stability, poor rate capability, low specific surface area, poor conductivity and the like. Improving the conductivity and the cycle stability of the metal oxide anode materialAnd (3) the performance of the lithium ion battery is the key of the application of the lithium ion battery in the potassium ion battery.
Through continuous research, reasonable structural design, such as nanocrystallization of materials, is found to avoid the problems. In recent years, various transition metal oxide nanotopography structures are successively reported to improve the electrochemical performance of the anode material. Another common method for improving the electrochemical performance of transition metal oxides is to compound them with other materials, such as carbon, conductive polymers, amorphous silicon, etc. The materials can stabilize the solid electrolyte interface on the particle surface, play a role in buffering, and ensure the integrity of the particles before and after charging and discharging, thereby improving the electrochemical performance of the materials. Through the means, the development of the high-performance iron oxide potassium ion battery cathode is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of an iron-iron oxide/porous carbon nanofiber composite anode material. The iron-iron oxide/carbon nanofiber composite material is obtained through electrostatic spinning technology and annealing treatment, the method is simple in process and easy to control, and the prepared sample is used as a negative electrode material to be applied to a potassium ion battery, so that the electrochemical performance of the potassium ion battery can be further improved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of an iron-iron oxide/porous carbon nanofiber composite potassium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: adding the pore-forming agent and the polymer into N, N-dimethylformamide according to a certain proportion, heating and stirring to obtain transparent viscous liquid.
Step two: and (3) adding an iron source compound into the transparent viscous liquid obtained in the step one in proportion, and stirring to obtain a red viscous liquid.
Step three: and (4) transferring the red viscous liquid obtained in the step two to an injector to set parameters for electrostatic spinning to obtain the composite fiber membrane.
Step four: and D, carrying out pre-oxidation treatment on the composite fiber membrane obtained in the step three to obtain a pre-oxidation membrane.
Step five: and (5) annealing the pre-oxidized film obtained in the fourth step in an inert gas atmosphere to finally obtain the iron-iron oxide/porous carbon nanofiber composite material.
As a preferable embodiment of the present invention, in the first step, the pore-forming agent is polymethyl methacrylate.
In a preferred embodiment of the present invention, the polymer in the first step is polyvinyl alcohol.
In a preferred embodiment of the present invention, the iron source compound in the first step is iron acetylacetonate.
As a preferable scheme of the invention, in the first step, the stirring temperature is 60 ℃, and the stirring time is 12-24 hours.
As a preferable scheme of the invention, in the second step, the stirring temperature is normal temperature, and the stirring time is 8-12 h.
As a preferable scheme of the invention, the pre-oxidation temperature in the fourth step is 280 ℃.
As a preferred scheme of the invention, in the fifth step, the calcination temperature is 600-800 ℃, and the heating rate of the temperature from room temperature to the target calcination temperature is 3-5 ℃/min.
Due to the adoption of the technical scheme, the beneficial effects are as follows:
1. the iron-iron oxide/porous carbon nanofiber composite material prepared by the method is simple in preparation process and high in repeatability.
2. In the prepared composite material, the iron oxide is nanoparticles which are uniformly distributed in the porous carbon fiber structure, and the elementary substance iron further increases the conductivity of the composite material.
3. The iron-iron oxide/porous carbon nanofiber composite material still has good flexibility and bendability after annealing treatment.
4. The prepared material has stable structure, is not easy to oxidize in the air, is easy to store, can be directly used as a battery cathode, and does not need the assistance of a conductive agent and a binder.
5. The cathode material is applied to a potassium ion battery, has excellent electrochemical performance, has a capacity retention rate of 41% after being cycled for 150 weeks under a current density of 0.5A g-1, and has excellent cycle life and rate capability.
The invention is suitable for the negative electrode material of the potassium ion battery.
The following description will be provided to further explain the present invention in detail by referring to the figures of the specification.
Description of the drawings:
FIG. 1 is an SEM image of a sample of an iron-iron oxide/porous carbon nanofiber composite made in accordance with example 1 of the present invention without annealing;
FIG. 2 is an SEM image of a sample of an iron-iron oxide/porous carbon nanofiber composite made in accordance with example 1 of the present invention;
FIG. 3 is a TEM image of a sample of an iron-iron oxide/porous carbon nanofiber composite made according to example 1 of the present invention;
FIG. 4 is an XRD pattern of a sample of iron-iron oxide/porous carbon nanofiber composite made in accordance with example 1 of the present invention;
FIG. 5 is an XPS plot of Fe 2p for an iron-iron oxide/porous carbon nanofiber composite sample made in accordance with example 1 of the present invention;
FIG. 6 is an XPS plot of O1 s for a sample of an iron-iron oxide/porous carbon nanofiber composite made in accordance with example 1 of the present invention;
FIG. 7 is a Raman plot of a sample of iron-iron oxide/porous carbon nanofiber composite made according to example 1 of the present invention;
FIG. 8 is a graph showing N in samples of iron-iron oxide/porous carbon nanofiber composites prepared in example 1 of the present invention 2 Adsorption/desorption isotherm plots and pore size distribution plots (inset);
FIG. 9 is a thermogram of a sample of an iron-iron oxide/porous carbon nanofiber composite made in accordance with example 1 of the present invention;
FIG. 10 is a graph showing the rate of application of the Fe-Fe oxide/porous carbon nanofiber composite as a negative electrode of a potassium ion battery in example 1 of the present invention;
FIG. 11 is a graph of the cycling performance of the iron-iron oxide/porous carbon nanofiber composite made in example 1 of the present invention as the negative electrode of a potassium ion battery.
Detailed Description
In order to make the technical solutions, advantages and final objects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described in more detail below. The examples do not show the specific conditions, and the general conditions or the conditions recommended by the manufacturer are followed. The reagents, instruments and the like according to the present invention are not particularly limited, and can be commercially available.
Example 1
1. A preparation method of an iron-iron oxide/porous carbon nanofiber composite material specifically comprises the following steps:
the method comprises the following steps: 1.00g of polymethyl methacrylate and 1.00g of polyvinyl alcohol are weighed and dissolved in 8.00g N N dimethylformamide solution, and the mixture is stirred for 12 hours under the conditions that the temperature is 60 ℃ and the rotating speed is 600rpm, so as to obtain transparent viscous liquid.
Step two: 1.00g of ferric acetylacetonate is weighed and added into the mixture, and the mixture is stirred for 12 hours under the conditions of normal temperature and 600rpm rotation speed, so that red viscous liquid is obtained.
Step three: the resulting red viscous liquid was transferred to a 20ml syringe and electrospun. The distance between the spinning nozzle and the receiving plate is 15cm, the voltage is 10-12 kV, the feeding speed is 0.0010mm/s, and the spinning time is 12 hours.
Step four: the collected electrospun film was dried in an oven at 60 ℃ for 24h to remove excess organic solvent.
Step five: the dried electrospun film is cut to a suitable size, placed in the middle of a graphite splint, and pre-oxidized in an oven to stabilize the material structure. The pre-oxidation is divided into 4 processes, the temperature is increased to 200 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 1h at the temperature of 200 ℃, the temperature is increased to 280 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2h at the temperature of 280 ℃, so that the pre-oxidation film is obtained.
Step six: the pre-oxidized film obtained above was calcined in a tube furnace under an argon atmosphere. Heating the mixture from room temperature to 600 ℃ at the heating rate of 3 ℃/min, and calcining the mixture for 2 hours at the temperature of 600 ℃ to obtain the final iron-iron oxide/porous carbon nanofiber composite material.
2. The assembly and performance test of the CR2025 button type potassium ion battery comprises the following steps:
the method comprises the following steps: and shearing the iron-iron oxide/porous carbon nanofiber composite material into a circular electrode plate to obtain the iron-iron oxide/porous carbon nanofiber composite electrode, wherein the diameter of the circular electrode plate is 12-14 mm.
Step two: and (2) taking the circular electrode slice obtained in the step one as a negative electrode slice, taking a potassium slice as an electrode positive electrode slice, taking a glass fiber filter membrane as a battery diaphragm, and assembling the circular electrode slice, the potassium slice and the glass fiber filter membrane into a CR2025 button type potassium ion battery in a glove box filled with argon by taking 0.8mol/L of bifluoride sulfimide potassium salt and ester solvents as electrolytes.
Step three: standing the potassium ion battery assembled in the second step for 12 hours at the voltage of 0.01V-3.0V and the voltage of 0.5A g -1 Carrying out charge-discharge cycle test on the current density; at 0.1A g -1 、0.2A g -1 、0.5A g -1 、1.0A g -1 、2.0A g -1 And carrying out rate performance test on the current density.
Example 2
1. A preparation method of an iron-iron oxide/porous carbon nanofiber composite material specifically comprises the following steps:
the method comprises the following steps: 0.50g of polymethyl methacrylate and 1.50g of polyvinyl alcohol are weighed and dissolved in 8.00g N N dimethylformamide solution, and the mixture is stirred for 12 hours under the conditions that the temperature is 60 ℃ and the rotating speed is 600rpm, so as to obtain transparent viscous liquid.
Step two: 1.00g of ferric acetylacetonate is weighed and added into the mixture, and the mixture is stirred for 12 hours under the conditions of normal temperature and 600rpm rotation speed, so that red viscous liquid is obtained.
Step three: the resulting red viscous liquid was transferred to a 20ml syringe and electrospun. The distance between the spinning nozzle and the receiving plate is 15cm, the voltage is 10-12 kV, the feeding speed is 0.0010mm/s, and the spinning time is 12 hours.
Step four: the collected electrospun film was dried in an oven at 60 ℃ for 24h to remove excess organic solvent.
Step five: the dried electrospun film is cut to a suitable size, placed in the middle of a graphite splint, and pre-oxidized in an oven to stabilize the material structure. The pre-oxidation is divided into 4 processes, the temperature is increased to 200 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 1h at the temperature of 200 ℃, the temperature is increased to 280 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2h at the temperature of 280 ℃, so that the pre-oxidation film is obtained.
Step six: the pre-oxidized film obtained above was calcined in a tube furnace under an argon atmosphere. Heating the mixture from room temperature to 600 ℃ at the heating rate of 3 ℃/min, and calcining the mixture for 2 hours at the temperature of 600 ℃ to obtain the final iron-iron oxide/porous carbon nanofiber composite material.
2. The assembly and performance test of the CR2025 button type potassium ion battery comprises the following steps:
the method comprises the following steps: and shearing the iron-iron oxide/porous carbon nanofiber composite material into a circular electrode plate to obtain the iron-iron oxide/porous carbon nanofiber composite electrode, wherein the diameter of the circular electrode plate is 12-14 mm.
Step two: and (2) taking the circular electrode slice obtained in the step one as a negative electrode slice, taking a potassium slice as an electrode positive electrode slice, taking a glass fiber filter membrane as a battery diaphragm, and assembling the circular electrode slice, the potassium slice and the glass fiber filter membrane into a CR2025 button type potassium ion battery in a glove box filled with argon by taking 0.8mol/L of bifluoride sulfimide potassium salt and ester solvents as electrolytes.
Step three: standing the potassium ion battery assembled in the second step for 12 hours at a voltage of 0.01V-3.0V and at a voltage of 0.5A g -1 Carrying out charge-discharge cycle test on the current density; at 0.1A g -1 、0.2A g -1 、0.5A g -1 、1.0A g -1 、2.0A g -1 And carrying out rate performance test on the current density.
Example 3
1. A preparation method of an iron-iron oxide/porous carbon nanofiber composite material specifically comprises the following steps:
the method comprises the following steps: 1.50g of polymethyl methacrylate and 0.50g of polyvinyl alcohol are weighed and dissolved in 8.00g N N dimethylformamide solution, and the mixture is stirred for 24 hours under the conditions that the temperature is 60 ℃ and the rotating speed is 600rpm, so as to obtain transparent viscous liquid.
Step two: 1.00g of ferric acetylacetonate is weighed and added into the mixture, and the mixture is stirred for 12 hours under the conditions of normal temperature and 600rpm rotation speed, so that red viscous liquid is obtained.
Step three: the resulting red viscous liquid was transferred to a 20ml syringe and electrospun. The distance between the spinning nozzle and the receiving plate is 15cm, the voltage is 10-12 kV, the feeding speed is 0.0010mm/s, and the spinning time is 12 hours.
Step four: the collected electrospun film was dried in an oven at 60 ℃ for 24h to remove excess organic solvent.
Step five: the dried electrospun film is cut to a suitable size, placed in the middle of a graphite splint, and pre-oxidized in an oven to stabilize the material structure. The pre-oxidation is divided into 4 processes, the temperature is increased to 200 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 1h at the temperature of 200 ℃, the temperature is increased to 280 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2h at the temperature of 280 ℃, so that the pre-oxidation film is obtained.
Step six: the pre-oxidized film obtained above was placed in a tube furnace and calcined in an argon atmosphere. Heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min, and calcining the mixture for 2 hours at the temperature of 800 ℃ to obtain the final iron-iron oxide/porous carbon nanofiber composite material.
2. The assembly and performance test of the CR2025 button type potassium ion battery comprises the following steps:
the method comprises the following steps: and shearing the iron-iron oxide/porous carbon nanofiber composite material into a circular electrode plate to obtain the iron-iron oxide/porous carbon nanofiber composite electrode, wherein the diameter of the circular electrode plate is 12-14 mm.
Step two: and (2) taking the circular electrode slice obtained in the first step as a negative electrode slice, taking a potassium slice as an electrode positive electrode slice, taking a glass fiber filter membrane as a battery diaphragm, and adopting 0.8mol/L potassium bis (fluorosulfonyl) imide and an ester solvent as electrolytes to prepare the CR2025 button type potassium ion battery in a glove box filled with argon.
Step three: standing the potassium ion battery assembled in the second step for 12 hours at a voltage of 0.01V-3.0V and at a voltage of 0.5A g -1 Carrying out charge-discharge cycle test on the current density; at 0.1A g -1 、0.2A g -1 、0.5A g -1 、1.0A g -1 、2.0A g -1 And (5) carrying out rate performance test on the current density.
Example 4
1. A preparation method of an iron-iron oxide/porous carbon nanofiber composite material specifically comprises the following steps:
the method comprises the following steps: 1.00g of polymethyl methacrylate and 1.00g of polyvinyl alcohol are weighed and dissolved in 8.00g N N dimethylformamide solution, and the mixture is stirred for 12 hours under the conditions that the temperature is 60 ℃ and the rotating speed is 600rpm, so as to obtain transparent viscous liquid.
Step two: 0.50g of ferric acetylacetonate is weighed and added into the mixture, and the mixture is stirred for 8 hours under the conditions of normal temperature and 600rpm rotation speed, so that red viscous liquid is obtained.
Step three: the resulting red viscous liquid was transferred to a 20ml syringe and electrospun. The distance between the spinning nozzle and the receiving plate is 15cm, the voltage is 10-12 kV, the feeding speed is 0.0010mm/s, and the spinning time is 12 hours.
Step four: the collected electrospun film was dried in an oven at 60 ℃ for 24h to remove excess organic solvent.
Step five: the dried electrospun film is cut to a suitable size, placed in the middle of a graphite splint, and pre-oxidized in an oven to stabilize the material structure. The pre-oxidation is divided into 4 processes, the temperature is increased to 200 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 1h at the temperature of 200 ℃, the temperature is increased to 280 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2h at the temperature of 280 ℃, so that the pre-oxidation film is obtained.
Step six: the pre-oxidized film obtained above was calcined in a tube furnace under an argon atmosphere. Heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining the mixture for 2 hours at the temperature of 600 ℃ to obtain the final iron-iron oxide/porous carbon nanofiber composite material.
2. The assembly and performance test of the CR2025 button type potassium ion battery comprises the following steps:
the method comprises the following steps: and (3) shearing the iron-iron oxide/porous carbon nanofiber composite material into a circular electrode plate to obtain the iron-iron oxide/porous carbon nanofiber composite electrode, wherein the diameter of the circular electrode plate is 12-14 mm.
Step two: and (2) taking the circular electrode slice obtained in the step one as a negative electrode slice, taking a potassium slice as an electrode positive electrode slice, taking a glass fiber filter membrane as a battery diaphragm, and assembling the circular electrode slice, the potassium slice and the glass fiber filter membrane into a CR2025 button type potassium ion battery in a glove box filled with argon by taking 0.8mol/L of bifluoride sulfimide potassium salt and ester solvents as electrolytes.
Step three: standing the potassium ion battery assembled in the second step for 12 hours at a voltage of 0.01V-3.0V and at a voltage of 0.5A g -1 Carrying out charge-discharge cycle test on the current density; at 0.1A g -1 、0.2A g -1 、0.5A g -1 、1.0A g -1 、2.0A g -1 And carrying out rate performance test on the current density.
Example 5
1. A preparation method of an iron-iron oxide/porous carbon nanofiber composite material specifically comprises the following steps:
the method comprises the following steps: 1.50g of polymethyl methacrylate and 1.50g of polyvinyl alcohol are weighed and dissolved in 8.00g N N dimethylformamide solution, and the solution is stirred for 24 hours under the conditions that the temperature is 60 ℃ and the rotating speed is 600rpm, so as to obtain transparent viscous liquid.
Step two: 1.00g of ferric acetylacetonate is weighed and added into the mixture, and the mixture is stirred for 12 hours under the conditions of normal temperature and 600rpm rotation speed, so that red viscous liquid is obtained.
Step three: the resulting red viscous liquid was transferred to a 20ml syringe and electrospun. The distance between the spinning nozzle and the receiving plate is 15cm, the voltage is 10-12 kV, the feeding speed is 0.0010mm/s, and the spinning time is 12 hours.
Step four: the collected electrospun film was dried in an oven at 60 ℃ for 24h to remove excess organic solvent.
Step five: the dried electrospun film is cut to a suitable size, placed in the middle of a graphite splint, and pre-oxidized in an oven to stabilize the material structure. The pre-oxidation is divided into 4 processes, the temperature is increased to 200 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 1h at the temperature of 200 ℃, the temperature is increased to 280 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2h at the temperature of 280 ℃, so that the pre-oxidation film is obtained.
Step six: the pre-oxidized film obtained above was calcined in a tube furnace under an argon atmosphere. Heating from room temperature to 800 ℃ at the heating rate of 5 ℃/min, and calcining for 2h at the temperature of 800 ℃ to obtain the final iron-iron oxide/porous carbon nanofiber composite material.
2. The assembly and performance test of the CR2025 button type potassium ion battery comprises the following steps:
the method comprises the following steps: and shearing the iron-iron oxide/porous carbon nanofiber composite material into a circular electrode plate to obtain the iron-iron oxide/porous carbon nanofiber composite electrode, wherein the diameter of the circular electrode plate is 12-14 mm.
Step two: and (2) taking the circular electrode slice obtained in the step one as a negative electrode slice, taking a potassium slice as an electrode positive electrode slice, taking a glass fiber filter membrane as a battery diaphragm, and assembling the circular electrode slice, the potassium slice and the glass fiber filter membrane into a CR2025 button type potassium ion battery in a glove box filled with argon by taking 0.8mol/L of bifluoride sulfimide potassium salt and ester solvents as electrolytes.
Step three: standing the potassium ion battery assembled in the second step for 12 hours at a voltage of 0.01V-3.0V and at a voltage of 0.5A g -1 Carrying out charge-discharge cycle test on the current density; at 0.1A g -1 、0.2A g -1 、0.5A g -1 、1.0A g -1 、2.0A g -1 And carrying out rate performance test on the current density.
The iron-iron oxide/porous carbon nanofiber composite potassium ion battery negative electrode material prepared in example 1 is taken as an example. The SEM image of the electrospun fiber membrane without calcination is shown in FIG. 1, the fiber surface without calcination is smooth, the average fiber diameter is about 1 μm, and the fiber diameter is uniformly distributed.
Fig. 2 is an SEM image of the iron-iron oxide/porous carbon nanofiber composite negative electrode material, in which the average diameter of the carbon nanofibers encapsulating iron oxide and iron is about 0.5 to 0.6 μm, and it can be clearly observed that particles encapsulated on the surface and inside of the carbon nanofibers are distributed uniformly, and the surface of the fibers has many obvious pores. The calcined material still can show an obvious fiber structure, the phenomena of fiber crushing and breaking and nanoparticle agglomeration do not occur, the hole structure and the fiber structure coexist well, and the iron source compound is uniformly dispersed in the spinning solution. The original material structure is well maintained, so that the volume expansion and crushing caused by the intercalation and deintercalation of potassium ions can be prevented in the charging and discharging processes. The property of the porous carbon nanofiber is beneficial to shortening the diffusion of potassium ions, and the active sites can be increased by the three-dimensional staggered porous fiber, so that the rate capability and the cycling stability of the potassium ion battery are improved.
Fig. 3 is a TEM image of the iron-iron oxide/porous carbon nanofiber composite negative electrode material, and it can be seen that the pore structure inside the carbon nanofiber, iron oxide and iron particles are uniformly dispersed inside and on the surface of the carbon nanofiber, and this structure is consistent with the SEM image.
The XRD patterns are shown in FIG. 4, and 30.24 degrees, 35.63 degrees and 43.28 degrees respectively correspond to Fe 2 O 3 The (220), (311), (400) crystal plane of (a), the characteristic peak 44.67 ° corresponding to the (110) crystal plane of Fe, further confirming the successful preparation of the material.
FIG. 5 is an X-ray photoelectron spectrum of Fe 2p in the Fe-Fe oxide/porous carbon nanofiber composite anode material prepared in example 1, wherein 2p exists in the Fe 2p spectrum 3/2 And 2p 1/2 Spectral peaks of which the first 2p 3/2 The peak position is 707eV, 2p 1/2 The position corresponding to the peak is 720eV, which is consistent with the peak of zero-valent iron; second 2p 3/2 The peak corresponds to 711eV, 2p 1/2 The peak corresponds to a position of 724.5eV, and the two satellite peaks are both at the same position as Fe 3+ The peaks of (a) are coincident, and it is thus understood that the valence states of Fe obtained in the sample prepared in example 1 are zero valence and three valence states.
FIG. 6 is an X-ray photoelectron spectrum of O1 s in the Fe-Fe oxide/porous carbon nanofiber composite anode material prepared in example 1, wherein a peak at 530eV in the O1 s spectrum corresponds to a Fe-O peak, further illustrating that Fe 2 O 3 Is present.
The Raman spectrum is shown in figure 7, wherein the Raman spectrum ranges from 200 cm to 650cm -1 Corresponding Fe appears between 2 O 3 A of (A) 1g And E g Peak of band. 1350cm in the figure -1 And-1580 cm -1 Corresponding to D and G peaks, I D /I G A value of about 1.13 indicates that there are a number of defects in the sample that not only shorten the transport path for potassium ions and electrons, but also provide more active sites for the reaction.
FIG. 8 is a drawing of example 1N for preparing cathode material 2 Adsorption/desorption isotherm plot and pore size distribution (inset). It can be observed from the figure that the isotherm shows a clear hysteresis loop at higher relative pressures, indicating that the sample has mesoporous properties. Pore-forming agent produces the pore structure on fibre surface and inside in the calcination process, and this structure is favorable to the even deposit of nano-particle to imbed carbon nanofiber, not only can effectively separate the nano-particle and prevent the reunion, can also stabilize fibrous structure and alleviate the structure collapse that volume expansion in the charge-discharge process leads to. The specific surface area of the sample measured by the BET method was 348.125m 2 g -1 The pore size was 3.8nm (as indicated by the major concentration range of the pore size in the inset).
Fig. 9 is a thermogravimetric plot of the anode material prepared in example 1, showing that the iron oxide content in the material is around 23.4%.
FIG. 10 is a graph of rate capability of the negative electrode material prepared in example 1, where 0.1A g is shown -1 、0.2A g -1 、0.5A g -1 、1.0A g -1 、2.0A g -1 Current density at 0.1A g for rate capability test -1 At current density, 711.6mAh g -1 Specific discharge capacity of 682mAh g -1 When passing through a larger current density, the charging specific capacity of the battery returns to 0.1A g -1 At current density, it still has 606.5mAh g -1 Specific discharge capacity and 603.1mAh g -1 The specific charge capacity of (a).
FIG. 11 shows that the negative electrode material prepared in example 1 is 0.5A g% -1 The discharge/charge specific capacity of the first circle is 982.2/717.4mAh g -1 The specific capacity of the lithium ion battery is stable at 398.7/394.8mAh g after circulating for 150 circles -1 The capacity retention rate was about 41%.
The above description is only a specific embodiment of the present invention, and is not intended to limit the present invention. It will be apparent to those skilled in the art that modifications and equivalents may be made in the embodiments and descriptions or in part of the technology described herein without departing from the spirit and principles of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (7)
1. A preparation method of an iron-iron oxide/porous carbon nanofiber composite anode material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: adding a pore-forming agent and a polymer into N, N-dimethylformamide according to a certain proportion, heating and stirring to obtain a transparent viscous liquid;
step two: adding an iron source compound into the transparent viscous liquid obtained in the step one in proportion, and stirring to obtain red viscous liquid;
step three: transferring the red viscous liquid obtained in the step two to an injector to set parameters for electrostatic spinning to obtain a composite fiber membrane;
step four: carrying out pre-oxidation treatment on the composite fiber membrane obtained in the step three to obtain a pre-oxidation membrane;
step five: and D, calcining the pre-oxidized film obtained in the step four in an inert gas atmosphere to finally obtain the iron-iron oxide/porous carbon nanofiber composite material.
2. The preparation method of the iron-iron oxide/porous carbon nanofiber composite anode material according to claim 1, characterized by comprising the following steps: in the first step, the pore-forming agent is polymethyl methacrylate, the polymer is polyvinyl alcohol, and in the second step, the iron source compound is ferric acetylacetonate.
3. The preparation method of the iron-iron oxide/porous carbon nanofiber composite potassium ion battery anode material according to claim 2, characterized by comprising the following steps: the mass ratio of the pore-forming agent, the polymer, the N, N dimethylformamide and the iron source compound in the first step and the second step is as follows: (0.50-1.50 g), 0.50-1.50 g, 8g and 0.50-1.00 g.
4. The preparation method of the iron-iron oxide/porous carbon nanofiber composite anode material according to claim 2, characterized by comprising the following steps: the stirring temperature in the first step is 60 ℃, the stirring time is 12-24 hours, the stirring temperature in the second step is normal temperature, and the stirring time is 8-12 hours.
5. The preparation method of the iron-iron oxide/porous carbon nanofiber composite anode material as claimed in claims 1-2, characterized in that: the pre-oxidation in the fourth step is 4 processes, the temperature is increased to 200 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 1h at the temperature of 200 ℃, the temperature is increased to 280 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2h at the temperature of 280 ℃.
6. The preparation method of the iron-iron oxide/porous carbon nanofiber composite anode material according to claims 1-2, characterized in that: and fifthly, the carbonization temperature is 600-800 ℃, and the heating rate is 3-5 ℃.
7. The preparation method of the iron-iron oxide/porous carbon nanofiber composite anode material according to any one of claims 1 to 6, characterized by comprising the following steps: the negative electrode material is an iron-iron oxide/porous carbon nanofiber composite material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210823792.7A CN114975975A (en) | 2022-07-14 | 2022-07-14 | Preparation method of iron-iron oxide/porous carbon nanofiber composite anode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210823792.7A CN114975975A (en) | 2022-07-14 | 2022-07-14 | Preparation method of iron-iron oxide/porous carbon nanofiber composite anode material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114975975A true CN114975975A (en) | 2022-08-30 |
Family
ID=82970622
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210823792.7A Pending CN114975975A (en) | 2022-07-14 | 2022-07-14 | Preparation method of iron-iron oxide/porous carbon nanofiber composite anode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114975975A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104153125A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible ferric oxide nanofiber membrane and preparation method |
CN105098172A (en) * | 2015-09-01 | 2015-11-25 | 扬州大学 | Preparation method of porous graphitic carbon-coated ferroferric oxide nanofiber product and application of porous graphitic carbon-coated ferroferric oxide nanofiber product in lithium ion battery |
CN105185994A (en) * | 2015-08-31 | 2015-12-23 | 中原工学院 | Graphene-doped porous carbon/ferroferric oxide nano-fiber lithium battery anode material and preparation method thereof |
CN113921768A (en) * | 2021-10-08 | 2022-01-11 | 北京化工大学 | Preparation method of flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material |
-
2022
- 2022-07-14 CN CN202210823792.7A patent/CN114975975A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104153125A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible ferric oxide nanofiber membrane and preparation method |
CN105185994A (en) * | 2015-08-31 | 2015-12-23 | 中原工学院 | Graphene-doped porous carbon/ferroferric oxide nano-fiber lithium battery anode material and preparation method thereof |
CN105098172A (en) * | 2015-09-01 | 2015-11-25 | 扬州大学 | Preparation method of porous graphitic carbon-coated ferroferric oxide nanofiber product and application of porous graphitic carbon-coated ferroferric oxide nanofiber product in lithium ion battery |
CN113921768A (en) * | 2021-10-08 | 2022-01-11 | 北京化工大学 | Preparation method of flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material |
Non-Patent Citations (1)
Title |
---|
王利媛: "金属氧化物/碳纳米纤维复合材料的制备及其储锂性能研究" * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111362254B (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
WO2020073915A1 (en) | Lithium ion battery negative electrode material and non-aqueous electrolyte battery | |
CN111188126A (en) | Flexible iron phosphide/carbon nanofiber membrane and preparation method and application thereof | |
CN102867963B (en) | Anode active material of lithium sulfur battery and preparation method of anode active material | |
CN101453006A (en) | Lithium ionic cell electrode material with micro hole construction and manufacturing method thereof | |
WO2022000589A1 (en) | Method for preparing silicon-based composite negative electrode material | |
US20140106215A1 (en) | High energy density secondary lithium batteries | |
CN112599770B (en) | Lithium/sodium ion battery negative electrode material and preparation method thereof | |
CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
CN111106311B (en) | Three-dimensional porous self-supporting electrode and preparation and application thereof | |
CN111769272A (en) | Bi @ C hollow nanosphere composite material and preparation method and application thereof | |
CN114944476B (en) | MoS (MoS) 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof | |
CN111900407A (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
CN111564610A (en) | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof | |
CN113571681B (en) | Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof | |
CN113422009B (en) | Lithium ion battery cathode material and preparation method and application thereof | |
CN116826060B (en) | Composite sodium supplementing material, preparation method, positive pole piece, sodium battery and electric equipment | |
CN111554905B (en) | Preparation method, product and application of zinc oxide-based carbon composite nano material | |
CN115188935A (en) | Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof | |
CN112265977B (en) | Method for preparing porous hollow carbon material by etching | |
CN113611866B (en) | Flexible self-supporting sodium ion battery negative electrode material and preparation method thereof | |
CN114975975A (en) | Preparation method of iron-iron oxide/porous carbon nanofiber composite anode material | |
CN114335475A (en) | Metal fluoride/porous carbon composite positive electrode material and positive plate and battery comprising same | |
CN113764636A (en) | Flexible self-supporting Li3VO4Preparation method of/C nanofiber lithium ion battery cathode material | |
CN110739453A (en) | carbon-coated germanium disulfide 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 | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220830 |
|
WD01 | Invention patent application deemed withdrawn after publication |