CN112670507A - Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery - Google Patents
Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery Download PDFInfo
- Publication number
- CN112670507A CN112670507A CN202011528387.XA CN202011528387A CN112670507A CN 112670507 A CN112670507 A CN 112670507A CN 202011528387 A CN202011528387 A CN 202011528387A CN 112670507 A CN112670507 A CN 112670507A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulfur battery
- metal selenide
- intermediate layer
- sulfur
- 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
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 28
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000012528 membrane Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002121 nanofiber Substances 0.000 claims abstract description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 21
- 238000001523 electrospinning Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011229 interlayer Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- 229920001021 polysulfide Polymers 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 11
- 239000005077 polysulfide Substances 0.000 abstract description 10
- 150000008117 polysulfides Polymers 0.000 abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 238000002156 mixing Methods 0.000 description 11
- 238000010041 electrostatic spinning Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000013519 translation Methods 0.000 description 4
- 229910016001 MoSe Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910001216 Li2S Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 separators Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了金属硒化物负载的碳纳米纤维的锂硫电池中间层的制备方法及锂硫电池，静电纺丝法制备纳米纤维膜前驱体：将金属乙酸盐与Se粉按比例混合在N,N‑二甲基甲酰胺中得溶液A；将聚丙烯腈溶于N,N‑二甲基甲酰胺中得溶液B，然后将A、B两溶液混合搅拌制得静电纺丝液，利用静电纺丝液进行静电纺丝，最终得到金属硒化物前驱体的纳米纤维膜；利用热退火法制得金属硒化物负载的碳纳米纤维膜。且基于上述方法制备的金属硒化物负载的碳纳米纤维膜，应用于锂硫电池作为中间层，可增强对多硫化物的吸附催化作用，有效的吸附阻止溶解于电解液的多硫化物向锂负极迁移，并促进其充放电过程中的氧化还原反应，从而有效提高锂硫电池的倍率性能和循环稳定性。The invention discloses a method for preparing a lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofibers and a lithium-sulfur battery. The nanofiber membrane precursor is prepared by an electrospinning method: metal acetate and Se powder are mixed in N , obtain solution A in N-dimethylformamide; dissolve polyacrylonitrile in N,N-dimethylformamide to obtain solution B, then mix and stir the two solutions of A and B to obtain an electrospinning solution, using The electrospinning solution is electrospinned to finally obtain a nanofiber film of a metal selenide precursor; a metal selenide-supported carbon nanofiber film is obtained by a thermal annealing method. And the metal selenide-loaded carbon nanofiber membrane prepared based on the above method can be used in lithium-sulfur batteries as an intermediate layer, which can enhance the adsorption and catalysis of polysulfides, and effectively prevent the polysulfides dissolved in the electrolyte from adsorbing to lithium. The anode migrates and promotes the redox reaction during its charge-discharge process, thereby effectively improving the rate performance and cycle stability of lithium-sulfur batteries.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a preparation method of a carbon nanofiber lithium-sulfur battery interlayer loaded by metal selenide and a lithium-sulfur battery.
Background
With the rapid development of electronic portable devices and the electric automobile industry, the demand of the new energy market for electrochemical energy storage devices is increasing. Among them, lithium ion batteries are the most widely used energy storage devices in the market due to their excellent stability and power density, but have high cost and specific capacity (300mAh g)-1) The defects of low and the like are increasingly unable to meet the living needs of people. Therefore, the development of energy storage devices with high power density, high energy density and low cost is a hot spot of current research.
The elemental sulfur of the lithium-sulfur battery is used as a positive electrode material and has higher theoretical specific capacity (1675 mAh.g)-1) And theoretical energy density (2600Wh/Kg), and in addition elemental sulfur is inexpensive and environmentally friendly, so lithium sulfur batteries are one of the most promising rechargeable batteries at present.
Although lithium sulfur batteries have many advantages, three disadvantages of sulfur itself limit their practical applications: (1) insulation of sulfur: S/Li2The poor intrinsic conductivity of S hinders the utilization of the active material, resulting in low specific discharge capacity and low rate performance. In addition, the slow conduction of electrons and ions causes the lithium sulfur voltage plateau curve to tend to show greater polarization at lower discharge plateaus, further reducing the practical energy density of the lithium sulfur battery. (2) Shuttle effect: polysulfide (Li)2SnAnd n is more than or equal to 4 and less than or equal to 8) is easy to dissolve in the electrolyte solution, so that a shuttle effect exists between the anode and the cathode. Wherein shuttle of soluble polysulphides to the negative electrode forms insoluble Li2S, resulting in irreversible loss of the active material and low charging efficiency. (3) Volume expansion:sulfur formation of insoluble Li during charging2And S, the density of which is less than that of sulfur, so that the volume expansion of the lithiated electrode is caused, the maximum volume expansion rate can reach 80%, and finally the electrode material falls off.
To address these deficiencies, researchers have taken a number of measures to improve the performance of lithium sulfur batteries. For example, improvements are made in terms of positive electrode materials, separators, intermediate layers, electrolytes, and the like. However, merely improving the shuttle effect by physical and chemical adsorption does not solve the problem at all, and therefore the most effective solution is to catalytically promote the conversion of lithium polysulphides into solid Li2S2/Li2S to reduce its dissolution in the electrolyte. Thereby remarkably improving the cycle performance and rate performance of the lithium-sulfur battery.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a metal selenide loaded carbon nanofiber lithium sulfur battery intermediate layer and a lithium sulfur battery provided with the intermediate layer, wherein the intermediate layer material of the lithium sulfur battery adopts metal selenide loaded carbon nanofiber, so that the adsorption catalysis effect on polysulfide can be enhanced, polysulfide dissolved in electrolyte is effectively prevented from migrating to a lithium cathode by adsorption, and the redox reaction in the charging and discharging processes of the polysulfide is promoted, so that the rate capability and the cycle stability of the lithium sulfur battery are effectively improved.
The technical scheme adopted by the invention is as follows:
the preparation method of the lithium-sulfur battery intermediate layer of the carbon nanofiber loaded by the metal selenide comprises the following steps:
s1, preparing a nanofiber membrane precursor by an electrostatic spinning method: mixing metal acetate and Se powder in a certain proportion in N, N-dimethylformamide to obtain a solution A; dissolving polyacrylonitrile in N, N-dimethylformamide to obtain a solution B, and mixing and stirring A, B two solutions to obtain an electrostatic spinning solution;
s2, carrying out electrostatic spinning on the electrostatic spinning solution to finally obtain a nanofiber membrane of the metal selenide precursor;
and S3, preparing the carbon nanofiber membrane loaded with the metal selenide by using a thermal annealing method.
Further, the metal acetate is Co (AC)2、Mo(AC)2Or Mn (AC)2；
Further, preparing metal acetate and Se powder in the mass ratio of (1-3): 1 in S1;
further, the parameters of the S2 electrospinning are set as follows: the working voltage is 12-15 kV, the translation distance is 100-130 mm, the injection rate is 0.08-0.1 mm/min, and the spinning distance is 20-25 cm.
Further, heating the nanofiber membrane prepared in the step S2 to 250-300 ℃ at a heating rate of 2-5 ℃/min in an air atmosphere, and preserving heat for pre-oxidation; and after cooling, heating the nanofiber membrane to 500-700 ℃ at a heating rate of 5-10 ℃/min in a nitrogen atmosphere, preserving heat, carbonizing and selenizing to obtain the metal selenide loaded carbon nanofiber membrane, and cutting the carbon nanofiber membrane by using a slicer to obtain the intermediate layer material of the lithium-sulfur battery.
The lithium-sulfur battery comprises a positive electrode, an intermediate layer, a diaphragm and a negative electrode, wherein the positive electrode, the intermediate layer, the diaphragm and the negative electrode are sequentially assembled in an argon atmosphere, and an electrolyte is added; the intermediate layer is the intermediate layer of the metal selenide-supported carbon nanofiber prepared by the method.
Further, the method for preparing the cathode material comprises the following steps: the CMK-3 and the sulfur powder with the mass ratio of 3:7 are subjected to heat preservation for 12 hours at the temperature of 155 ℃ by a melting method to prepare a sulfur composite material; preparing a sulfur composite material into slurry containing a conductive agent, a bonding agent and an organic solvent; coating the slurry on an aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery, wherein the surface loading capacity is 1mg/cm2。
Further, the mass ratio of the sulfur composite material to the conductive agent to the adhesive is 7: 2: 1.
the invention has the beneficial effects that:
from the material aspect: the metal selenide has excellent catalytic action and adsorption capacity, and the transition metal has strong catalytic action, so that soluble polysulfide can be anchored and adsorbed in the charging and discharging process to prevent the soluble polysulfide from migrating to a lithium cathode, and the shuttle effect of the polysulfide is effectively improved. And strong catalytic property promotes the conversion of polysulfide in the charge-discharge process, and enhances the redox reaction degree in the cycle process. And the carbon nanofiber structure can enhance the conductivity of the lithium-sulfur battery, so that the lithium-sulfur battery has good reaction kinetics and electrochemical performance.
From the aspect of morphology: in the interlayer material, the carbon nano fibers form a mutually crossed net structure, and the metal selenide nano particles are uniformly dispersed on the surfaces of the carbon nano fibers, are uniform in appearance and are dispersed, so that more metal active sites are exposed, and Li (lithium) in the discharging process2S/Li2S2Uniform nucleation on the surface thereof, thereby improving the utilization rate of the active material and obtaining excellent electrochemical properties.
Drawings
FIG. 1 is a scanning electron micrograph of an interlayer material prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of an interlayer material prepared in example 1;
FIG. 3 is a graph of rate performance of a lithium sulfur cell assembled with an interlayer material prepared in example 1;
fig. 4 is a graph of long cycle performance of a lithium sulfur battery assembled from example 1 and comparative example materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the lithium-sulfur battery intermediate layer of the carbon nanofiber loaded by the metal selenide comprises the following steps:
s1, preparation Co (AC)2Se/PAN electrospinning solution: first 4.5g Co (AC)2Mixing 1.5g Se powder with 2mL DMF solvent, stirring for 12h to obtain solution A, mixing 0.5g PAN with 5mL DMF solvent, stirring for 12h to obtain solution B, mixing solution A and solution B at 60 deg.C, stirring for 12h to obtain Co (AC)2-Se/PAN electrospinning solution;
s2 Synthesis of Co (AC) by electrospinning)2Se/PAN nanofiber membranes: performing electrostatic spinning on the prepared electrostatic spinning solution, wherein the working voltage is set to be 15kV, the injection rate is 0.1mm/min, the translation distance is 120mm, and the distance is set to be 25cm, so as to obtain Co (AC)2Se/PAN nanofibrous membranes.
S3, preparing a CoSe @ NC nanofiber membrane by a thermal annealing method: first, Co (AC)2And (3) raising the temperature of the-Se/PAN nanofiber membrane to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and preserving the temperature for 2h for pre-oxidation. And then heating the preoxidized nanofiber membrane to 550 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 3 hours, carbonizing and selenizing to obtain the CoSe @ NC nanofiber membrane, and cutting the CoSe @ NC nanofiber membrane into an intermediate layer material with the diameter of 14mm by using a slicing machine.
FIG. 1 is a scanning electron micrograph of the CoSe @ NC interlayer prepared in example 1 at high magnification. It can be seen that the material has a network of nanofibers with a diameter of 200mm crossing each other and surface-loaded with uniformly sized nanoparticles.
Fig. 2 is an X-ray diffraction pattern of the CoSe @ NC interlayer prepared in example 1, and it can be seen that this material has amorphous carbon and CoSe, i.e., a CoSe-supported carbon nanofiber material was prepared.
Fig. 3 is a graph of rate performance of a lithium sulfur cell assembled with a CoSe @ NC interlayer prepared in example 1, and it can be seen that this material has excellent rate performance.
Example 2
The preparation method of the lithium-sulfur battery intermediate layer of the carbon nanofiber loaded by the metal selenide comprises the following steps:
s1, preparation of Mo (AC)2Se/PAN electrospinning solution: firstly 4.5g Mo (AC)2Mixing 1.5g Se powder with 2mL DMF solvent, stirring for 12h to obtain solution A, mixing 0.5g PAN with 5mL DMF solvent, stirring for 12h to obtain solution B, mixing solution A and solution B at 60 deg.C, stirring for 12h to obtain Mo (AC)2-Se/PAN electrospinning solution;
s2 Synthesis of Mo (AC) by electrospinning2Se/PAN nanofiber membranes: carrying out electrostatic spinning on the prepared electrostatic spinning solution, wherein the working voltage is set to be 15kV, the injection rate is 0.1mm/min, the translation distance is 120mm, the distance is set to be 25cm,to obtain Mo (AC)2Se/PAN nanofibrous membranes.
S3, preparing the MoSe @ NC nanofiber membrane by a thermal annealing method: firstly, Mo (AC)2And (3) raising the temperature of the-Se/PAN nanofiber membrane to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and preserving the temperature for 2h for pre-oxidation. And then heating the preoxidized nanofiber membrane to 550 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 3 hours for carbonization and selenization to obtain the MoSe @ NC nanofiber membrane, and cutting the MoSe @ NC nanofiber membrane into an intermediate layer material with the diameter of 14mm by using a slicing machine.
Example 3
The preparation method of the lithium-sulfur battery intermediate layer of the carbon nanofiber loaded by the metal selenide comprises the following steps:
s1 preparation of Mn (AC)2Se/PAN electrospinning solution: first 4.5g Mn (AC)2Mixing 1.5g Se powder with 2mL DMF solvent, stirring for 12h to obtain solution A, mixing 0.5g PAN with 5mL DMF solvent, stirring for 12h to obtain solution B, mixing solution A and solution B at 60 deg.C, stirring for 12h to obtain Mn (AC)2-Se/PAN electrospinning solution;
s2 Synthesis of Mn (AC) by electrospinning2Se/PAN nanofiber membranes: performing electrostatic spinning on the prepared electrostatic spinning solution, wherein the working voltage is set to be 13kV, the injection rate is 0.1mm/min, the translation distance is 120mm, the distance is set to be 25cm, and Mn (AC) is obtained2Se/PAN nanofibrous membranes.
S3, preparing a MnSe @ NC nanofiber membrane by a thermal annealing method: firstly, Mn (AC)2And (3) raising the temperature of the-Se/PAN nanofiber membrane to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and preserving the temperature for 2h for pre-oxidation. And then heating the pre-oxidized nanofiber membrane to 550 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, preserving the heat for 3 hours, carbonizing and selenizing to obtain the MnSe @ NC nanofiber membrane, and cutting the MnSe @ NC nanofiber membrane into an intermediate layer material with the diameter of 14mm by using a slicing machine.
The application also designs a lithium-sulfur battery which comprises a positive electrode, a middle layer, a diaphragm and a negative electrode, wherein the positive electrode, the middle layer, the diaphragm and the negative electrode are sequentially assembled in an argon atmosphere, and 40 mu L of electrolyte is added(ii) a The intermediate layer is the intermediate layer of the metal selenide-supported carbon nanofiber prepared by the above method. The method for manufacturing the anode comprises the following steps: and (3) performing heat preservation on the CMK-3 and the sulfur powder in a mass ratio of 3:7 at 155 ℃ for 12 hours by using a melting method to prepare the sulfur composite material. The sulfur composite material was made into a slurry containing a conductive agent (Super P), a binder (PVDF), and an organic solvent (NMP). Wherein the mass ratio of the sulfur composite material to the conductive agent to the adhesive is 7: 2: 1, coating the slurry on an aluminum foil current collector to serve as a positive pole piece of the lithium-sulfur battery, wherein the surface loading is 1mg/cm2。
Comparative example 1
Comparative example 1 differs from example 1 in that: the remaining preparation method and conditions were the same as in example 1 without adding the interlayer material.
Comparative example 2
Comparative example 2 differs from example 1 in that: interlayer Material without Addition of Co (AC)2And Se powder, the other preparation method and conditions are the same as in example 1. Combining the long cycle performance profiles of the lithium sulfur cell assembled from example 1 and the comparative example material shown in fig. 4, it can be seen that the CoSe @ NC interlayer of example 1 possessed 823mAh g after 100 cycles at 0.1C-1Compared with the comparative example, the specific capacity of the catalyst obviously improves the cycling stability. Therefore, the metal selenide supported carbon nanofiber interlayer material prepared by the invention has excellent electrochemical performance.
The above embodiments are only used for illustrating the design idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention accordingly, and the protection scope of the present invention is not limited to the above embodiments. Therefore, all equivalent changes and modifications made in accordance with the principles and concepts disclosed herein are intended to be included within the scope of the present invention.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011528387.XA CN112670507B (en) | 2020-12-22 | 2020-12-22 | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011528387.XA CN112670507B (en) | 2020-12-22 | 2020-12-22 | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112670507A true CN112670507A (en) | 2021-04-16 |
| CN112670507B CN112670507B (en) | 2022-05-20 |
Family
ID=75407592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011528387.XA Active CN112670507B (en) | 2020-12-22 | 2020-12-22 | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112670507B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113346084A (en) * | 2021-05-31 | 2021-09-03 | 华中科技大学 | Conductive catalytic composite material interlayer for battery, and preparation method and application thereof |
| CN113823791A (en) * | 2021-09-14 | 2021-12-21 | 西安交通大学 | A kind of lithium-sulfur battery cathode barrier material and preparation method thereof |
| CN114267818A (en) * | 2021-12-24 | 2022-04-01 | 淮北师范大学 | Preparation method and application of cathode polysulfide buffer layer for improving cycle performance of lithium-sulfur battery |
| CN114512658A (en) * | 2022-02-28 | 2022-05-17 | 新锦彦(广东)新能源有限公司 | FeTiO3-TiO2Porous carbon nanofiber membrane material loaded by heterostructure and application of porous carbon nanofiber membrane material in sodium-selenium battery |
| CN114725333A (en) * | 2022-03-08 | 2022-07-08 | 华中科技大学 | A composite cathode material for lithium-sulfur battery, its preparation and application |
| CN115036504A (en) * | 2022-07-22 | 2022-09-09 | 济南易航新材料科技有限公司 | Flower-like vanadium diselenide @ carbon fiber nano material, preparation method and application thereof, and magnesium-lithium double-ion battery |
| CN116764660A (en) * | 2023-05-22 | 2023-09-19 | 大连理工大学 | A highly active cathode material catalyst for lithium-sulfur batteries and its preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586950A (en) * | 2012-02-24 | 2012-07-18 | 长春理工大学 | Method for preparing zinc selenide (ZnSe) nanofiber |
| CN107170974A (en) * | 2017-05-26 | 2017-09-15 | 中南大学 | A kind of carbon coating MoSe2/ graphene electro spinning nano fiber and preparation method thereof |
| CN109811428A (en) * | 2019-01-31 | 2019-05-28 | 湘潭大学 | A kind of electrospinning preparation method of flexible SnSe/C nanofibers |
| CN110438798A (en) * | 2019-08-09 | 2019-11-12 | 陕西科技大学 | A kind of lithium-sulfur cell self-supporting positive electrode and its method for manufacturing electric spinning |
-
2020
- 2020-12-22 CN CN202011528387.XA patent/CN112670507B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586950A (en) * | 2012-02-24 | 2012-07-18 | 长春理工大学 | Method for preparing zinc selenide (ZnSe) nanofiber |
| CN107170974A (en) * | 2017-05-26 | 2017-09-15 | 中南大学 | A kind of carbon coating MoSe2/ graphene electro spinning nano fiber and preparation method thereof |
| CN109811428A (en) * | 2019-01-31 | 2019-05-28 | 湘潭大学 | A kind of electrospinning preparation method of flexible SnSe/C nanofibers |
| CN110438798A (en) * | 2019-08-09 | 2019-11-12 | 陕西科技大学 | A kind of lithium-sulfur cell self-supporting positive electrode and its method for manufacturing electric spinning |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113346084A (en) * | 2021-05-31 | 2021-09-03 | 华中科技大学 | Conductive catalytic composite material interlayer for battery, and preparation method and application thereof |
| CN113823791A (en) * | 2021-09-14 | 2021-12-21 | 西安交通大学 | A kind of lithium-sulfur battery cathode barrier material and preparation method thereof |
| CN113823791B (en) * | 2021-09-14 | 2023-03-28 | 西安交通大学 | Lithium-sulfur battery positive electrode barrier layer material and preparation method thereof |
| CN114267818A (en) * | 2021-12-24 | 2022-04-01 | 淮北师范大学 | Preparation method and application of cathode polysulfide buffer layer for improving cycle performance of lithium-sulfur battery |
| CN114512658A (en) * | 2022-02-28 | 2022-05-17 | 新锦彦(广东)新能源有限公司 | FeTiO3-TiO2Porous carbon nanofiber membrane material loaded by heterostructure and application of porous carbon nanofiber membrane material in sodium-selenium battery |
| CN114512658B (en) * | 2022-02-28 | 2024-04-05 | 许新安 | FeTiO 3 -TiO 2 Heterostructure-supported porous carbon nanofiber membrane material and application thereof in sodium-selenium battery |
| CN114725333A (en) * | 2022-03-08 | 2022-07-08 | 华中科技大学 | A composite cathode material for lithium-sulfur battery, its preparation and application |
| CN115036504A (en) * | 2022-07-22 | 2022-09-09 | 济南易航新材料科技有限公司 | Flower-like vanadium diselenide @ carbon fiber nano material, preparation method and application thereof, and magnesium-lithium double-ion battery |
| CN116764660A (en) * | 2023-05-22 | 2023-09-19 | 大连理工大学 | A highly active cathode material catalyst for lithium-sulfur batteries and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112670507B (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112670507B (en) | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery | |
| CN109103399B (en) | Functional separator for lithium-sulfur battery, preparation method thereof, and application in lithium-sulfur battery | |
| CN111403658A (en) | A kind of preparation method of separator with electrocatalytic function and its application in lithium-sulfur battery | |
| CN111900407B (en) | A kind of lithium-sulfur battery cathode material and preparation method thereof | |
| CN115259132B (en) | Preparation method and application of ultra-high first-effect hard carbon anode material | |
| CN110148739A (en) | A kind of carbon@allyl sulfides itrile group polymer composite anode active material, anode and its preparation and the application in lithium-sulfur cell | |
| CN113506862B (en) | Nano carbon fiber composite material for lithium-sulfur battery anode and preparation method and application thereof | |
| CN104752682A (en) | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery | |
| CN114204218A (en) | A kind of preparation method of positive electrode side separator for lithium-sulfur battery loaded with hollow Co3O4 cube | |
| CN110620226A (en) | Preparation method of nitrogen and boron co-doped carbon fiber loaded molybdenum selenide electrode material | |
| CN118754099A (en) | A method for preparing high-initial-efficiency nano-block sodium-ion battery negative electrode biomass hard carbon | |
| CN113363452A (en) | Self-supporting phosphorus/carbon three-dimensional conductive network composite electrode material and preparation method and application thereof | |
| CN112510170B (en) | Nitrogen and sulfur double-doped porous carbon lithium-sulfur battery cathode material and its preparation method and application | |
| CN115764162A (en) | Preparation method of a cobalt nanocrystal-supported nitrogen-doped porous carbon framework and its application in lithium-sulfur batteries | |
| CN113921746A (en) | Preparation method of biochar and coating double-protection lithium-sulfur battery positive electrode | |
| CN117416947A (en) | Preparation method of sodium ion battery negative electrode carbon material derived from foam waste | |
| CN112436151B (en) | A kind of preparation method of lithium-sulfur battery current collector | |
| CN116314710A (en) | Metal organic framework derived cobalt ditelluride-reduced graphene oxide composite material and preparation method and application thereof | |
| CN113097482A (en) | Negative electrode material, preparation method thereof and lithium battery with negative electrode material | |
| CN115020914B (en) | Cattail-structured ceramic composite diaphragm interlayer for lithium/sodium-sulfur battery and preparation method thereof | |
| CN120048889B (en) | A sulfur battery positive electrode material containing graphene oxide composite and preparation method thereof | |
| CN111740109B (en) | Preparation method of boron and phosphorus doped graphitized carbon-nitrogen compound cathode material activated by KOH | |
| CN116487558A (en) | Flexible self-supporting lithium-sulfur battery composite positive electrode material and preparation method thereof | |
| Yue et al. | Hollow Mo 2 C Nanofibers Improve the Electrochemical Performance of Cathode for Lithium-Sulfur Battery | |
| CN115472810A (en) | Vanadium-based carbon nanofiber composite negative electrode material of potassium ion battery and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |