CN113328201B - Lithium-sulfur battery diaphragm with functional interlayer and preparation method thereof - Google Patents
Lithium-sulfur battery diaphragm with functional interlayer and preparation method thereof Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011229 interlayer Substances 0.000 title claims description 47
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002091 nanocage Substances 0.000 claims abstract description 24
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 14
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
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- 239000013543 active substance Substances 0.000 abstract description 8
- 238000007789 sealing Methods 0.000 abstract description 7
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- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 5
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
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- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 4
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- 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
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- General Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of modification of lithium-sulfur battery diaphragms, and provides a lithium-sulfur battery diaphragm with a functional intermediate layer and a preparation method thereof, wherein a ZIF-8 template is firstly prepared, then in-situ synthesis of ZIF-67 is carried out on the template, then annealing is carried out under the protection of inert atmosphere, metal ions of the prepared precursor are removed by etching with sulfuric acid under high-temperature high-pressure sealing, and potassium hydroxide is used for activation under the protection of inert gas to obtain N/O-nanocages/CNTs, and finally the lithium-sulfur battery diaphragm with the functional intermediate layer is prepared, and the rich hierarchical structure of micropores and mesopores is favorable for ion migration and volume expansion for containing active substances; the N/O double doping has strong chemical affinity to polysulfide, can inhibit shuttle of polysulfide, and the in-situ growth of CNTs on the surface of a main body promotes electron migration, improves reaction kinetics and improves the utilization rate of active substances of the lithium-sulfur battery. The problems of low utilization rate and short cycle life of the existing active substances of the lithium-sulfur battery are effectively solved.
Description
Technical Field
The invention belongs to the technical field of modification of lithium-sulfur battery diaphragms, and particularly relates to a lithium-sulfur battery diaphragm with a functional interlayer and a preparation method thereof.
Background
The lithium-sulfur battery has the advantages of high material theoretical specific capacity and battery theoretical specific energy, economy, environmental protection, easy obtainment, harmlessness and the like, and is known to be one of the lithium secondary battery systems with the most research value and application prospect at present. However, the current problems of low utilization rate of active materials, low cycle life, poor safety and the like exist, and the development of the lithium-sulfur battery is severely restricted. The lithium-sulfur battery takes a sulfur simple substance as a positive electrode and metal lithium as a negative electrode, and realizes the charge and discharge of the battery through the fracture and regeneration of a sulfur-sulfur bond. Among them, the high-solubility long-chain multimer easily diffuses into the electrolyte, resulting in irreversible capacity fading. In addition, the poor conductivity of sulfur is not favorable for the capacity of the battery under high current density, and in the process of converting sulfur into polysulfide, the volume expansion destroys the material skeleton, resulting in the loss of elemental sulfur.
The diaphragm is used as an important component in the lithium-sulfur battery, is used for separating two poles of the battery, avoids short circuit of the battery and is beneficial to the transmission of free lithium ions between the electrodes. During the discharge process of the lithium-sulfur battery, polysulfide generated by the lithium-sulfur battery is extremely easy to dissolve in electrolyte, so that the capacity attenuation of the battery cannot be changed, and the cycle performance and the coulombic efficiency of the lithium-sulfur battery are seriously influenced. However, the conventional lithium-sulfur battery separator hardly suppresses the diffusion of polysulfide, resulting in irreversible destruction of the sulfur structure of the positive electrode. The defects of the diaphragm cause a series of problems of poor cycle stability, low actual specific capacity and the like of the lithium-sulfur battery. Therefore, there is a need to develop a lithium sulfur battery separator capable of improving the cycle stability of a lithium sulfur battery.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a lithium-sulfur battery separator having a functional interlayer and a method for preparing the same.
The invention provides a preparation method of a lithium-sulfur battery diaphragm with a functional interlayer, which is characterized by comprising the following steps: step S1, weighing 5 g-15 g Zn (NO)3)2·6H2Dissolving O in 100-400 ml of methanol, weighing 5-15 g of 2-methylimidazole and dissolving in 100-400 ml of methanol, mixing the two solutions to obtain a first mixed product, carrying out centrifugal washing on the first mixed product to obtain a first centrifugally washed mixed product, and drying the first centrifugally washed mixed product to obtain white powder marked as ZIF-8; step S2, weighing 0.5 g-1 g ZIF-8 and 0.5 g-1 g Co (NO)3)2·6H2Placing O in 100-200 mL of methanol, marking as a solution A, weighing 0.5-1 g of 2-methylimidazole, dissolving in 50-100 mL of methanol, marking as a solution B, mixing the solution A with the solution B to obtain a second mixed product, carrying out centrifugal washing on the second mixed product to obtain a centrifugally washed second mixed product, and then drying the centrifugally washed second mixed product to obtain light purple powder, marking as ZIF-8@ ZIF-67; step S3, putting ZIF-8@ ZIF-67 in a tubular furnace for high-temperature pyrolysis treatment, and preserving heat for 1-5 h at the temperature of 600-1000 ℃ in an inert atmosphere to obtain an intermediate product; step S4, using 1M-5M H at 50-150 DEG C2SO4The solution is used for etching the intermediate product, black powder is obtained after etching for 10-24 h, the black powder is placed in a tube furnace for high-temperature pyrolysis treatment, potassium hydroxide is added for activation in inert atmosphere, and heat preservation is carried out at the temperature of 600-1000 ℃ for 0.5-2 h, so that N/O-nanocage/CNT is obtained; step S5, mixing N/O-nanocage/CNT with polyvinylidene fluoride according to the mass ratio of 5: 1-10: 1 for 30 min-1.5 h, dripping 1-5mL of N-methylpyrrolidone to prepare slurry, then coating the slurry on a commercial diaphragm, and drying to obtain the lithium-sulfur battery diaphragm with the functional intermediate layer.
In the method for preparing the lithium-sulfur battery separator with the functional interlayer provided by the invention, the method can also have the following characteristics: wherein, in the step S1, the drying temperature is 50-150 ℃, and the drying time is 1-2 days.
In the method for preparing the lithium-sulfur battery separator with the functional interlayer provided by the invention, the method can also have the following characteristics: wherein, in the step S2, the drying temperature is 50-150 ℃, and the drying time is 1-2 days.
In the method for preparing the lithium-sulfur battery separator with the functional interlayer provided by the invention, the method can also have the following characteristics: in step S5, the drying temperature is 50-100 ℃, and the drying time is 6-12 h.
The invention also provides a lithium-sulfur battery diaphragm with the functional interlayer.
Action and Effect of the invention
According to the preparation method of the lithium-sulfur battery diaphragm with the functional intermediate layer, firstly, a ZIF-8 template is prepared, then, in-situ synthesis of ZIF-67 is carried out on the template, annealing is carried out at a certain temperature under the protection of inert atmosphere, metal ions of the prepared precursor are etched and removed by sulfuric acid under the condition of high-temperature high-pressure sealing, finally, potassium hydroxide is used for activation under the protection of inert gas at a certain temperature to obtain N/O-nanocages/CNTs, the design structure of the nanocages is anchored by using a carbon nano tube which is derived from a coupling structure of the ZIF-8@ ZIF-67, because the ZIF-8@ ZIF-67 is a layered structure with rich micropores and mesopore structures, ion migration is facilitated, the volume expansion of active substances is contained, and the double doping of N/O has strong chemical affinity to polysulfide, can inhibit the shuttle of polysulfide, so can avoid the loss of active material, improve the utilization ratio of the active material of the lithium-sulfur battery, thereby improving the service life of the lithium-sulfur battery. In addition, in situ growth of CNTs on the surface of the host promotes electron transfer and improves reaction kinetics. In conclusion, the lithium-sulfur battery diaphragm with the functional interlayer prepared by the preparation method of the lithium-sulfur battery diaphragm with the functional interlayer provided by the invention enables the lithium-sulfur battery to have good multiplying power and long cycle performance.
Drawings
FIG. 1 is an X-ray (XRD) pattern of N/O-nanocage/CNT prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of N/O-nanocages/CNTs prepared in example 1 of the present invention at different wavelengths;
fig. 3 is a graph of Cyclic Voltammograms (CVs) at different scan rates for a lithium sulfur battery separator cell with a functional interlayer prepared in example 1 of the present invention versus a commercial separator cell prepared in example 3;
fig. 4 is a lithium ion reaction kinetics of the lithium sulfur battery separator cell with a functional interlayer prepared in example 1 of the present invention and the commercial separator cell prepared in example 3;
fig. 5 is a graph of long cycle performance at different rates for a lithium sulfur battery separator cell with a functional interlayer prepared in example 1 of the present invention versus a commercial separator cell prepared in example 3; and
fig. 6 is an impedance test pattern of the lithium sulfur battery separator cell having the functional interlayer prepared in example 2 of the present invention before and after the cycle and the commercial separator cell prepared in example 3.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the lithium sulfur battery separator with the functional interlayer and the preparation method thereof are specifically described below with reference to the embodiment and the accompanying drawings.
Unless otherwise specified, the starting materials and reagents used in the present invention are derived from commonly available routes.
The invention provides a preparation method of a lithium-sulfur battery diaphragm with a functional interlayer, which comprises the following steps:
step S1, weighing 5 g-15 g Zn (NO)3)2·6H2Dissolving O in 100-400 ml of methanol, weighing 5-15 g of 2-methylimidazole and dissolving in 100-400 ml of methanol, mixing the two solutions to obtain a first mixed product, and mixing the first mixed productCarrying out centrifugal washing to obtain a first mixed product after centrifugal washing, and then drying the first mixed product after centrifugal washing to obtain white powder marked as ZIF-8;
in the step, the drying temperature is 50-150 ℃, and the drying time is 1-2 days.
Step S2, weighing 0.5g to 1g of ZIF-8 and 0.5g to 1g of Co (NO)3)2·6H2Placing O in 100 mL-200 mL of methanol, marking as a solution A, weighing 0.5 g-1 g of 2-methylimidazole, dissolving in 50 mL-100 mL of methanol, marking as a solution B, mixing the solution A with the solution B to obtain a second mixed product, carrying out centrifugal washing on the second mixed product to obtain a centrifugally washed second mixed product, and then drying the centrifugally washed second mixed product to obtain light purple powder, wherein the mark is ZIF-8@ ZIF-67;
in the step, the drying temperature is 50-150 ℃, and the drying time is 1-2 days.
Step S3, putting the ZIF-8@ ZIF-67 in a tubular furnace for high-temperature pyrolysis treatment, and preserving heat for 1-5 h at the temperature of 600-1000 ℃ in an inert atmosphere to obtain an intermediate product;
step S4, using 1M-5M H at 50-150 DEG C2SO4The solution is used for etching the intermediate product, black powder is obtained after etching for 10-24 h, the black powder is placed in a tubular furnace for high-temperature pyrolysis treatment, potassium hydroxide is added in an inert atmosphere for activation, and heat preservation is carried out at the temperature of 600-1000 ℃ for 0.5-2 h, so that N/O-nanocage/CNT is obtained;
step S5, mixing the N/O-nanocage/CNT with polyvinylidene fluoride according to the mass ratio of 5: 1-10: 1 for 30 min-1.5 h, dripping 1-5mL of N-methylpyrrolidone to prepare slurry, then coating the slurry on a commercial diaphragm, and drying to obtain the lithium-sulfur battery diaphragm (modified diaphragm) with the functional intermediate layer.
In the step, the drying temperature is 50-100 ℃, and the drying time is 6-12 h.
Assembling the battery and testing: multi-walled carbon nanotubes (MWCNTs) and sublimed sulfur were mixed at a ratio of 1: 1-1: 5 for 0.5 to 1 hour, then dropwise adding 1 to 5mL of carbon disulfide to fully dissolve the carbon disulfide, grinding for 0.5 to 1 hour, after fully mixing the materials uniformly, transferring the materials into an ampoule tube, sealing the ampoule tube in a nitrogen atmosphere, and reacting for 8 to 10 hours at 150 to 160 ℃ to obtain the S/C cathode material. Mixing and grinding the obtained S/C positive electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 until the materials are completely and uniformly mixed, adding 1-5mL of N-methyl pyrrolidone to obtain uniform black slurry, coating the uniform black slurry on an aluminum foil, putting the uniform black slurry into a blast drying oven, drying the uniform black slurry at 60 ℃ to obtain a positive electrode plate of the battery, and finally assembling the positive electrode plate, a lithium-sulfur battery diaphragm (modified diaphragm) with a functional intermediate layer, a lithium sheet, a gasket, a shrapnel and a negative electrode shell into the lithium-sulfur battery in sequence in a glove box. The prepared lithium-sulfur battery is tested for electrochemical performance through an electrochemical workstation and a blue testing system.
< example 1>
The embodiment specifically describes a preparation method of a lithium-sulfur battery diaphragm with a functional interlayer, and specifically comprises the following steps:
step S1, fetch 5g of Zn (NO)3)2·6H2O was dissolved in 150ml of methanol, 6g of 2-methylimidazole were dissolved in 150ml of methanol, and the two solutions were stirred for 1 hour in a constant temperature water bath (50 ℃). The two solutions were then mixed and stirred for 18h, after which they were centrifuged for 5min at 8000r/min and washed 4 times with methanol, and finally dried in a forced air drying cabinet at 80 ℃ for 1 day to give a white powder (labeled as ZIF-8).
Step S2, taking 0.6g of dried white powder ZIF-8 and 0.5g of Co (NO)3)2·6H2O was dispersed in 150mL of methanol and sonicated for 1h (labeled solution A), 0.6g of 2-methylimidazole was dissolved in 100mL of methanol (labeled solution B), solution B was poured into solution A and mixed for 1h, then centrifuged at 8000r/min for 5min and washed 4 times with methanol, and finally dried in a forced air drying oven at 80 ℃ for 1 day to give a pale purple powder (labeled ZIF-8@ ZIF-67).
Step S3, the prepared light purple powder ZIF-8@ ZIF-67 is placed in a tube furnace for high-temperature pyrolysis treatment, the temperature is kept for 2 hours at 700 ℃ in an argon atmosphere, and the heating rate is 1 ℃ for min-1。
Step S4, use 2M H at 100 ℃2SO4Solution, etching the product prepared in the step S3 for 12h to obtain black powder, putting the black powder into a tube furnace for high-temperature pyrolysis treatment, adding potassium hydroxide for activation in nitrogen atmosphere, and keeping the temperature at 600 ℃ for 0.5h at the heating rate of 5 ℃ for min-1. Finally obtaining the N/O-nano cage/CNT.
Step S5, mixing N/O-nanocage/CNT with polyvinylidene fluoride (PVDF) in a ratio of 8:1 for 1 hour, dripping 2mL of N-methylpyrrolidone (NMP) to prepare slurry, then coating the slurry on a commercial diaphragm by using a scraper, putting the commercial diaphragm into a blast drying oven, drying the commercial diaphragm at 60 ℃, and obtaining the lithium-sulfur battery diaphragm (modified diaphragm) with the functional interlayer after 8 hours.
Assembling the battery and testing: multi-walled carbon nanotubes (MWCNTs) and sublimed sulfur were mixed at a ratio of 1: 3 for 1 hour, then dropwise adding 2mL of carbon disulfide to fully dissolve the carbon disulfide, grinding for 1 hour, fully mixing uniformly, transferring the mixture into an ampoule tube, sealing the ampoule tube in a nitrogen atmosphere, and reacting for 10 hours at 155 ℃ to obtain the S/C cathode material. Mixing and grinding the obtained S/C positive electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 until the materials are completely and uniformly mixed, adding 2mL of N-methyl pyrrolidone to obtain black uniform slurry, coating the slurry on an aluminum foil, putting the slurry into a forced air drying oven, drying at 60 ℃ to obtain a positive electrode plate of the battery, and finally assembling the positive electrode plate, a lithium-sulfur battery diaphragm (modified diaphragm) with a functional interlayer, a lithium sheet, a gasket, a shrapnel and a negative electrode shell into the lithium-sulfur battery in sequence in a glove box. The prepared lithium-sulfur battery is tested for electrochemical performance through an electrochemical workstation and a blue test system.
< example 2>
The embodiment specifically describes a preparation method of a lithium-sulfur battery diaphragm with a functional interlayer, and specifically comprises the following steps:
step S1, take 6g of Zn (NO)3)2·6H2O was dissolved in 200ml of methanol, 8g of 2-methylimidazole was dissolved in 200ml of methanol, and the two solutions were stirred in a constant temperature water bath (50 ℃ C.) for 1 hour. The two solutions were then mixed and stirred for 18h, after which they were centrifuged for 5min at 8000r/min and washed 4 times with methanol, and finally dried in a forced air drying cabinet at 80 ℃ for 1 day to give a white powder (labeled as ZIF-8).
Step S2, take 0.6g of dried white powder ZIF-8 and 0.7g of Co (NO)3)2·6H2O was dispersed in 200mL of methanol and sonicated for 2h (labeled solution A), 0.6g of 2-methylimidazole was dissolved in 100mL of methanol (labeled solution B), solution B was poured into solution A and mixed for 1h, then centrifuged at 8000r/min for 5min and washed 4 times with methanol, and finally dried in a forced air drying oven at 80 ℃ for 1 day to give a pale purple powder (labeled ZIF-8@ ZIF-67).
Step S3, the prepared light purple powder ZIF-8@ ZIF-67 is placed in a tube furnace for high-temperature pyrolysis treatment, the temperature is kept for 2 hours at 800 ℃ in an argon atmosphere, and the heating rate is 3 ℃ for min-1。
Step S4, use 3M H at 100 ℃2SO4Solution, etching the product prepared in the step S3 for 12h to obtain black powder, putting the black powder into a tube furnace for high-temperature pyrolysis treatment, adding potassium hydroxide for activation in nitrogen atmosphere, and keeping the temperature at 800 ℃ for 1h at the heating rate of 8 ℃ for min-1. Finally obtaining the N/O-nano cage/CNT.
Step S5, mixing N/O-nanocage/CNT with polyvinylidene fluoride (PVDF) in a ratio of 8:1 for 1 hour, 2mL of NMP is dripped into the mixture to prepare slurry, the slurry is coated on a commercial diaphragm by a scraper and is dried in a blast drying oven at 60 ℃, and after 8 hours, the lithium-sulfur battery diaphragm (modified diaphragm) with the functional interlayer is obtained.
Assembling the battery and testing: multi-walled carbon nanotubes (MWCNTs) and sublimed sulfur were mixed at a ratio of 1: 3 for 1 hour, then dropwise adding 2mL of carbon disulfide to fully dissolve the carbon disulfide, grinding for 1 hour, fully mixing uniformly, transferring the mixture into an ampoule tube, sealing the ampoule tube in a nitrogen atmosphere, and reacting for 10 hours at 155 ℃ to obtain the S/C cathode material. Mixing and grinding the obtained S/C positive electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 until the materials are completely and uniformly mixed, adding 2mL of N-methyl pyrrolidone to obtain black uniform slurry, coating the slurry on an aluminum foil, putting the slurry into a forced air drying oven, drying at 60 ℃ to obtain a positive electrode plate of the battery, and finally assembling the positive electrode plate, a lithium-sulfur battery diaphragm (modified diaphragm) with a functional interlayer, a lithium sheet, a gasket, a shrapnel and a negative electrode shell into the lithium-sulfur battery in sequence in a glove box. The prepared lithium-sulfur battery is tested for electrochemical performance through an electrochemical workstation and a blue test system.
< example 3>
Assembling the battery and testing: multi-walled carbon nanotubes (MWCNTs) and sublimed sulfur were mixed at a ratio of 1: 3 for 1 hour, then dropwise adding 2mL of carbon disulfide to fully dissolve the carbon disulfide, grinding for 1 hour, fully mixing uniformly, transferring the mixture into an ampoule tube, sealing the ampoule tube in a nitrogen atmosphere, and reacting for 10 hours at 155 ℃ to obtain the S/C cathode material. Mixing and grinding the obtained S/C positive electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 until the materials are completely and uniformly mixed, adding 2mL of N-methyl pyrrolidone to obtain black uniform slurry, coating the black uniform slurry on an aluminum foil, putting the slurry into a forced air drying oven to be dried at the temperature of 60 ℃ to obtain a positive electrode plate of the battery, and finally assembling the positive electrode plate, a commercial diaphragm, a lithium plate, a gasket, a shrapnel and a negative electrode shell into the lithium-sulfur battery in a glove box in sequence. The prepared lithium-sulfur battery is tested for electrochemical performance through an electrochemical workstation and a blue testing system.
< test example >
The N/O-nanocage/CNT prepared in example 1 was examined by an X-ray diffractometer, and the results are shown in FIG. 1.
FIG. 1 is an X-ray (XRD) pattern of N/O-nanocage/CNT prepared in example 1 of the present invention.
As shown in fig. 1, the peaks of N/O-nanocage/CNT near 26 ° and 44 ° correspond to (002) and (100) diffraction of low graphitized carbon, which results from carbonization of ZIF-8@ ZIF-67.
The N/O-nanocage/CNT prepared in example 1 is detected by a scanning electron microscope, and the detection result is shown in FIG. 2.
FIG. 2(a, b, c) are Scanning Electron Microscope (SEM) images of the N/O-nanocages/CNTs prepared in example 1 of the present invention at 1 μm, 500nm, and 100nm, respectively.
As shown in FIG. 2(a, b), ZIF-8@ ZIF-67 and ZIF-8 exhibit similar rhombic dodecahedral structure and grain size, indicating that the epitaxial growth of the ZIF-67 layer is very thin. As shown in fig. 2(c), the high-magnification SEM image also revealed a tubular morphology on the surface of the nanocages, indicating that the synthesized material was indeed N/O-nanocages/CNTs.
Electrochemical performance tests were performed on the lithium sulfur battery separator (modified separator) cell with the functional interlayer prepared in example 1 and the commercial separator cell prepared in example 3 using an electrochemical workstation and a blue test system, and the test results are shown in fig. 3-6.
FIG. 3(a) is a graph of cyclic voltammetry Curves (CV) at 0.1mV s-1 scan rate for the lithium-sulfur battery separator (modified separator) cell with a functional intermediate layer prepared in example 1 of the present invention and the commercial separator cell prepared in example 3, FIG. 3(b) is a graph of cyclic voltammetry Curves (CV) at 0.1 to 0.5mV s-1 scan rate for the commercial separator cell prepared in example 3, and FIG. 3(c) is a graph of cyclic voltammetry Curves (CV) at 0.1 to 0.5mV s-1 scan rate for the lithium-sulfur battery separator (modified separator) cell with a functional intermediate layer prepared in example 1 of the present invention.
As shown in FIG. 3(a), a reduction peak appears at 2.3 and 2.03V respectively, which correspond to a solid-liquid conversion process of cyclic sulfur into long-chain polysulfide and a liquid-liquid conversion process of long-chain polysulfide into short-chain polysulfide. An oxidation peak occurs at 2.37V, which corresponds to the conversion of short-chain polysulfides to long-chain polysulfides/active substance sulphur. For commercial separator cells, a small spike at the oxidation peak position is due to the shift from short-chain polysulfides to long-chain onesPolysulfide conversion is slow. Since the coating of the separator resulted in an increase in the thickness of the film, in order to determine whether the mobility of lithium ions was affected or not, we performed a test of the reaction kinetics of lithium ions at 0.1-0.5 mV s, as shown in FIG. 3(b, c)-1It is evident from CV tests carried out in the scanning rate range that the redox current of the lithium-sulphur battery separator cell with a functional interlayer is greater, which facilitates the catalytic conversion of polysulphides in the cell and thus improves the deposition of insulating substances and reduces the polarization voltage.
Fig. 4 is a lithium ion reaction kinetics of the lithium sulfur battery separator (modified separator) cell with a functional interlayer prepared in example 1 of the present invention and the commercial separator cell prepared in example 3.
As shown in fig. 4, the mobility of the lithium-sulfur battery separator (modified separator) battery with the functional interlayer is significantly improved, because the doping of the N/O element increases the adsorption of the lithium ions in the battery, and the N/O element acts as a bridging function to accelerate the transfer of the lithium ions, thereby reducing the internal impedance of the battery to some extent.
Fig. 5(a) is a long cycle performance graph at a rate of 1C of the lithium sulfur battery separator (modified separator) battery having the functional interlayer prepared in example 1 of the present invention and the commercial separator battery prepared in example 3, fig. 5(b) is a long cycle performance graph at a rate of 2C of the lithium sulfur battery separator (modified separator) battery having the functional interlayer prepared in example 1 of the present invention, and fig. 5(C) is a performance test graph at rates of 0.1C, 0.2C, 0.3C, 0.5C, 1C, 2C, 0.5C, 0.3C, and 0.1C of the lithium sulfur battery separator (modified separator) battery having the functional interlayer prepared in example 1 of the present invention.
As shown in FIG. 5(a), the initial specific capacity of the lithium-sulfur battery separator (modified separator) cell with the functional interlayer at 1C was 1000mAh g-1The specific capacity is 450mAh g after 1000 cycles of circulation-1The attenuation rate per cycle was 0.05%, and the sulfur utilization rate of the lithium-sulfur battery separator (modified separator) cell having a functional interlayer reached 59.7%, and was greatAnd (5) lifting. While the initial specific capacity of the commercial diaphragm battery is 800mAh g-1Only 400mAh g after 500 cycles-1The specific capacity of (A) was remained, and the attenuation rate per turn was 0.1%. After that, a long cycle performance test was performed at 2C, and as shown in fig. 5(b), the initial specific capacity of the lithium-sulfur battery separator (modified separator) battery with the functional interlayer was 600mAh g at a rate of 2C-1400mAh g still remained after 1000 cycles of circulation-1The specific capacity is remained, and the attenuation rate of each circle is 0.03%. As shown in fig. 5(C), the performance measured at 0.1, 0.2, 0.3, 0.5, 1, 2, 0.5, 0.3 and 0.1C rate was greatly improved in specific capacity compared to commercial separator batteries, and it was found that the lithium-sulfur battery separator (modified separator) battery having a functional intermediate layer had good rate performance and reversible cycle performance.
Fig. 6(a) is a resistance test chart before cycle of the lithium sulfur battery separator (modified separator) battery with a functional interlayer prepared in example 2 of the present invention and the commercial separator battery prepared in example 3, and fig. 6(b) is a resistance test chart after cycle 200 cycles of the lithium sulfur battery separator (modified separator) battery with a functional interlayer prepared in example 2 of the present invention and the commercial separator battery prepared in example 3.
As shown in fig. 6(a), the lithium sulfur battery separator (modified separator) cell with the functional interlayer prior to cell cycling had less ohmic resistance and charge transfer resistance due to the higher conductivity of the carbon material, which leads to a reduction in overall cell resistance compared to commercial separators with higher charge transfer. As shown in fig. 6(b), after 200 cycles, electrochemical resistance tests were performed, and it was found that the ohmic resistance and the charge transfer resistance of both the lithium-sulfur battery separator (modified separator) cell having the functional interlayer and the commercial separator cell were reduced because the contact between the interfaces during the cycling of the cell was more compact to facilitate the transfer of charges, and the functional interlayer accelerated the migration of lithium ions to reduce the internal resistance of the cell to some extent.
Effects and effects of the embodiments
According to the preparation method of the lithium-sulfur battery diaphragm with the functional intermediate layer, the ZIF-8 template is prepared firstly, the in-situ synthesis of ZIF-67 is carried out on the template, then the annealing is carried out at a certain temperature under the protection of inert atmosphere, the prepared precursor is etched by sulfuric acid under the condition of high temperature and high pressure sealing to remove metal ions, finally the activation is carried out by potassium hydroxide under the protection of inert gas at a certain temperature to obtain N/O-nanocage/CNT, the design structure of the nanocage takes the carbon nano tube as anchoring, the carbon nano tube is derived from the coupling structure of the ZIF-8@ ZIF-67, because the ZIF-8@ ZIF-67 has a layered structure with abundant micropore and mesopore structures, the ion migration and the volume expansion of active substances are favorably accommodated, and the double doping of N/O has strong chemical affinity to polysulfide and can inhibit the shuttling of polysulfide, so that the loss of active substances can be avoided, the utilization rate of the active substances of the lithium-sulfur battery is improved, and the service life of the lithium-sulfur battery is prolonged. In addition, in situ growth of CNTs on the surface of the host promotes electron transport and improves reaction kinetics. In conclusion, the lithium-sulfur battery diaphragm with the functional interlayer prepared by the preparation method of the lithium-sulfur battery diaphragm with the functional interlayer enables the lithium-sulfur battery to have good multiplying power and long cycle performance.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (5)
1. A preparation method of a lithium-sulfur battery diaphragm with a functional interlayer is characterized by comprising the following steps:
step S1, weighing 5 g-15 g Zn (NO)3)2·6H2Dissolving O in 100-400 ml of methanol, weighing 5-15 g of 2-methylimidazole, dissolving in 100-400 ml of methanol, mixing the two solutions to obtain a first mixed product, carrying out centrifugal washing on the first mixed product to obtain a first mixed product after centrifugal washing, and drying the first mixed product after centrifugal washing to obtain white powder marked as ZIF-8;
step S2, weighing 0.5 g-1 g of the ZIF-8 and 0.5g～1gCo(NO3)2·6H2Placing O in 100-200 mL of methanol, marking as a solution A, weighing 0.5-1 g of 2-methylimidazole, placing the solution in 50-100 mL of methanol, marking as a solution B, mixing the solution A with the solution B to obtain a second mixed product, carrying out centrifugal washing on the second mixed product to obtain a centrifugally washed second mixed product, and then drying the centrifugally washed second mixed product to obtain light purple powder, marking as ZIF-8@ ZIF-67;
step S3, putting the ZIF-8@ ZIF-67 in a tubular furnace for high-temperature pyrolysis treatment, and preserving heat for 1-5 h at the temperature of 600-1000 ℃ in an inert atmosphere to obtain an intermediate product;
step S4, using 1M-5M H at 50-150 DEG C2SO4The solution is used for etching the intermediate product, black powder is obtained after etching for 10-24 h, the black powder is placed in a tubular furnace for high-temperature pyrolysis treatment, potassium hydroxide is added for activation in an inert atmosphere, and heat preservation is carried out at the temperature of 600-1000 ℃ for 0.5-2 h, so that N/O-nanocage/CNT is obtained;
step S5, mixing the N/O-nanocage/CNT with polyvinylidene fluoride according to the mass ratio of 5: 1-10: 1 for 30 min-1.5 h, dripping 1-5mL of N-methylpyrrolidone to prepare slurry, coating the slurry on a commercial diaphragm, and drying to obtain the lithium-sulfur battery diaphragm with the functional intermediate layer.
2. The method of preparing a lithium sulfur battery separator with a functional interlayer according to claim 1, characterized in that:
wherein, in the step S1, the drying temperature is 50-150 ℃, and the drying time is 1-2 days.
3. The method of preparing a lithium sulfur battery separator with a functional interlayer according to claim 1, characterized in that:
wherein, in the step S2, the drying temperature is 50-150 ℃, and the drying time is 1-2 days.
4. The method of preparing a lithium sulfur battery separator with a functional interlayer according to claim 1, characterized in that:
in step S5, the drying temperature is 50-100 ℃, and the drying time is 6-12 h.
5. A lithium-sulfur battery separator with a functional interlayer, characterized in that the lithium-sulfur battery separator with a functional interlayer is prepared by the method for preparing the lithium-sulfur battery separator with a functional interlayer according to any one of claims 1 to 4.
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