CN114614198A - Phase change diaphragm for lithium-sulfur battery and preparation method thereof - Google Patents
Phase change diaphragm for lithium-sulfur battery 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 33
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- 239000000243 solution Substances 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
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- 230000000694 effects Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
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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
- H01M50/431—Inorganic material
-
- 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
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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
-
- 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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Abstract
The invention discloses a phase change diaphragm for a lithium-sulfur battery and a preparation method thereof, wherein the phase change diaphragm comprises the following components: a metal organic framework MOF/BP heterojunction complex is assembled on an interface in an oil-water system; preparing a Polyacrylonitrile (PAN) solution and a paraffin PW solution into a nanofiber membrane (PPW) with a core-shell structure by a coaxial electrostatic spinning technology; and dispersing the MOF/BP heterojunction powder in deionized water to form an MOF/BP heterojunction dispersion liquid, depositing the MOF/BP heterojunction dispersion liquid on the nanofiber membrane PPW by a vacuum filtration method, and drying in vacuum to obtain the PPW/MOF/BP phase change membrane. Thus obtaining the phase-change diaphragm material for the high-safety and high-performance lithium-sulfur battery. According to the invention, the safety performance of the lithium sulfur battery is improved through the phase-change nanofiber membrane, the shuttle effect in a lithium sulfur system is inhibited through the MOF/BP heterojunction, and the cycle performance of the battery is improved, so that the high-safety and high-performance lithium sulfur battery is constructed.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and relates to a phase change diaphragm for a lithium-sulfur battery and a preparation method thereof.
Background
With the demand of emerging market application for higher energy density secondary batteries, the energy density of secondary batteries is required to reach 300Wh kg in fields such as hybrid electric vehicles (PHEV) and Pure Electric Vehicles (PEV)-1。
Theoretical energy of lithium-sulfur batteryThe mass density reaches 2600Wh kg-1The method is more practical, rich in resources, low in price, environment-friendly and the like, and is widely researched.
However, the main problems impeding the development of current lithium sulfur batteries are: the elemental sulfur anode can form a soluble polysulfide intermediate product in the charging and discharging processes, polysulfide is continuously dissolved and diffused in electrolyte and is continuously deposited on the surface of a lithium cathode through a diaphragm, so that the internal impedance of the battery is increased, the sulfur loss of an active substance and the electrochemical performance are sharply reduced, and therefore, the inhibition of the shuttle effect of the polysulfide is the key point for improving the comprehensive performance of the current lithium-sulfur battery. Meanwhile, the potential safety hazard of combustion and explosion exists in the operation process of the battery, so that the lithium-sulfur battery is difficult to apply to actual life.
Disclosure of Invention
The purpose is as follows: in order to overcome the defects in the prior art and solve the problems of potential safety hazards of the existing commercial diaphragm and incapability of inhibiting shuttle effect in the lithium-sulfur battery, the invention provides a phase-change diaphragm for the lithium-sulfur battery and a preparation method thereof, so as to improve the safety and performance of the lithium-sulfur battery.
Black Phosphorus (BP) is the most thermodynamically stable allotrope of phosphorus with low resistivity between 0.48 and 0.77 Ω. cm and ultra-high room temperature pore mobility of-1000 cm2 V-1s-1. BP also had a low density of 2.69g cm-3Good volume conductivity of 3S cm-1High diffusion constant of lithium ions and high binding energy with sulfur. These properties indicate that BP has the ability to chemically bind lithium polysulfide while its high conductivity and high lithium ion diffusion constant are effective in promoting the kinetics of the reaction of lithium polysulfide to lithium sulfide. The literature also demonstrates the excellent properties of black phosphorus for efficient adsorption and conversion of lithium polysulfides. However, black phosphorus is easily oxidized and decomposed in air, limiting its application in lithium sulfur batteries. The organic metal framework MOF is taken as a porous material, the fixed pore size can provide rapid passage and uniform deposition of lithium ion transmission, and the penetration of lithium polysulfide can be blocked by the action of a physical barrierShuttles, have also found widespread use in lithium sulfur batteries. However, most MOFs are poorly conductive and have poor catalytic ability for the lithium polysulfide conversion kinetics, which is detrimental to the electrochemical performance of the cell. In conclusion, the combination of the black phosphorus and the MOF is a method for effectively making up the defects of the black phosphorus and the MOF, the MOF on the surface of the black phosphorus can play a role in blocking oxygen, the air stability of the black phosphorus is improved, and the high conductivity and the high catalytic capability of the black phosphorus can also improve the application of the MOF in the lithium-sulfur battery.
The preparation method (1) develops a method for preparing the MOF/BP heterojunction by self-assembly at an oil-water interface, thereby solving the problem that BP is easily oxidized in the air. (2) Develops a nano-fiber phase change diaphragm PPW taking polyacrylonitrile PAN as a shell and paraffin PW as a core, and improves the safety performance of battery operation. (3) The finally obtained PPW/MOF/BP phase change diaphragm can effectively inhibit the shuttle effect of lithium polysulfide, realizes a high-safety and high-performance lithium sulfur battery, and has wide application prospect.
The technical scheme is as follows: the invention adopts the preferable technical scheme that:
according to a first aspect of the present invention, there is provided a method of manufacturing a phase change separator, comprising:
step (a) preparation of MOF/BP heterojunction: forming a metal organic framework/black phosphorus (MOF/BP) heterojunction through interface assembly in an oil-water system, and washing and drying to obtain MOF/BP heterojunction powder;
preparing a phase-change nanofiber membrane (PPW) in the step (b): preparing a Polyacrylonitrile (PAN) solution and a paraffin PW solution into a nanofiber membrane (PPW) with a core-shell structure by a coaxial electrostatic spinning technology;
step (c) preparation of a PPW/MOF/BP phase-change membrane: and dispersing the MOF/BP heterojunction powder in deionized water to form an MOF/BP heterojunction dispersion liquid, depositing the MOF/BP heterojunction dispersion liquid on the nanofiber membrane PPW by a vacuum filtration method, and drying in vacuum to obtain the PPW/MOF/BP phase change membrane.
In some embodiments, in step (a), the oil and water system is a hexane/water system;
the metal organic framework MOF is UiO-66, and black phosphorus is black phosphorus nanosheets.
In some embodiments, the preparation of step (a) a MOF/BP heterojunction comprises: dispersing the black phosphorus nanosheets in deionized water, adding amino terephthalic acid and acetic acid, adding n-hexane after ultrasonic mixing, ultrasonically mixing, adding a zirconium oxychloride aqueous solution, reacting a reaction system in an oil bath, and centrifuging, washing and drying after the reaction is finished to obtain the MOF/BP heterojunction powder.
In some embodiments, in step (b), the solvent of the polyacrylonitrile PAN solution is N, N-Dimethylformamide (DMF), preferably the concentration of the polyacrylonitrile PAN solution is 10 wt%; the solvent of the paraffin PW solution is kerosene; the preferred concentration of the paraffin solution is 40% (v/v).
In some embodiments, the preparing of the phase-change nanofiber membrane PPW of step (b) comprises: adding Polyacrylonitrile (PAN) solution and Paraffin (PW) solution into an injector respectively, and preparing the nanofiber membrane (PPW) with the core-shell structure by a coaxial electrostatic spinning technology.
Further, in the coaxial electrospinning technology, the electrospinning parameter is 18.5kV, the distance between the receiver and the needle is 17cm, and the advancing speed of the polyacrylonitrile PAN solution and the paraffin PW solution is 0.5 mL/h.
In some embodiments, the concentration of the MOF/BP heterojunction dispersion in step (c) is 0.5-5 mg/mL, preferably 1-2 mg/mL.
In some embodiments, the vacuum drying temperature in step (c) is 60 to 80 ℃, preferably 70 ℃.
According to a second aspect of the invention, a PPW/MOF/BP phase-change membrane is provided, which is prepared by the preparation method.
According to a third aspect of the invention, the application of the PPW/MOF/BP phase-change membrane in a lithium sulfur battery is provided.
Has the advantages that: according to the phase change diaphragm for the lithium-sulfur battery and the preparation method thereof, the MOF/BP heterojunction is prepared at the oil-water interface in a self-assembly manner, so that the problem that black phosphorus is easy to oxidize and decompose in the air is solved, the shuttle effect in the lithium-sulfur battery is effectively inhibited, and the cycle performance of the battery is improved. And compounding with a phase-change diaphragm to obtain the high-safety high-performance lithium-sulfur diaphragm material. Has the following advantages:
(1) the method for preparing the MOF/BP heterojunction through self-assembly at the oil-water interface solves the problem that BP is easily oxidized in air.
(2) The nanometer fiber phase change diaphragm PPW takes polyacrylonitrile PAN as a shell and paraffin PW as a core, and improves the safety performance of battery operation.
(3) The finally obtained PPW/MOF/BP phase change diaphragm can effectively inhibit the shuttle effect of lithium polysulfide, realizes a high-safety and high-performance lithium sulfur battery, and has wide application prospect.
Drawings
FIG. 1 is an electron micrograph of a MOF/BP heterojunction prepared in example 1;
FIG. 2 is an electron micrograph of a PPW/MOF/BP phase change membrane prepared in example 1;
FIG. 3 is a graph of the temperature change of an example PPW/MOF/BP phase change membrane under heating;
FIG. 4 is a graph of the cycling performance of a PPW/MOF/BP phase change separator in a lithium sulfur battery.
Detailed Description
The invention is further described with reference to the following figures and examples.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
For the purposes of the present specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and appended claims, are to be understood as being modified in all instances by the term "about". Moreover, all ranges disclosed herein are inclusive of the endpoints and independently combinable.
Example 1
(1) Preparation of MOF/BP heterojunctions
Firstly, 20mg of black phosphorus nanosheets are dispersed in 10mL of deionized water in a 50mL single-neck flask, then 50mg of aminoterephthalic acid and 2mL of acetic acid are added, 10mL of n-hexane solution is added after 5 minutes of ultrasonic treatment, after 20 minutes of continuous ultrasonic treatment, 1mL of aqueous solution of zirconium oxychloride octahydrate (50mg/mL) is finally added, and the reaction system is reacted in an oil bath at 70 ℃ for 24 hours. After the reaction is finished, obtaining a crude product by centrifugation, then washing with DMF and methanol to remove unreacted monomers, and drying in vacuum at 50 ℃ to obtain MOF/BP heterojunction powder.
FIG. 1 is a topographical electron micrograph of a prepared MOF/BP heterojunction; wherein: FIG. 1a is pure black phosphorus nanoplatelets, FIG. 1b is MOF UiO-66 prepared by conventional hydrothermal method, and FIG. 1c is MOF/BP heterojunction prepared in oil water system in example. It can be seen that the MOF/BP heterojunction is successfully self-assembled in an oil-water interface system, and meanwhile, the prepared MOF particles are smaller, so that the black phosphorus is protected, and the stability of the black phosphorus in the air is improved.
(2) Preparation of phase-change nanofiber membrane PPW
1g of PAN powder was dissolved in 10mL of DMF under heating at 50 ℃ to prepare a 10wt% PAN solution. The paraffin wax was melted by heating, and then 4mL of the liquid paraffin wax was added to 6mL of kerosene to prepare a 40% (v/v) paraffin wax solution. Respectively adding the PAN solution and the paraffin solution into an injector, and preparing the phase-change nanofiber membrane PPW with the core-shell structure by a coaxial electrostatic spinning technology. The electrostatic spinning process comprises the following steps: the voltage was 18.5kV, the distance between the receiver and the needle was 17cm, and the advancing rate of the PAN and PW solutions was 0.5 mL/h. And (3) after spinning is finished, separating the film from the receiver, and performing vacuum drying at 70 ℃ for 24 hours to obtain the PPW film.
(3) Preparation of PPW/MOF/BP composite membrane
Cutting the PPW in (2) to 4X 4cm2The method comprises the following steps of (1) placing the square specification on a vacuum filtration device, then dispersing 10mg of the obtained MOF/BP heterojunction powder in 10mL of water, depositing the powder on the surface of a PPW (polypropylene random-access) membrane by a vacuum filtration method, then carrying out vacuum drying at 70 ℃ for 24 hours to obtain a PPW/MOF/BP phase-change membrane, and cutting the membrane into round pieces with the diameter of 19mm for useCycling tests of lithium sulfur batteries.
Example 2
(1) Preparation of MOF/BP heterojunctions
The preparation of MOF/BP heterojunctions was carried out as in example 1.
(2) Preparation of phase-change nanofiber membrane PPW
The preparation of the phase-change nanofibrous membrane PPW was carried out according to example 1.
(3) Preparation of PPW/MOF/BP composite membrane
Cutting the PPW in (2) to 4X 4cm2The method comprises the following steps of (1) placing the square specification on a vacuum filtration device, then dispersing 15mg of the obtained MOF/BP heterojunction powder in 10mL of water, depositing the powder on the surface of a PPW membrane by a vacuum filtration method, then carrying out vacuum drying at 70 ℃ for 24 hours to obtain a PPW/MOF/BP phase-change membrane, and cutting the membrane into round pieces with the diameter of 19mm for the cycle test of the lithium-sulfur battery.
FIG. 2 is an electron micrograph of a PPW/MOF/BP phase change membrane prepared in example 2;
as can be seen from fig. 2a, the nanofiber membrane is successfully prepared by the electrostatic spinning technology, and the alternately interlaced nanofiber framework can construct a diaphragm with rich pores, which is beneficial to the infiltration of electrolyte and the transmission of lithium ions. The contrast difference between the core and the shell of the transmission electron microscope image in fig. 2b indicates that the nanofiber phase change membrane with the core-shell structure is successfully prepared, wherein the shell is Polyacrylonitrile (PAN), the core is Paraffin (PW), the paraffin is encapsulated in the PAN, and the nanofiber membrane formed by electrostatic spinning is marked as PPW. FIG. 2c is a PPW/MOF/BP membrane showing that the MOF/BP heterojunction was successfully deposited on the surface of the membrane by vacuum filtration, with a thickness layer of about 16 microns.
FIG. 3 is a graph of the temperature change of a PPW/MOF/BP phase change membrane under heating;
commercial membranes, PPW and PPW/MOF/BP, were placed on a hot plate and the management of thermal runaway by phase change membranes was studied by temperature increase. It can be seen from fig. 3 that after heating for 10min, the surface temperature of the PPW/MOF/BP is much lower than that of the commercial separator, because paraffin absorbs heat during melting, thereby reducing the temperature of the system, and during transient thermal runaway behavior during battery operation, the paraffin melts rapidly to reduce the temperature of the whole system of the battery, thereby making the battery operate more safely.
FIG. 4 is a graph of the cycling performance of a PPW/MOF/BP phase change separator in a lithium sulfur battery;
as can be seen from FIG. 4, the PPW/MOF/BP membrane prepared in example 2 still has a capacity retention rate of 97.5% after 100 cycles of 0.2C operation, while the capacity of the commercial membrane rapidly decays to 476.8mAh/g after 100 cycles of operation, and the capacity retention rate is only 51.7%. This is due to the shuttling effect of lithium polysulfide and from the cycling performance, it is also shown that PPW/MOF/BP can effectively block shuttling of lithium polysulfide, thereby improving cycling performance of the battery.
Example 3
(1) Preparation of MOF/BP heterojunctions
The preparation of MOF/BP heterojunctions was carried out as in example 1.
(2) Preparation of phase-change nanofiber membrane PPW
The preparation of the phase-change nanofibrous membrane PPW was carried out according to example 1.
(3) Preparation of PPW/MOF/BP composite membrane
Cutting the PPW in (2) to 4X 4cm2The method comprises the following steps of (1) placing the square specification on a vacuum filtration device, then dispersing 20mg of the obtained MOF/BP heterojunction powder in 10mL of water, depositing the powder on the surface of a PPW membrane by a vacuum filtration method, then carrying out vacuum drying at 70 ℃ for 24 hours to obtain a PPW/MOF/BP phase-change membrane, and cutting the membrane into round pieces with the diameter of 19mm for the cycle test of the lithium-sulfur battery.
The cycle performance of the PPW/MOF/BP phase change membrane material prepared in the above examples 1-3 is shown in Table 1, and the cycle performance of the phase change membrane is greatly improved compared with that of a commercial membrane.
TABLE 1 Cyclic Properties of PPW/MOF/BP phase-Change Membrane materials
The invention successfully synthesizes the heterojunction of MOF/BP in an oil-water system, and improves the stability of black phosphorus in the air. Meanwhile, the phase-change nanofiber membrane PPW with the core-shell structure is prepared by utilizing a coaxial electrostatic spinning process, so that the problem of thermal runaway of the battery in the operation process can be effectively solved. The MOF/BP and the PPW are compounded together through a simple suction filtration process, the MOF/BP can effectively inhibit the shuttle effect of lithium polysulfide in the lithium-sulfur battery, the cycle performance of the lithium-sulfur battery is obviously improved, and the PPW phase change diaphragm can regulate the thermal runaway problem of the battery and improve the running safety of the battery. The prepared PPW/MOF/BP phase change membrane remarkably improves the cycle performance of the lithium-sulfur battery, and is expected to be applied to actual life in the future.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for producing a phase change separator, comprising:
step (a) preparation of MOF/BP heterojunction: forming a metal organic framework/black phosphorus (MOF/BP) heterojunction through interface assembly in an oil-water system, and washing and drying to obtain MOF/BP heterojunction powder;
preparing a phase-change nanofiber membrane (PPW) in the step (b): preparing a Polyacrylonitrile (PAN) solution and a paraffin PW solution into a nanofiber membrane (PPW) with a core-shell structure by a coaxial electrostatic spinning technology;
step (c) preparation of a PPW/MOF/BP phase-change membrane: and dispersing the MOF/BP heterojunction powder in deionized water to form MOF/BP heterojunction dispersion liquid, depositing the MOF/BP heterojunction dispersion liquid on the nanofiber membrane PPW by a vacuum filtration method, and carrying out vacuum drying to obtain the PPW/MOF/BP phase change membrane.
2. The method according to claim 1, wherein in the step (a), the oil-water system is a hexane/water system;
and/or the metal organic framework MOF is UiO-66, and black phosphorus is black phosphorus nanosheet.
3. A method according to claim 1 or 2, wherein the step (a) of preparing the MOF/BP heterojunction comprises: dispersing the black phosphorus nanosheets in deionized water, adding amino terephthalic acid and acetic acid, adding n-hexane after ultrasonic mixing, ultrasonically mixing, adding a zirconium oxychloride aqueous solution, reacting a reaction system in an oil bath, and centrifuging, washing and drying after the reaction is finished to obtain the MOF/BP heterojunction powder.
4. The method according to claim 1, wherein in step (b), the solvent of polyacrylonitrile PAN solution is N, N-Dimethylformamide (DMF), preferably the concentration of polyacrylonitrile PAN solution is 10 wt%;
and/or, the solvent of the paraffin PW solution adopts kerosene; the preferred concentration of the paraffin solution is 40% (v/v).
5. The preparation method according to claim 1 or 3, wherein the step (b) of preparing the phase-change nanofiber membrane PPW comprises: adding Polyacrylonitrile (PAN) solution and Paraffin (PW) solution into an injector respectively, and preparing the nanofiber membrane (PPW) with the core-shell structure by a coaxial electrostatic spinning technology.
6. The method according to claim 1, 3 or 5, wherein in the coaxial electrospinning technique, the electrospinning parameters are voltage of 18.5kV, the distance between the receiver and the needle is 17cm, and the advancing rates of the polyacrylonitrile PAN solution and the paraffin PW solution are 0.5 mL/h.
7. The preparation method according to claim 1, wherein in the step (c), the concentration of the MOF/BP heterojunction dispersion is 0.5-5 mg/mL, preferably 1-2 mg/mL.
8. The preparation method according to claim 1, wherein in the step (C), the vacuum drying temperature is 60-80 ℃, preferably 70 ℃.
9. A PPW/MOF/BP phase change membrane prepared by the preparation method of any one of claims 1 to 8.
10. Use of the PPW/MOF/BP phase change membrane of claim 9 in a lithium sulfur battery.
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