CN113178659B - Modified diaphragm, preparation method thereof and lithium-sulfur battery - Google Patents
Modified diaphragm, preparation method thereof and lithium-sulfur battery Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a modified diaphragm, a preparation method thereof and a lithium-sulfur battery, belonging to the technical field of new electrochemical materials, wherein the modified diaphragm consists of a basic diaphragm and a composite material modified layer, wherein the composite material modified layer is formed by compounding a porphyrin-based MOF material and a conductive agent; the preparation method mainly uses meso-tetra (4-carboxyphenyl) porphin, copper nitrate trihydrate and a conductive agent such as graphene, carbon nano tubes and the like as raw materials to prepare Cu 2 And loading the composite material of TCPP-MOF and a conductive agent on the surface of the basic diaphragm through suction filtration, and finally preparing the modified diaphragm. When the modified diaphragm prepared by the method is applied to the lithium-sulfur battery, the shuttle effect of the lithium-sulfur battery can be inhibited, and the specific capacity, the cycling stability and the rate capability of the battery are improved.
Description
Technical Field
The invention relates to the technical field of novel electrochemical materials, in particular to a modified diaphragm, a preparation method thereof and a lithium-sulfur battery.
Background
The consumption of fossil energy such as coal, petroleum and the like in the world is huge at present, and the development and utilization of renewable clean energy are important measures for improving the energy structure and guaranteeing the energy safety. Battery systems are currently the focus of research in the new energy industry as an effective medium for energy storage and release. Since commercialization, lithium ion batteries have been widely used due to their advantages of light weight, environmental friendliness, and long service life, but the theoretical energy density thereof has been difficult to satisfy large-scale industrial applications such as electric vehicles.
In response, researchers have found some alternative battery systems. Wherein the lithium-sulfur battery has a lithium-sulfur battery capacity of 1675 mAh.g -1 Theoretical specific capacity of (1) 2600 Wh.kg -1 The energy density of (a) and the abundance of positive electrode sulfur are attracting attention. However, large-scale industrialization still faces great challenges. The insulation of sulfur and lithium sulfide leads to a decrease in the utilization of active materials both electronically and ionically, and the polysulfide Li, an intermediate product in the battery reaction process 2 S n (n is more than or equal to 4 and less than or equal to 8) is easily dissolved in the electrolyte, so that the active material is lost into the electrolyte, and part of the active material returns to the positive electrode after the discharge is finished.Part of the lithium polysulfide returns to the sulfur positive electrode again after being formed into low-order lithium polysulfide at the negative electrode to generate oxidation reaction, namely, the oxidation reaction is equivalent to internal short circuit, so that the coulomb efficiency of the battery is reduced, and the shuttle effect of the lithium sulfur battery is also a large factor influencing the performance of the lithium sulfur battery.
In order to solve these problems, researchers have conducted many studies such as the compounding of sulfur with other materials, the modification of electrolytes, and the modification of separators. The diaphragm is used as an important component of the battery and plays an important role in separating positive and negative electrodes and transferring ions, which shows that the shuttle effect of the lithium-sulfur battery can be well inhibited by modifying the composition of the diaphragm or designing the two sides of the diaphragm.
In recent years, Metal Organic Frameworks (MOFs) materials have been studied and applied to the preparation of battery anodes and separators. For example, patent CN111403663A discloses a modified diaphragm of a lithium-sulfur battery, which can solve the problem of shuttle effect of the lithium-sulfur battery to a certain extent by alternately filtering Ce-MOF and CNTs on a common commercial diaphragm, thereby improving the specific capacity, coulombic efficiency and cycle life of the battery; however, such a process requires alternate laying of CeO derived from Ce-MOF and enriched in oxygen vacancies 2-x the/C material layer and the activated CNTs layer are used as composite modified layers, the process is complex, and large-scale production is not facilitated, so that a simpler and more effective membrane modification method needs to be developed and designed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a modified diaphragm and a preparation method thereof, when the modified diaphragm is applied to a lithium-sulfur battery, the shuttle effect of the lithium-sulfur battery can be effectively inhibited, the specific capacity, the coulombic efficiency, the rate capability and the cycle life of the battery are improved, the process and the structure are simplified, the large-scale production is favorably realized, and the production cost is reduced.
The invention also aims to provide a lithium-sulfur battery, which adopts the modified diaphragm, and greatly improves the specific capacity, coulombic efficiency, rate capability and cycle life of the battery.
The purpose of the invention can be realized by the following technical scheme:
the modified diaphragm comprises a basic diaphragm and a composite material modified layer, wherein the composite material modified layer is arranged on one side of the basic diaphragm, and the composite material modified layer comprises a conductive agent and Cu 2 TCPP-MOF。
As a further improvement of the invention, the basic diaphragm is one of a PE diaphragm, a PP diaphragm and a PE/PP composite diaphragm.
As a further improvement of the present invention, the conductive agent is graphene or carbon nanotubes.
As a further improvement of the invention, the loading capacity of the composite material modified layer is 0.3-0.6 mg/cm 2 。
A preparation method of a modified diaphragm comprises the following steps:
a. mixing and dispersing copper nitrate trihydrate and a conductive agent in a solvent A to obtain a dispersion liquid A;
b. dissolving meso-tetra (4-carboxyphenyl) porphin in a solvent B to obtain a solution B;
c. mixing and stirring the dispersion liquid A and the solution B, and heating the mixture in an ultrasonic and oil bath to synthesize Cu 2 TCPP-MOF and obtaining Cu 2 A composite of TCPP-MOF and a conductive agent;
d. and washing the obtained composite material, uniformly dispersing the composite material in a solvent C to obtain a dispersion liquid B, carrying out suction filtration on the dispersion liquid B on one side of a basic diaphragm, and naturally drying to obtain a modified diaphragm, wherein the modified diaphragm comprises the basic diaphragm and a composite material modified layer.
As a further development of the invention, both solvent a and solvent B in step a and step B are prepared from dimethylformamide and ethanol according to a ratio of 3: 1, and the conductive agent is used for synthesizing Cu 2 The TCPP-MOF was mixed in solvent A.
As a further improvement of the invention, in the step c, the ultrasonic frequency is 25 k-30 kHz, the oil bath heating temperature is 80-85 ℃, and the reaction time is 10-12 h.
As a further improvement of the invention, the solvent C in the step d is ethanol, and the solvent C is repeatedly washed by the ethanol, so that the Cu is filtered and filtered on the basic diaphragm 2 TCPP-MThe mass ratio OF OF to the conductive agent is 1: 1 to 3.
The lithium-sulfur battery comprises a negative electrode, a positive electrode and electrolyte, and is characterized in that the lithium-sulfur battery further comprises the modified diaphragm, and the composite material modified layer of the modified diaphragm is arranged right opposite to the positive electrode of the lithium-sulfur battery.
The invention has at least the following beneficial effects:
the modified diaphragm provided by the invention consists of a basic diaphragm and a composite material modified layer, wherein the composite material modified layer comprises Cu 2 TCPP-MOF and a conductive agent. Wherein Cu 2 TCPP-MOF has exposed N sites that can bind effectively to polysulfides to block it and thereby impair the shuttling effect of lithium sulfur batteries; the conductive agent (such as graphene) is used for providing conductivity and promoting electron transfer, and the combination of the conductive agent and the electron transfer greatly improves the specific capacity, rate performance, coulombic efficiency and cycling stability of the lithium-sulfur battery.
Compared with the prior art, the preparation method of the modified diaphragm provided by the invention has the advantages that the process is simple, the large-scale production is favorably realized, and the production cost is reduced.
Compared with the prior art, the lithium-sulfur battery provided by the invention has the advantages that the specific capacity, the coulombic efficiency, the rate capability and the cycle life of the battery are greatly improved by adopting the modified diaphragm.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given in detail for the purpose of better understanding the contents of the present invention and are not intended to limit the scope of the present invention.
Example 1
The embodiment provides a modified diaphragm for a lithium-sulfur battery, which comprises a basic diaphragm and a composite material modified layer, wherein the composite material modified layer is arranged on one side of the basic diaphragm, and the composite material modified layer comprises a conductive agent and Cu 2 TCPP-MOF. Wherein, Cu 2 TCPP-MOF has exposed N sites that can bind effectively to polysulfides to block it and thereby impair the shuttling effect of lithium sulfur batteries; the conductive agent is used for providing conductivityThe transfer of electrons is promoted, and the combination of the two greatly improves the specific capacity, the rate capability, the coulombic efficiency and the cycling stability of the lithium-sulfur battery.
Optionally, the base separator is a Polyethylene (PE) separator, a polypropylene (PP) separator, a PE/PP composite single-layer separator, or the like, and may be one or more of them. I.e., the base separator is one or more of the current commercial battery separators, in this embodiment, the base separator is selected from the group consisting of polypropylene (PP) separator Celgard 2500.
Optionally, the conductive agent is graphene or carbon nanotubes. In this embodiment, the conductive agent is graphene.
The preparation method of the modified diaphragm for the lithium-sulfur battery provided by the embodiment comprises the following specific steps:
a. 21.7mg of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 0) Mixing with 12.5mg of Graphene (GO) and dispersing in a mixed solution of 30ml of Dimethylformamide (DMF) and 10ml of ethanol to obtain a dispersion A;
b. dissolving 10.76mg of meso-tetra (4-carboxyphenyl) porphin (TCPP) in a mixed solution of 15ml of Dimethylformamide (DMF) and 5ml of ethanol to obtain a solution B;
c. mixing and stirring the dispersion liquid A and the solution B obtained in the step a and the step B, performing ultrasonic treatment, and heating in an oil bath kettle at the temperature of 80 ℃ for 10 hours to synthesize Cu 2 TCPP-MOF and obtaining Cu 2 A composite of TCPP-MOF and a conductive agent;
d. and washing the obtained composite material, uniformly dispersing the composite material in ethanol to form dispersed heat B, then carrying out suction filtration on one side of the basic diaphragm by using the dispersed liquid B, and naturally drying to obtain the modified diaphragm for the lithium-sulfur battery, wherein the modified diaphragm comprises the basic diaphragm and a composite material modified layer. Wherein the loading capacity of the composite material modified layer is 0.41mg/cm 2 ， Cu 2 The mass ratio of TCPP-MOF to Graphene (GO) is 1: 1.
e. finally, the modified diaphragm prepared in the embodiment is cut into round pieces with a preset size, such as 19mm diameter round pieces, by a slicer, and then the modified diaphragm can be applied to lithium-sulfur batteries.
As a preferred example, in this example, solvent a for preparing dispersion a and solvent B for preparing solution B were prepared using a mixture of dimethylformamide and ethanol in a ratio of 3: 1, wherein dimethylformamide acts primarily as a solvent and a small amount of ethanol acts to balance the polarity of the solution and partially volatilize during the reaction to provide pressure inside the reaction vessel.
As a preferred embodiment, the conductive agent in this embodiment is synthesized with Cu 2 The TCPP-MOF was previously mixed in solvent A to allow direct growth of the MOF on the conductive agent.
As a preferred embodiment, the temperature of the oil bath is 80 ℃ and the heating time is 10 hours in this embodiment, but not limited thereto, optionally, the temperature of the oil bath is 80-85 ℃ and the reaction time is 10-12 hours, and the raw materials can completely react to form the MOF at the temperature and the reaction time without decomposition or generation of byproducts.
In this embodiment, the ultrasonic wave is used to make the mixture of the dispersion liquid A and the solution B more uniform, and preferably, the frequency of the ultrasonic wave is 25k to 30kHz, which is a frequency at which the solute can be dispersed sufficiently uniformly.
The modified separator prepared in this example is assembled into a lithium sulfur battery, and the electrochemical properties of the modified separator of this example are described below. The specific steps of assembling the lithium-sulfur battery with the modified separator of this example are as follows:
(1) preparation of the positive electrode: in the experiment, sulfur is used as a positive electrode active substance, carbon black is used as a conductive carrier, polyvinylidene fluoride (PVDF) is used as a binder, and the mass ratio of the sulfur to the carbon black is 7: 2: 1, adding a dispersing agent NMP, magnetically stirring for 10 hours in a sealed environment, then uniformly coating the uniformly mixed slurry on an aluminum foil, and drying for 12 hours in a vacuum drying oven at 60 ℃. The resulting sheet was cut into 12mm diameter pieces using a microtome.
(2) Assembling the battery: and (3) assembling a button cell in a glove box by using a lithium sheet as a negative electrode, using the sulfur/carbon composite positive electrode prepared in the step (1) as a positive electrode and using the modified diaphragm prepared in the example 1, wherein one side of the modified diaphragm, which is provided with the composite material modified layer, faces the positive electrode. The electrolyte is prepared by dissolving 1.0M LiTFSI and 0.1M LiNO 3 Is prepared from DME and DOL (volume ratio is 1: 1).
(3) And (3) electrochemical performance testing: and (3) placing the prepared battery into a 30 ℃ thermostat, and performing charge and discharge tests, wherein the voltage window is 1.7-2.8V.
(4) Comparative experiment: in order to improve the performance of the lithium-sulfur battery compared with the modified diaphragm of the lithium-sulfur battery, a blank Celgard 2500 diaphragm which is not modified is assembled into a button battery under the same condition, and a charge-discharge test is carried out.
Test results show that the lithium-sulfur battery assembled by the modified diaphragm in the embodiment has the initial capacity of 957mAh/g after 1C constant-current charge and discharge, the capacity is 536mAh/g after 500 cycles, and the capacity retention rate is 56%; while the initial capacity of the lithium-sulfur battery assembled by the blank Celgard 2500 diaphragm is only 753mAh/g, the capacity is still 364mAh/g after 300 cycles, and the capacity retention rate is only 48%. Therefore, the modified diaphragm can effectively improve the specific capacity of the lithium-sulfur battery, prolongs the cycle life and enhances the rate capability.
Example 2
This example was prepared in the same manner as example 1 except that Cu was supported on Celgard 2500 separator 2 The mass ratio of TCPP-MOF to GO is 1: 2, the other conditions were the same.
Compared with example 1, the specific capacity, cycling stability and rate capability of the lithium-sulfur battery assembled by the modified diaphragm of the embodiment are similar and slightly improved. When 1C is charged and discharged at constant current, the initial capacity reaches 978mAh/g, the capacity still reaches 571mAh/g after 500 cycles, the capacity retention rate is 58%, and the rate capability is correspondingly improved.
Example 3
The preparation method of this example is the same as that of example 1 except that Cu is supported on Celgard 2500 separator 2 The mass ratio of TCPP-MOF to GO is 1: 3, the other conditions were the same.
Compared with the embodiment 1, the lithium-sulfur battery assembled by the modified diaphragm of the embodiment has similar and slightly improved specific capacity, cycling stability and rate performance. In 1C constant current charge and discharge, the initial capacity reaches 966mAh/g, the capacity still reaches 554mAh/g after 500 cycles, the capacity retention rate is 57%, and the rate capability is correspondingly improved.
The above examples 1-3 illustrate the specific capacity, cycling stability and rate capability of lithium sulfur batteries with Cu on the base separator 2 The mass ratio of TCPP-MOF to GO is not positively correlated, but has a preferable region, and the invention discovers that Cu is obtained through a plurality of experimental innovations 2 The mass ratio of TCPP-MOF to GO is preferably: 1: 1 to 3.
Experimental example 4
The preparation method of this example is the same as that of example 1, except that the loading amount of the composite material modified layer on the Celgard 2500 diaphragm is 0.68mg/cm 2 、 0.59mg/cm 2 、0.51mg/cm 2 、0.30mg/cm 2 、0.22mg/cm 2 Other conditions were the same. The test results are given in table 1 below.
TABLE 1 electrochemical Properties of different loadings of modified layers of composite materials
As can be seen from the electrochemical performances of different loading amounts of the composite material modified layer in the table 1, the electrochemical performance of the battery is not increased along with the increase of the loading amount, but has a preferable interval, and multiple experimental innovations show that the loading amount of the composite material modified layer is preferably 0.3-0.6 mg/cm 2 More preferably, the loading amount of the composite material modified layer is 0.41-0.5 mg/cm 2 。
Experimental example 5
The preparation method of this example is the same as example 1, except that no conductive agent is added to the composite material modified layer, i.e. only pure Cu is added 2 TCPP-MOF, the conditions being otherwise the same.
The lithium sulfur battery assembled with the modified separator of this example had a reduced specific capacity, cycling stability and rate performance compared to example 1. In 1C constant current charge and discharge, the initial capacity reaches 834mAh/g, the capacity still has 426mAh/g after 500 cycles, the capacity retention rate is 51%, and the rate capability is also reduced. This proves that Cu 2 The TCPP-MOF modified layer can enhance the performance of the lithium-sulfur batteryBut the reinforcing effect of the composition with the conductive agent is better.
Experimental example 6
The preparation method of this example is the same as example 1 except that Cu is not added to the modified layer 2 The conditions of other implementation are the same as TCPP-MOF, i.e. only pure conductive agent is added, and graphene is used as the conductive agent in this example.
The lithium-sulfur battery assembled with the modified separator of this example had a reduced specific capacity, cycling stability and rate performance compared to example 1. In 1C constant-current charge and discharge, the initial capacity reaches 853mAh/g, the capacity is still 446mAh/g after 500 cycles, and the capacity retention rate is 54%, which indicates that the pure conductive agent has no good effect of enhancing the battery performance.
In summary, the invention innovatively proposes forming a composite material modified layer by the porphyrin-based MOF material and the conductive agent, and innovatively proposes forming a composite material modified layer by meso-tetra (4-carboxyphenyl) porphin (TCPP) and copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 0) And the conductive agent such as Graphene (GO), Carbon Nanotubes (CNTs) and the like are used as raw materials to prepare Cu 2 And (3) loading the composite material of TCPP-MOF and a conductive agent on the surface of the basic diaphragm through suction filtration. Experimental test results show that the shuttle effect of the lithium-sulfur battery can be effectively inhibited by the modified diaphragm prepared by the method, and the specific capacity, the cycling stability and the rate capability of the lithium-sulfur battery are improved. Compared with the prior art, the preparation method of the modified diaphragm provided by the invention has the advantages that the process is simple, the multilayer modified layers are formed without alternative suction filtration, the large-scale production is favorably realized, and the production cost is reduced. Compared with the prior art, the lithium-sulfur battery provided by the invention has the advantages that the specific capacity, the coulombic efficiency, the rate capability and the cycle life of the battery are greatly improved by adopting the modified diaphragm.
While the preferred embodiments of the present invention have been described in detail, those skilled in the art will appreciate that various modifications and changes can be made to the embodiments without departing from the spirit of the present invention.
Claims (9)
1. The modified diaphragm is characterized by comprising a basic diaphragm and a composite material modified layer, wherein the composite material modified layer is arranged on one side of the basic diaphragm, and the composite material modified layer comprises a conductive agent and Cu 2 TCPP-MOF。
2. The modified membrane of claim 1, wherein: the basic diaphragm is one of a PE diaphragm, a PP diaphragm and a PE/PP composite diaphragm.
3. The modified membrane of claim 1, wherein: the conductive agent is graphene or carbon nanotubes.
4. The modified membrane of claim 1, wherein: the loading capacity of the composite material modified layer is 0.3-0.6 mg/cm 2 。
5. A preparation method of a modified diaphragm is characterized by comprising the following steps:
a. mixing and dispersing copper nitrate trihydrate and a conductive agent in a solvent A to obtain a dispersion liquid A;
b. dissolving meso-tetra (4-carboxyphenyl) porphin in a solvent B to obtain a solution B;
c. mixing and stirring the dispersion liquid A and the solution B, and heating the mixture in an ultrasonic and oil bath to synthesize Cu 2 TCPP-MOF and obtaining Cu 2 A composite of TCPP-MOF and a conductive agent;
d. and washing the obtained composite material, uniformly dispersing the composite material in a solvent C to obtain a dispersion liquid B, carrying out suction filtration on the dispersion liquid B on one side of a basic diaphragm, and naturally drying to obtain a modified diaphragm, wherein the modified diaphragm comprises the basic diaphragm and a composite material modified layer.
6. The method for producing a modified separator according to claim 5, wherein: both solvent a and solvent B in step a and step B were prepared from dimethylformamide and ethanol according to 3: 1, and the conductive agent is used for synthesizing Cu 2 Mixing in solvent A before TCPP-MOF。
7. The method for producing a modified separator according to claim 5, wherein: in the step c, the ultrasonic frequency is 25 k-30 kHz, the oil bath heating temperature is 80-85 ℃, and the reaction time is 10-12 h.
8. The method for producing a modified separator according to claim 5, wherein: in the step d, the solvent C is ethanol, and the solvent C is repeatedly washed by the ethanol, so that the Cu which is filtered and filtered on the basic diaphragm is obtained 2 The mass ratio of TCPP-MOF to the conductive agent is 1: 1 to 3.
9. A lithium-sulfur battery comprising a negative electrode, a positive electrode and an electrolyte, wherein the lithium-sulfur battery further comprises the modified separator of any one of claims 1 to 4, and the composite modified layer of the modified separator is arranged opposite to the anode of the lithium-sulfur battery.
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| CN114583389A (en) * | 2022-02-25 | 2022-06-03 | 广东工业大学 | Co-based MOF-derived metal/carbon composite (Co/C) membrane and preparation method and application thereof |
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