CN117673655A - Composite diaphragm for lithium-sulfur battery, preparation method of composite diaphragm and lithium-sulfur battery - Google Patents
Composite diaphragm for lithium-sulfur battery, preparation method of composite diaphragm and lithium-sulfur battery Download PDFInfo
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Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite diaphragm for a lithium-sulfur battery, a preparation method of the composite diaphragm and the lithium-sulfur battery, and belongs to the technical field of lithium-sulfur battery diaphragm materials. The composite diaphragm for the lithium-sulfur battery comprises a base film and a two-dimensional-two-dimensional composite structure interlayer deposited on the surface of the base film; the two-dimensional-two-dimensional composite structure interlayer is prepared by mixing MXene and LDH in a solution, and then vacuum-filtering the mixture on the surface of a base film; MXene and LDH self-assemble into two-dimensional-two-dimensional mutual under electrostatic adsorption effectAn interlaced layered structure; the mass ratio of the MXene to the LDH is 1:0.75-1.5. The lithium sulfur battery diaphragm prepared by the invention can improve the self-stacking phenomenon of MXene sheets and promote Li + Shuttle of (a); the lithium sulfur battery can also effectively adsorb polysulfide, can be used as a conductive matrix, promotes the transformation and utilization of polysulfide, reduces the irreversible loss of active substances, thereby relieving the capacity attenuation of the lithium sulfur battery, has simple preparation process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery diaphragm materials, in particular to a composite diaphragm for a lithium-sulfur battery, a preparation method of the composite diaphragm and the lithium-sulfur battery.
Background
The information disclosed in the background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an admission or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
The lithium-sulfur battery has extremely high theoretical capacity (1675 mAh g) -1 ) And energy density (2600 Wh kg) -1 ) The high abundance of sulfur element on the earth also makes the sulfur element have the advantage of low cost, so that the sulfur element becomes a next-generation high-performance secondary battery candidate, is hopeful to replace a lithium ion battery, and has wide development prospect.
Lithium sulfur batteries also face a number of problems. Positive electrode active material sulfur and discharge product Li of battery 2 S is an insulating material, is difficult to discharge when being used independently, and needs to be added with a conductive agent to discharge; sulfur undergoes higher polysulfide, lower polysulfide and eventually goes to Li during charge and discharge 2 S, wherein high-order polysulfide is easily dissolved in electrolyte, and migrates to and from a negative electrode through a diaphragm, so that a shuttle effect is caused by migration back and forth, and the electrochemical performance of a lithium-sulfur battery is seriously influenced; sulfur and Li 2 The volume expansion caused by the density difference of S damages the electrode structure; lithium dendrites grow during dissolution/deposition of the lithium anode, reducing battery capacity and coulombic efficiency. The problems can cause irreversible capacity loss of the battery, and the rate performance is reduced, so that the practical application of the lithium-sulfur battery is seriously hindered.
The conductive intermediate layer is added between the positive electrode and the diaphragm of the lithium-sulfur battery, so that the shuttle effect of the lithium-sulfur battery can be effectively inhibited, the utilization of polysulfide is promoted, and the cycling stability of the lithium-sulfur battery is improved. The adhesion of the intermediate layer to the membrane to construct the integrated composite membrane is an efficient intermediate layer preparation mode. Although the performance of the lithium-sulfur battery is obviously improved by preparing the composite diaphragm, the problems of complex preparation, high cost and the like of some intermediate layer materials still exist at present, and the large-scale production of the lithium-sulfur battery is difficult to realize. The MXene material has good conductivityThe unique two-dimensional structure is applied to the middle layer of the lithium-sulfur battery to a certain extent, however, in the preparation process, the MXene material is seriously accumulated in the same dimension, and the self-stacking phenomenon exists, so that Li is caused + Is blocked.
Patent CN 113948816B (publication date: 2022.09.23) discloses a MXene composite material modified membrane for lithium-sulfur battery and a preparation method thereof, wherein a base membrane is used as a filter membrane, and folds MXene@SnS are modified on the base membrane by vacuum filtration 2 The ZnO composite material can obviously improve the capacity of a lithium-sulfur battery and the rate capability of the battery, and well solve the problems caused by the shuttle effect. However, the membrane preparation process of the patent needs to adopt complicated steps to prepare the folded MXene, and involves multi-step high-temperature hydrothermal reaction and high-temperature sintering steps, so that the preparation cost is high.
Therefore, how to provide a method which has simple preparation process, low cost, avoids the self-stacking phenomenon of MXene and improves Li + The mobility and the capacity fading of the lithium sulfur battery can be reduced by inhibiting polysulfide shuttling of the lithium sulfur battery, so that the problem to be solved is urgent.
Disclosure of Invention
In view of the above, the invention provides a composite diaphragm for a lithium sulfur battery, a preparation method thereof and a lithium sulfur battery, wherein the composite diaphragm for the lithium sulfur battery is formed by attaching a two-dimensional-two-dimensional MXene-LDH composite interlayer to a diaphragm base film, two-dimensional nano sheets of MXene and LDH are self-assembled into a mutually-interweaved two-dimensional-two-dimensional composite layered structure through electrostatic action, so that the stacking phenomenon of the two-dimensional nano sheets can be effectively inhibited, the shuttle of polysulfide of the lithium sulfur battery can be inhibited, the capacity attenuation of the lithium sulfur battery can be reduced, the preparation process is simple, the cost is low, and the composite diaphragm is suitable for industrial production.
In a first aspect, the invention provides a composite membrane for a lithium-sulfur battery, which comprises a base membrane and a two-dimensional-two-dimensional composite structure interlayer deposited on the surface of the base membrane; the two-dimensional-two-dimensional composite structure interlayer is prepared by mixing MXene and LDH in a solution, and then vacuum-filtering the mixture on the surface of a base film; MXene and LDH are self-assembled into a two-dimensional-two-dimensional mutually-interweaved layered structure under the action of electrostatic adsorption; the mass ratio of the MXene to the LDH is 1:0.75-1.5.
Preferably, the MXene includes, but is not limited to, ti 3 C 2 、Ti 2 C、Ti 2 N、V 2 C、V 2 N、V 3 C 4 、Ti 3 One or more of the CNs.
Preferably, the LDH includes, but is not limited to, one or more of NiFe-LDH, niCo-LDH, feAl-LDH, niAl-LDH, niTi-LDH; further preferred is NiCo-LDH.
Preferably, the thickness of the two-dimensional-two-dimensional composite structure interlayer is 0.001-5 μm.
Preferably, the base film includes, but is not limited to, one of a polyethylene based film, a polypropylene based film, a glass fiber film, a cellulose film.
Preferably, the base film thickness is 2 to 100 μm.
Preferably, the base film is a microporous film, and the pore diameter of micropores is 1-100 nm.
In a second aspect, the invention provides a preparation method of the composite separator for the lithium-sulfur battery, which comprises the following steps:
slowly dropwise adding LDH dispersion liquid into MXene dispersion liquid under the stirring condition to prepare mixed dispersion liquid; stirring the mixed dispersion liquid after ultrasonic treatment, and then taking a base film as a filter film, and carrying out vacuum suction filtration on the mixed dispersion liquid to obtain a composite membrane for the lithium-sulfur battery; in the mixed dispersion, MXene and LDH form a two-dimensional-two-dimensional interlaced layered structure by electrostatic self-assembly.
Preferably, in the mixed dispersion liquid, the total mass concentration of the MXene and the LDH is 0.05-10 mg/mL; the ultrasonic time is 20-40 min.
Preferably, the MXene has a platelet size of 0.02-60 μm and the LDH has a platelet size of 0.02-60 μm.
Preferably, the ratio of the area of the base film to the amount of the mixed dispersion is 1cm 2 1-10 mL, wherein the surface loading of the two-dimensional-two-dimensional composite structure interlayer is 0.01-0.5mg/cm 2 。
Preferably, the method further comprises the step of vacuum drying the composite diaphragm for the lithium-sulfur battery after the vacuum filtration step; preferably, the temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 4-12 h.
In a third aspect, the present invention provides a lithium sulfur battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte;
the diaphragm comprises the composite diaphragm for the lithium-sulfur battery prepared by the technical scheme or the preparation method of the technical scheme.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the composite diaphragm for the lithium-sulfur battery, provided by the invention, through suction filtration and deposition of the mixed dispersion liquid, MXene and LDH are self-assembled into a two-dimensional-two-dimensional composite structure film under the action of electrostatic adsorption, so that the self-stacking phenomenon of MXene sheets is greatly improved, and Li is promoted + Shuttle of (a); meanwhile, the two-dimensional-two-dimensional composite structure film can effectively adsorb polysulfide, prevent the polysulfide from diffusing to the cathode, and can also be used as a conductive matrix to promote the conversion and utilization of the polysulfide and reduce the irreversible loss of active substances, thereby relieving the capacity attenuation of the lithium-sulfur battery;
(2) The preparation method of the composite diaphragm for the lithium-sulfur battery is simple, the reaction process does not involve high-temperature hydrothermal reaction or high-temperature calcination reaction, the energy consumption is low, and the cost is low; meanwhile, the chemical reaction is not involved in the formation process of the composite diaphragm, so that the mass loss is avoided, the dosage between MXene and LDH is convenient to regulate and control, and the assembly difficulty of the lithium-sulfur battery is reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. It will be obvious to those skilled in the art that other figures may be obtained from these figures without the inventive effort.
FIG. 1 is a surface Scanning Electron Microscope (SEM) image, a cross-sectional SEM image and an EDS element map of the composite separator prepared in example 1, comparative example 2 of the present invention; wherein (a-c) are surface SEM images of composite separator films of example 1, comparative example 2, and comparative example 1, in that order; (d-f) cross-sectional SEM images of composite separator films of example 1, comparative example 2, and comparative example 1, in that order; (g-k) EDS element mapping for the composite separator of example 1, comparative example 2, comparative example 1;
fig. 2 is a cycle curve (a) of the separator-assembled lithium sulfur battery prepared in example 1, comparative examples 1 to 3 of the present invention and a rate capability (b) of the composite separator-assembled lithium sulfur battery of example 1.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytically pure or conventional purity used in the field of lithium-sulfur battery separator preparation.
In one exemplary embodiment of the invention, a composite separator for a lithium-sulfur battery is provided, comprising a base film and a two-dimensional-two-dimensional composite structural interlayer deposited on the surface of the base film; the two-dimensional-two-dimensional composite structure interlayer is prepared by mixing MXene and LDH in a solution, and then vacuum-filtering the mixture on the surface of a base film; MXene and LDH are self-assembled into a two-dimensional-two-dimensional mutually-interweaved layered structure under the action of electrostatic adsorption; the mass ratio of the MXene to the LDH is 1:0.75-1.5.
As described in the background art, MXene undergoes self-stacking when forming a self-supporting film by vacuum filtration, which causes a decrease in conductivity and makes it difficult to function effectively. The invention adopts LDH (layered double hydroxide) with layered structure and positively charged surface, and in the vacuum filtration process, the LDH and MXene are self-assembled to form a two-dimensional-two-dimensional composite structure interlayerGreatly improves the self-stacking phenomenon of MXene, enlarges the interlayer pore space, and is favorable for Li + Thereby improving the electrochemical performance of the lithium sulfur battery. The MXene surface has negative charges, the LDH surface has positive charges, and the electrostatic action between the two is a physical action, and no chemical action occurs, so that the mass loss is effectively avoided.
It should be noted that the mass ratio of MXene to LDH has a more critical effect, and when the amount of LDH added is too small, it is difficult to perform an effective intercalation function; when the amount of LDH added is too large, the conductivity of the composite separator will be reduced because LDH itself is not conductive, resulting in a decrease in electrochemical performance of the lithium-sulfur battery.
The proper mass ratio can ensure that the two can fully play a synergistic effect, can simultaneously play the excellent conductivity of MXene, chemisorb polysulfide and promote the quick conversion of the MXene, and the LDH has good adsorption and catalytic capability on the polysulfide, and the two-dimensional-two-dimensional composite structure after intercalation has higher porosity, thereby being beneficial to Li + In addition, can promote the uniform nucleation and deposition of metallic lithium. The mass ratio of the MXene to the LDH is preferably 1:0.75-1.5; further preferably 1:1.
The present invention is not particularly limited in the type of MXene, and can be carried out by using the type of MXene commonly used in the art, including but not limited to Ti 3 C 2 、Ti 2 C、Ti 2 N、V 2 C、V 2 N、V 3 C 4 、Ti 3 One of the CNs.
The invention does not limit the type of LDH, and common LDH can be adopted, including but not limited to one of NiFe-LDH, niCo-LDH, feAl-LDH and NiAl-LDH; the invention is preferably a NiCo-LDH. The introduction of transition metal can enhance chemical interaction between LDH and sulfur species, thereby generating strong fixing effect and catalytic effect, and further realizing quick and durable sulfur electrochemical reaction. In addition, MXene and LDH lamellar are stacked in a staggered manner to form staggered pore distribution, so that the nano-sheets in the pores can be used as supporting walls of the pores, and further, the strength and the stability are better on the basis of guaranteeing the bulk and higher adsorption performance.
The two-dimensional-two-dimensional composite structure interlayer is deposited on at least one surface of the base film, and particularly can be deposited on one surface of the base film, or the two-dimensional-two-dimensional composite structure interlayer can be deposited on both surfaces of the base film.
The thickness of the two-dimensional-two-dimensional composite structure interlayer is not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art, so that the lithium sulfur battery is of a better integral coating structure, and the cycle performance and the safety performance of the lithium sulfur battery are improved, wherein the thickness of the two-dimensional-two-dimensional composite structure interlayer is 0.001-5 mu m.
The invention is in principle not particularly limited in the selection of the base film, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention is better to ensure the compatibility with the MXene and LDH two-dimensional-two-dimensional composite structure interlayer, simultaneously facilitate the formation of the composite structure interlayer, and improve the adsorption performance and Li + Preferably, the base film is a microporous film having a microporous pore size of 1 to 100nm. The base film is preferably one of a polyethylene base film, a polypropylene base film, a glass fiber film and a cellulose film; the thickness of the base film is 2-100 mu m.
The two-dimensional-two-dimensional composite structure interlayer with the capability of absorbing and converting polysulfide provided by the invention adopts a two-dimensional-two-dimensional mutually-crossed structural design, has good compatibility with a base film, and can achieve good absorption effect; the integral coating structure of the composite diaphragm for the lithium-sulfur battery provides excellent comprehensive performance, can improve the cycle performance and the safety performance of the lithium-sulfur battery, effectively solves the defects of the common diaphragm, and solves the problems of high compactness, poor air permeability and poor electric conductivity of the MXene film prepared by a vacuum suction filtration method.
In another exemplary embodiment of the present invention, there is provided a method for preparing the above composite separator for lithium sulfur battery, comprising the steps of:
slowly dropwise adding LDH dispersion liquid into MXene dispersion liquid under the stirring condition to prepare mixed dispersion liquid; stirring the mixed dispersion liquid after ultrasonic treatment, and then taking a base film as a filter film, and carrying out vacuum suction filtration on the mixed dispersion liquid to obtain a composite membrane for the lithium-sulfur battery; in the mixed dispersion, MXene and LDH form a two-dimensional-two-dimensional interlaced layered structure by electrostatic self-assembly.
The structure, composition and parameters of the raw materials involved in the preparation method and the corresponding preferred principles of the invention can correspond to those of the materials in the composite separator for the lithium sulfur battery and the corresponding preferred principles, and are not described in detail herein.
The specific preparation steps of the MXene dispersion liquid of the present invention are not particularly limited, and a method for preparing a MXene dispersion liquid commonly used in the art may be adopted, and the method for preparing a MXene dispersion liquid of the present invention is preferably as follows: the MAX phase is stripped by LiF and HCl etching to obtain layered MXene, and the layered MXene is dispersed in water to obtain a dispersion liquid of MXene, wherein the thickness of a sheet layer of MXene is 1-10nm.
The preferred stripping method of the invention is as follows: adding MAX phase into LiF and hydrochloric acid solution, stirring for 20-30 h at 30-40 ℃, washing with water, ultrasonic and centrifuging to obtain layered MXene.
The method for preparing the LDH dispersion is not particularly limited, and the method can be a common preparation method in the field, such as a coprecipitation method or a hydrothermal method. The invention preferably comprises the following steps: preparing layered double hydroxide LDH by a coprecipitation method, grinding, ion exchanging and stripping to obtain an oligolayer LDH, and dispersing the oligolayer LDH into water to obtain LDH dispersion liquid.
The step of preparing the layered double hydroxide LDH by the coprecipitation method is not particularly limited, and the method for preparing the LDH by the conventional coprecipitation method in the field is adopted, and the method is preferably as follows: dissolving the bimetallic salt and ammonium fluoride in water, dropwise adding ammonia water, stirring for 4-10 h, centrifuging, washing and drying in vacuum to obtain the catalyst. When the bimetallic salt is a nickel salt and a cobalt salt, the molar ratio of nickel to cobalt is preferably 2:0.8 to 1.2.
The specific mode and specific parameters of the grinding process are not particularly limited, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, so that the intercalation condition of LDH is better improved, the adsorption performance is improved, the cycle performance and the safety performance of the lithium-sulfur battery are further improved, and the grinding time is preferably 40-90 min, more preferably 60min.
The ion exchange method is not particularly limited, and the ion exchange method commonly used in the field is adopted, wherein the preferred ion exchange method comprises the following steps: placing the ground LDH into NaCl and hydrochloric acid solution, stirring for 20-30 h, centrifugally washing, vacuum drying, grinding again for 3-10 min, and placing into NaNO 3 Stirring the mixture in the solution for 20 to 30 hours, and carrying out centrifugal washing and vacuum drying to obtain LDH-NO 3 。
The specific mode of the stripping treatment is not particularly limited, and the stripping treatment mode commonly used in the field is adopted, wherein the preferred stripping treatment method comprises the following specific steps: ion-exchanged LDH-NO 3 Dissolving in formamide, vibrating for 20-30 h, carrying out ultrasonic treatment for 20-40 min, and centrifuging to obtain supernatant, namely LDH dispersion liquid. The exfoliation treatment is to obtain single-layer LDH nanoplatelets.
The present invention does not particularly limit the total mass concentration of MXene and LDH in the mixed dispersion liquid as long as a two-dimensional-two-dimensional composite structure interlayer of a specific thickness range can be formed. In order to construct a suitable coating structure, the total mass concentration of MXene and LDH according to the invention is preferably 0.05-10 mg/mL. In order to uniformly mix the MXene and LDH, the ultrasonic time is preferably 20 to 40 minutes.
The present invention is not particularly limited in terms of the MXene platelet size, the LDH platelet size, and the amount of the mixed dispersion, as long as a two-dimensional-two-dimensional composite structural interlayer of a specific thickness range can be formed. The sheet size of the MXene is 0.02-60 mu m, more preferably 20-600nm, most preferably 300-500nm; the sheet size of the LDH is 0.02-60 μm, more preferably 20-600nm, most preferably 300-500nm; the ratio of the area of the base film to the amount of the mixed dispersion is preferably 1cm 2 1-10 mL, wherein the surface loading of the two-dimensional-two-dimensional composite structure interlayer is 0.01-0.5mg/cm 2 。
The invention also comprises the step of vacuum drying the composite diaphragm for the lithium-sulfur battery after the vacuum filtration step; preferably, the temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 4-12 h.
In another exemplary embodiment of the present invention, there is provided a lithium sulfur battery including a positive electrode, a negative electrode, a separator, and an electrolyte;
the diaphragm comprises the composite diaphragm for the lithium-sulfur battery prepared by the technical scheme or the preparation method of the technical scheme.
The definition and kind of the lithium sulfur battery are not particularly limited in principle, and can be selected and adjusted according to practical application, product requirements and quality requirements by those skilled in the art according to conventional definition and kind of lithium sulfur battery known to those skilled in the art.
The composite diaphragm for the lithium-sulfur battery has better adsorption and conversion performance on lithium polysulfide and can promote Li + The transmission of the lithium sulfur battery can effectively improve the performance of the lithium sulfur battery.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
(1) Preparation of MXene Dispersion:
MXene strips titanium aluminum carbide (Ti) by LiF/HCl etching 3 AlC 2 ) The preparation method comprises the following specific steps: 0.99g LiF was added to 10mL 12M hydrochloric acid and 1g Ti was added while stirring 3 AlC 2 Stirring in water bath at 35deg.C for 24 hr, washing the obtained dispersion with water for 5-6 times until pH is 6. After that, it was sonicated for 1 hour and centrifuged for 1 hour (3500 rpm) to remove bottom sediment, resulting in a exfoliated layered MXene dispersion. An additional amount of deionized water was added to sonicate for 2 hours to prepare a 2mg/mL MXees dispersion.
(2) Preparation of NiCo-LDH dispersion:
4mmol Ni%NO 3 ) 2 ·6H 2 O，2mmol Co(NO 3 ) 2 ·6H 2 O and 0.67g NH 4 F, adding 250mL of water, stirring to form pink, dropwise adding 2.75mL of 25% ammonia water, stirring and reacting for 6 hours to form dark blue; transferring into a centrifuge tube, centrifuging at 8000rpm for 5min, washing twice with water and ethanol, combining into a test tube, and vacuum drying at 60deg.C for 24 hr to give a grass green color;
grinding the prepared NiCo-LDH for 1h, dissolving 0.375mol of NaCl in 250mL of water, stirring, adding 0.105mL of concentrated hydrochloric acid (12M), pouring the NiCo-LDH into the solution, stirring for 24h to be slightly acidic, at 800 rpm, centrifuging for 5min for several times to obtain NiCo-LDH-Cl, vacuum drying at 60 ℃ for 24h, and grinding for 5min; preparing NaNO of 0.15mol/L 3 Adding NiCo-LDH-Cl, stirring for 24h, stirring for 7000rpm, centrifuging for several times in 5min, and vacuum drying at 60deg.C for 24h to obtain NiCo-LDH-NO 3 The method comprises the steps of carrying out a first treatment on the surface of the NiCo-LDH-NO 3 Dissolving in formamide, vibrating for 24 hours, performing ultrasonic treatment for 30 minutes, centrifuging for several times at 300rpm for 3 minutes, removing precipitates to obtain NiCO-LDH dispersion liquid, calculating the concentration, and dispersing into a certain amount of deionized water to prepare 2mg/mL NiCO-LDH dispersion liquid;
(3) Preparation of composite separator for lithium-sulfur cell (mass ratio of MXene to NiCo-LDH is 1:1):
7.5mL of 2mg/mL of MXene dispersion was dissolved in 285mL of deionized water, 7.5mL of 2mg/mL of NiCo-LDH dispersion was added while stirring, the mixture was sonicated for 30min, stirred for 2h, and placed on a vacuum filter for suction filtration with a polypropylene membrane model 3501 to obtain a composite membrane for lithium-sulfur batteries, designated as LDH/MXene-1.
FIG. 1c is a cross-sectional SEM image of an LDH/MXene-1 composite membrane prepared in this example, and it can be seen from the figure that the cross-sectional thickness is 1164nm, which is a loose porous two-dimensional-two-dimensional network composite structure, demonstrating that the introduction of two-dimensional metal compounds NiCo-LDHs inhibits the stacking of sheets of MXene.
Fig. 1a is a surface SEM image of the LDH/MXene-1 composite membrane prepared in this example, from which it can be seen that a distinct lamellar structure is observed, the smaller lamellar structure being LDHs, the larger MXene nanoplatelets, confirming that the two materials are uniformly composited together.
Comparative example 1
The difference from example 1 is that the mass ratio of MXene to NiCo-LDH of the comparative example is 1:0.5, and the preparation process of the composite separator for lithium sulfur batteries is as follows:
10mL of 2mg/mL of MXenes dispersion is dissolved in 285mL of deionized water, 5mL of 2mg/mL of LDH solution is added while stirring, after mixing, ultrasonic treatment is carried out for 30min, stirring is carried out for 2h, and the mixture is placed on a vacuum suction filter to carry out suction filtration by using a polypropylene diaphragm with the model of 3501, thus obtaining the composite diaphragm for lithium-sulfur batteries, which is marked as LDH/MXene-0.5.
FIG. 1f is a cross-sectional SEM image of an LDH/MXene-0.5 composite membrane prepared in this example, and it can be seen from the figure that the cross-sectional thickness is 779nm, the pores are small when the LDH addition amount is small, and the lamellar structure cannot be opened well.
Comparative example 2
The difference from example 1 is that the mass ratio of MXene to NiCo-LDH of the comparative example is 1:2, and the preparation process of the composite separator for the lithium sulfur battery is as follows:
5mL of the MXenes dispersion liquid with 2mg/mL is dissolved in 285mL of deionized water, 10mL of the LDH solution with 2mg/mL is added under stirring, the mixture is subjected to ultrasonic treatment for 30min after mixing, the mixture is stirred for 2h, and the mixture is placed on a vacuum suction filter to carry out suction filtration by using a polypropylene diaphragm with the model of 3501, so that a composite diaphragm for a lithium-sulfur battery is obtained and is marked as LDH/MXene-2.
FIG. 1e is a cross-sectional SEM image of the LDH/MXene-2 composite membrane prepared in this comparative example, and it can be seen from the figure that the cross-sectional thickness is 1150nm, and the LDHs usage is increased, but the cross-sectional thickness is increased but the pores of the LDH/MXene-1 cross-section are smaller.
Comparative example 3
The separator of this comparative example used an unmodified polypropylene separator model 3501.
Test examples
The separators prepared in examples and comparative examples were used to assemble lithium sulfur batteries and tested for performance.
Assembling a lithium-sulfur battery: mixing sublimed sulfur, acetylene black and LA133 according to the mass ratio of 70:20:10, uniformly coating the slurry on a current collector aluminum foil, vacuum drying at 60 ℃ for 12 hours, and cutting into (10 multiplied by 10) mm 2 Is a pole piece. Subsequent poleThe tablets were dried under vacuum at 60℃for 12h and transferred to a glove box for further use. The metal lithium sheet is used as a counter electrode, and 1% LiNO is used 3 1,3 Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) dissolved in 1M LiTFSI (volume ratio of 1:1) was used as an electrolyte, and examples 1 and comparative examples 1 to 3 were used as separators, respectively. In a glove box under argon atmosphere (H 2 O＜0.1ppm，O 2 < 0.1 ppm) was assembled into a CR2016 button lithium sulfur battery.
The electrochemical performance test method of the lithium sulfur battery comprises the following steps: testing the battery on a battery testing system, wherein the charging and discharging voltage ranges from 1.7V to 2.8V, and the initial capacities of the battery under the conditions of current densities of 0.1C, 0.2C, 0.5C, 1C and 2C are achieved; at the same time, the capacity after 100 cycles at 0.1C (1C=1675 mAh.g) -1 ). In Table 1, the amounts of the modifying solutions were 25.12mL.
Table 1 test parameters of examples, comparative separator and corresponding lithium sulfur battery
Fig. 1 (a) is a surface Scanning Electron Microscope (SEM) image of the LDH/MXene-1 composite membrane prepared in example 1, which is a two-dimensional sheet structure, and the two are interpenetrated after being compounded, so that the structure is compact, and it can be seen that LDHs are uniformly dispersed on the surface of MXene, and meanwhile, due to some stacking phenomenon generated after membrane drawing, a wrinkled sheet structure can be observed. FIG. 1 (b-c) are surface SEM images of LDH/MXene-2 (comparative example 2) and LDH/MXene-0.5 (comparative example 1) separators, respectively, and a significant lamellar structure was observed at higher LDH content. Meanwhile, three groups of membranes with different proportions are observed in cross section, and fig. 1 (d-f) are respectively pictures of the cross sections of the membranes of the example 1, the comparative example 2 and the comparative example 1, a remarkable two-dimensional interweaved composite structure can be observed, the cross section thickness of the LDH/MXene-1 (example 1) composite membrane is 1164nm, and the two-dimensional-two-dimensional network composite structure with loose holes is proved that the introduction of the two-dimensional metal compound LDHs enlarges the lamellar spacing of the MXene. The LDH/MXene-2 (comparative example 2) composite membrane has a thickness of 1150nm, which is also a loose porous two-dimensional network composite structure, but the pores between the sheets are obviously smaller than that of the LDH/MXene-1 composite membrane; the porosity of LDH/MXene-0.5 (comparative example 1) was the worst and the cross-sectional thickness was only 779nm. The two-dimensional interweaved composite structure can block the migration of polysulfide to the negative electrode through physical action, inhibit the shuttle effect, and simultaneously facilitate the wetting of electrolyte and improve the ionic conductivity.
As shown in the EDS energy spectrum of FIG. 1 (g-h), four elements C, ti, co, ni are uniformly distributed on the surface of the LDH/MXene diaphragm. Wherein C, ti is derived from MXene, co and Ni are derived from NiCo-LDH, which shows that the MXene and the LDH are well dispersed in the compounding process.
FIG. 2 (a) is a graph of 100 cycles at 0.1C for a sulfur electrode and three different ratio separators. The pure sulfur electrode had a specific discharge capacity of only 729.1mAh/g at 0.1C, and a capacity fade of 343.7mAh/g after 100 cycles. The electrode using LDH/MXene-0.5 had an initial specific capacity of 848.7mAh/g at 0.1C and a capacity of 564.6mAh/g after 100 cycles. MXenes act to enhance conductivity and physical adsorption, but higher levels of MXenes tend to self-stack, affecting cell discharge. The LDH/MXene-2 had an initial specific capacity of 866.9mAh/g at 0.1C and a capacity of 384.9mAh/g after 100 cycles. When the content of LDHs is high, the MXene is easily coated by the LDHs so as to reduce the conductivity, and the insufficient content of the MXene can lead to insufficient adsorption capacity to polysulfide and has limited performance improvement. It can be seen that the cells using LDH/MXene-1 separator exhibited an optimal initial specific discharge capacity at 0.1C of 1137.6mAh/g at 0.1C and a capacity of 622.6mAh/g after 100 cycles, significantly superior to pure sulfur electrodes and electrodes with other ratios of separators. FIG. 2 (b) is the rate capability of an LDH/MXene-1 separator assembled cell, the specific capacity of the electrode at 0.2C was 806.1mAh/g, and at a rate of 1C, the specific capacity remained at 481.9mAh/g, indicating that the separator improved the discharge performance of the cell.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The composite diaphragm for the lithium-sulfur battery is characterized by comprising a base film and a two-dimensional-two-dimensional composite structure interlayer deposited on the surface of the base film; the two-dimensional-two-dimensional composite structure interlayer is prepared by mixing MXene and LDH in a solution, and then vacuum-filtering the mixture on the surface of a base film; MXene and LDH are self-assembled into a two-dimensional-two-dimensional mutually-interweaved layered structure under the action of electrostatic adsorption; the mass ratio of the MXene to the LDH is 1:0.75-1.5.
2. The composite separator for lithium sulfur battery of claim 1 wherein said MXene comprises, but is not limited to, ti 3 C 2 、Ti 2 C、Ti 2 N、V 2 C、V 2 N、V 3 C 4 、Ti 3 One or more of the CNs.
3. The composite separator for a lithium-sulfur battery of claim 1 wherein said LDH includes, but is not limited to, one or more of NiFe-LDH, niCo-LDH, feAl-LDH, niAl-LDH, niTi-LDH.
4. The composite separator for lithium-sulfur battery according to claim 1, wherein the thickness of the two-dimensional-two-dimensional composite structural interlayer is 0.001 to 5 μm; the thickness of the base film is 2-100 mu m.
5. The composite separator for lithium-sulfur battery according to claim 1, wherein the base film is one selected from the group consisting of a polyethylene-based film, a polypropylene-based film, a glass fiber film, and a cellulose film; the base film is a microporous film, and the aperture of the micropores is 1-100 nm.
6. The method for producing a composite separator for lithium-sulfur batteries according to any one of claims 1 to 5, comprising the steps of:
slowly dropwise adding LDH dispersion liquid into MXene dispersion liquid under the stirring condition to prepare mixed dispersion liquid; stirring the mixed dispersion liquid after ultrasonic treatment, and then taking a base film as a filter film, and carrying out vacuum suction filtration on the mixed dispersion liquid to obtain a composite membrane for the lithium-sulfur battery; in the mixed dispersion, MXene and LDH form a two-dimensional-two-dimensional interlaced layered structure by electrostatic self-assembly.
7. The process of claim 6, wherein the MXene has a platelet size of 0.02-60 μm and the LDH has a platelet size of 0.02-60 μm.
8. The process according to claim 6, wherein the total mass concentration of MXene and LDH in the mixed dispersion is 0.05 to 10mg/mL; the ultrasonic time is 20-40 min; the ratio of the area of the base film to the amount of the mixed dispersion was 1cm 2 1-10 mL, wherein the surface loading of the two-dimensional-two-dimensional composite structure interlayer is 0.01-0.5mg/cm 2 。
9. The method according to claim 6, further comprising a step of vacuum-drying the composite separator for lithium-sulfur battery after the vacuum-filtration step; the temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 4-12 h.
10. A lithium sulfur battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte;
the separator comprises the composite separator for a lithium-sulfur battery according to any one of claims 1 to 5 or the composite separator for a lithium-sulfur battery prepared by the preparation method according to any one of claims 6 to 9.
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