CN114368788B - Composite material and battery composite diaphragm - Google Patents

Composite material and battery composite diaphragm Download PDF

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Publication number
CN114368788B
CN114368788B CN202111569146.4A CN202111569146A CN114368788B CN 114368788 B CN114368788 B CN 114368788B CN 202111569146 A CN202111569146 A CN 202111569146A CN 114368788 B CN114368788 B CN 114368788B
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composite material
montmorillonite
battery
composite
lithium
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CN114368788A (en
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庞浩
吴炼
洪培萍
赵一芳
高树曦
廖兵
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Institute of Chemical Engineering of Guangdong Academy of Sciences
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Institute of Chemical Engineering of Guangdong Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

The invention discloses a composite material and a battery composite diaphragm. A composite material comprising a transition metal sulfide intercalated and a coated montmorillonite; the chemical formula of the transition metal sulfide is MS 2 M includes any one or more of Fe, cu, mo, ti, co, ni, mn, nb, zr, W, re and Ta. A battery composite separator comprising a substrate; the surface of the substrate is coated with a coating; the coating comprises a composite material. The composite material provided by the invention organically combines the strong adsorption effect of montmorillonite on lithium polysulfide with the catalytic effect of transition metal sulfide, so that adsorption and catalytic synergistic effect are formed by utilizing the adsorption and catalytic active sites inside and outside the composite material, thereby realizing the reinforcement of the adsorption and conversion process of polysulfide in the charge-discharge process of the lithium sulfur battery, effectively inhibiting the shuttle effect of polysulfide, and further greatly improving the cycle stability of the lithium sulfur battery.

Description

Composite material and battery composite diaphragm
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to a composite material and a battery composite diaphragm.
Background
The rapid development of emerging technologies such as electric vehicles and power grid energy storage has put higher demands on the energy density of secondary batteries.The lithium sulfur battery has extremely high theoretical energy density (2600 Wh kg -1 ) And is an important point and hot spot for research in the field of secondary batteries. However, the problem of slow shuttle effect and redox reaction kinetics of lithium polysulfide is still a key problem that hinders the realization of large-scale commercial application of lithium sulfur batteries. Research shows that the strategy of adsorption and catalysis is an effective way for solving the key problems of the lithium sulfur battery. The strategy of "adsorption+catalysis" mainly comprises: (1) Heteroatom doping of carbon materials (porous carbon, carbon nanotubes, graphene, etc.); (2) Introducing electrocatalysts such as metal oxygen/sulfur/nitride and the like into the nonpolar carbon material; (3) Electrocatalysts such as metal oxide/sulfur/nitride are introduced into polar materials such as MOFs, MXene and the like. On the basis of anchoring lithium polysulfide by physical/chemical adsorption, catalytic active sites are introduced into the material to promote rapid conversion of the lithium polysulfide anchored on the surface of the material, so that accumulation of lithium polysulfide in the electrolyte is avoided, and shuttle effect is greatly inhibited.
The natural montmorillonite clay mineral material has a special two-dimensional layered structure and extremely strong lithium polysulfide adsorption capacity, and has good thermal stability, chemical stability and mechanical stability, so that the natural montmorillonite clay mineral material is increasingly used for adsorbing and anchoring lithium polysulfide in a lithium sulfur battery to inhibit a shuttle effect. In the prior art, wook Ahn et al (W.Ahn, S.N.Lim, D.U.Lee, K.B.Kim, Z.Chen, S.H.Yeon, interaction mechanism between a functionalized protective layer and dissolved polysulfide for extended cycle life of lithium sulfur batteries, J.Mater.chem.A., 2015,3,9461-9467.) report that a surface modified composite membrane prepared by coating montmorillonite onto the diaphragm surface of a lithium sulfur battery can effectively anchor adsorption of lithium polysulfide on the positive electrode side of the lithium sulfur battery, thereby effectively inhibiting shuttle effect and greatly improving the cycle stability of the lithium sulfur battery. However, the above prior art merely uses the chemisorption of montmorillonite to inhibit the shuttle effect of lithium polysulfide, and cannot catalyze the transformation of lithium polysulfide, so that it is difficult to realize the application of lithium sulfur battery with high energy density. The surface coating modified lithium-sulfur battery diaphragm in the prior art has insufficient adsorption or catalysis effect on lithium polysulfide, and the surface coating is easy to block the pore channel structure of the diaphragm, so that the shuttle effect problem is difficult to effectively overcome due to the reduction of the lithium ion transmission performance of the composite diaphragm.
Disclosure of Invention
In order to overcome the problem that the conventional separator is difficult to realize application in a lithium sulfur battery with high energy density due to the shuttle effect of lithium polysulfide in the prior art, one of the purposes of the invention is to provide a composite material, and the other purpose of the invention is to provide a battery composite separator.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a composite material comprising a transition metal sulfide intercalated and a coated montmorillonite; the chemical formula of the transition metal sulfide is MS 2 M includes any one or more of Fe, cu, mo, ti, co, ni, mn, nb, zr, W, re and Ta.
Preferably, in the composite material, the transition metal sulfide has the chemical formula of MS 2 M includes any one or more of Fe, cu, mn, zr, co, ni; further preferably, M comprises any one or more of Fe, cu, mn, zr and Ni; still further preferably, M comprises any one or more of Fe, cu and Mn; still more preferably, M is Fe.
Further preferably, in the composite material, nano transition metal sulfide particles are intercalated between montmorillonite layers, and transition metal sulfide crystallites are coated on the surface of montmorillonite.
Preferably, in the composite material, the mass ratio of the transition metal sulfide to the montmorillonite is (0.5-20): 1; it is further preferable that the mass ratio of the transition metal sulfide to the montmorillonite is (0.6-1.8): 1.
The invention also provides a preparation method of the composite material, which comprises the following steps: and adding transition metal salt into the montmorillonite suspension, adding a sulfur source, and performing hydrothermal reaction to obtain the composite material.
Preferably, in the preparation method of the composite material, transition metal salt is added into montmorillonite suspension, after sufficient cation exchange treatment, a sulfur source is added, and hydrothermal reaction is carried out, so that the composite material is obtained; further preferably, the transition metal salt is added into the montmorillonite suspension, stirred for more than 2 hours, and then the sulfur source is added for hydrothermal reaction, so that the composite material is obtained.
Preferably, in the preparation method of the composite material, after the transition metal salt is added into the montmorillonite suspension, stirring is carried out for more than 2 hours at the temperature of 50-70 ℃; further preferably, the montmorillonite suspension is stirred for more than 2 hours at the temperature of 55-65 ℃ after the transition metal salt is added; still more preferably, the transition metal salt is added to the montmorillonite suspension and then stirred at 60℃for 2 hours or more.
Preferably, in the preparation method of the composite material, after adding the sulfur source, stirring is carried out under the room temperature condition; further preferably, the stirring time is 0.5-1.5h under room temperature conditions; still more preferably, the stirring time is 0.8-1.2 hours at room temperature; still more preferably, the stirring time is 1h at room temperature.
Preferably, in the preparation method of the composite material, the temperature of the hydrothermal reaction is 160-240 ℃; further preferably, the temperature of the hydrothermal reaction is 180-220 ℃; still further preferably, the temperature of the hydrothermal reaction is 190-210 ℃; still more preferably, the temperature of the hydrothermal reaction is 200 ℃.
Preferably, in the preparation method of the composite material, the hydrothermal reaction time is 18-30 hours; further preferably, the hydrothermal reaction time is 20 to 26 hours; still further preferably, the hydrothermal reaction time is from 23 to 25 hours; still more preferably, the hydrothermal reaction time is 24 hours.
Preferably, in the preparation method of the composite material, the mass concentration of the montmorillonite suspension is 0.5-6wt%; further preferably, the montmorillonite suspension has a mass concentration of 1-4wt%; still further preferred, the montmorillonite suspension has a mass concentration of 1.5-3wt%; still more preferably, the montmorillonite suspension has a mass concentration of 2wt%.
Preferably, in the preparation method of the composite material, the transition metal salt is ferrous salt, and the ferrous salt is FeSO 4 ·7H 2 O。
Preferably, in the preparation method of the composite material, the mass ratio of montmorillonite to transition metal salt is 1g: (5-15) mmol; further preferably, the mass ratio of montmorillonite to transition metal salt is 1g: (8-12) mmol; still further preferably, the mass ratio of montmorillonite to transition metal salt is 1g:10mmol.
Preferably, in the preparation method of the composite material, the sulfur source comprises thiosulfate, thiourea and elemental sulfur; further preferably, the thiosulfate comprises at least one of sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate; still more preferably, the thiosulfate is sodium thiosulfate.
Further preferably, in the preparation method of the composite material, the molar mass ratio of the transition metal salt to the thiosulfate is 1: (0.8-1.2); still further preferred is a transition metal salt to thiosulfate molar mass ratio of 1:1.
further preferably, in the preparation method of the composite material, the molar mass ratio of the transition metal salt to the elemental sulfur is 1: (0.4-0.6); still further preferably, the molar mass ratio of transition metal salt to elemental sulfur is 1:0.5.
preferably, the preparation method of the composite material further comprises the steps of filtering to obtain a filter cake, and washing and drying the obtained filter cake to obtain the composite material; further preferably, the filter cake is washed with deionized water for 2-6 times.
The invention also provides a battery composite membrane, which comprises a base material; the surface of the substrate is coated with a coating; the coating comprises the composite material.
Preferably, such a battery composite separator is a lithium sulfur battery composite separator.
Preferably, the battery composite separator has a coating layer containing a composite material with a mass of 0.1-2mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the It is further preferred that the coating contains the composite material in a mass of 0.4-1.6mg/cm 2 。
Preferably, the substrate of the battery composite separator comprises at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyacrylonitrile, polyacrylic acid, polyethylene oxide, polymethyl methacrylate and polyethyleneimine.
The invention also provides a preparation method of the battery composite diaphragm, which comprises the following steps: mixing the composite material with a binder and a solvent to obtain slurry; and coating the slurry on the surface of a substrate, and drying to obtain the battery composite diaphragm.
Preferably, in the preparation method of the battery composite separator, the binder comprises at least one of polyvinylidene fluoride (PVDF), polyethylene oxide, polytetrafluoroethylene, polyvinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, polyethyleneimine, polyacrylic acid, gelatin, sodium alginate and styrene butadiene rubber.
Preferably, in the preparation method of the battery composite membrane, the solvent comprises at least one of Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO); further preferably, the solvent is N-methylpyrrolidone (NMP).
Preferably, in the preparation method of the battery composite membrane, the mass ratio of the composite material to the binder is (6-12): 1, a step of; further preferably, the mass ratio of the composite material to the binder is (7-11): 1, a step of; still further preferred, the mass ratio of the composite material to the binder is (8-10): 1, a step of; still more preferably, the mass ratio of the composite material to the binder is 9:1.
preferably, in the method for preparing the battery composite separator, the drying is performed under vacuum.
Preferably, in the preparation method of the battery composite membrane, the drying temperature is 50-70 ℃; further preferably, the drying temperature is 55-65 ℃; still more preferably, the temperature of drying is 60 ℃.
Preferably, in the preparation method of the battery composite membrane, the drying time is 10-14h; further preferably, the drying time is 11-13 hours; still more preferably, the drying time is 12 hours.
The invention also provides application of the composite material and/or the battery composite diaphragm in a lithium-sulfur battery.
The beneficial effects of the invention are as follows:
the composite material provided by the invention comprises the transition metal sulfide intercalated and coated montmorillonite, and the strong adsorption effect of the montmorillonite on lithium polysulfide is organically combined with the catalytic effect of the transition metal sulfide, so that the adsorption and catalytic synergistic effect is formed by utilizing the adsorption and catalytic active sites inside and outside the composite material, the reinforcement of the adsorption and conversion process of polysulfide in the charge and discharge process of a lithium sulfur battery is realized, the shuttle effect of polysulfide is effectively inhibited, and the cycling stability of the lithium sulfur battery is greatly improved.
The invention utilizes the intercalation function of transition metal sulfide to montmorillonite, and constructs a high-speed lithium ion transmission channel structure between montmorillonite layers, thereby effectively improving the lithium ion transmission performance of lithium sulfur battery diaphragm and greatly improving the multiplying power performance of lithium sulfur battery.
According to the invention, a simple hydrothermal synthesis method is adopted, a crystal in-situ growth technology is utilized to synthesize nano transition metal sulfide particles in situ between montmorillonite layers, and transition metal sulfide microcrystals are generated on the surfaces of the montmorillonite, so that the prepared composite material has a composite structure of transition metal sulfide intercalation and coated montmorillonite, and the organic combination of the montmorillonite and the transition metal sulfide is realized, so that the composite material has the synergistic effect of adsorption and catalysis on polysulfide, the shuttle effect is effectively inhibited, and the cycle stability of the lithium-sulfur battery is promoted.
Compared with the lithium sulfur battery diaphragm modified by montmorillonite or transition metal sulfide in the prior art, the composite material prepared by the invention has the advantages that the performance is obviously improved: on one hand, the catalysis of transition metal sulfide is introduced on the basis of strong chemical adsorption of montmorillonite, so that the synergistic effect of adsorption and catalysis is achieved on polysulfide generated in the charge and discharge process of the lithium sulfur battery, the electrochemical reaction kinetics process of the lithium sulfur battery is greatly promoted, accumulation of polysulfide in electrolyte is avoided, and the influence of the shuttle effect of polysulfide on the battery performance is effectively relieved. On the other hand, a high-speed lithium ion transmission channel is constructed in the transition metal sulfide intercalation and cladding montmorillonite composite material, so that the high-speed migration of lithium ions in the charge and discharge process of the battery is greatly promoted, and the rate capability of the battery is greatly improved.
Compared with the lithium sulfur battery assembled by the lithium sulfur battery diaphragm based on montmorillonite or transition metal sulfide coating modification in the prior art, the cycle stability and the multiplying power performance of the lithium sulfur battery assembled by the lithium sulfur battery diaphragm prepared by the preparation method are obviously improved.
Drawings
FIG. 1 is a FeS obtained in example 1 2 SEM images of intercalated and coated montmorillonite composites.
FIG. 2 is a FeS produced in example 1 2 TEM image of intercalated and coated montmorillonite composites.
Fig. 3 is a surface SEM image of the battery composite separator manufactured in example 1.
Fig. 4 is an SEM image of a lithium sulfur battery separator without surface coating modification.
Fig. 5 is a graph showing charge-discharge cycle stability of the lithium sulfur batteries assembled in the examples and the comparative examples.
Fig. 6 is a graph showing the rate performance of the assembled lithium sulfur batteries in examples and comparative examples.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or by prior art methods unless otherwise specified. Unless otherwise indicated, assays or testing methods are routine in the art.
Example 1
2g of montmorillonite is added into 100mL of deionized water, stirred and dispersed uniformly to obtain a suspension, and 20mmol of FeSO is added into the suspension 4 ·7H 2 Stirring for 2h at 60 ℃ after O, then adding 20mmol of sodium thiosulfate and 10mmol of elemental sulfur, stirring for 1h at room temperature, transferring the mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 200 ℃, naturally cooling, filtering to recover a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying at 80 ℃ for 12h to obtain FeS 2 An intercalated and coated montmorillonite composite material, the morphology and structure of which are shown in fig. 1 and 2. The above-mentioned compositeAdding the material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to the mass ratio of 9:1, fully stirring to form a viscous slurry, coating the slurry on one side surface of a commercial polypropylene lithium sulfur battery diaphragm by adopting a simple blade coating mode, and vacuum drying for 12 hours at 60 ℃ to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS 2 The amount of intercalated and coated montmorillonite composite material was 0.5mg/cm 2 And the composite separator is applied to a lithium-sulfur battery. The SEM image of the surface of the composite separator is shown in fig. 3. SEM images of the lithium sulfur battery separator without surface coating modification are shown in fig. 4.
As shown in FIG. 1, the montmorillonite is coated with FeS with particle size of 200-300nm 2 Microcrystals, and a large amount of FeS can be clearly seen between montmorillonite sheets 2 Is present. As shown in FIG. 2, feS between montmorillonite layers 2 The particle size of the nano particles is not more than 10nm. As shown in FIG. 3, it can be clearly seen that the surface of the battery composite diaphragm prepared by the invention is modified with a layer of FeS 2 The intercalation and cladding montmorillonite composite material particles are uniformly distributed on the surface of the diaphragm to form a coating layer with a porous structure. As shown in fig. 4, it can be seen that the lithium sulfur battery separator without surface coating modification has a through-hole structure and uniform pore distribution.
Example 2
The difference from example 1 is FeS formed between montmorillonite layers and on the surface 2 The amounts of (3) are different, specifically:
2g of montmorillonite is added into 100mL of deionized water, stirred and dispersed uniformly to obtain a suspension, 10mmol of FeSO is added into the suspension 4 ·7H 2 Stirring for 2h at 60 ℃ after O, then adding 10mmol of sodium thiosulfate and 5mmol of elemental sulfur, stirring for 1h at room temperature, transferring the mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 200 ℃, naturally cooling, filtering to recover a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying at 80 ℃ for 12h to obtain FeS 2 Intercalated and coated montmorillonite composites. The composite material and PVDF (polyvinylidene fluoride) are added into a certain volume in a mass ratio of 9:1The NMP (N-methyl pyrrolidone) solvent is fully stirred into a thick slurry, the slurry is coated on one side surface of a commercial polypropylene lithium sulfur battery diaphragm by adopting a simple blade coating mode, and the battery composite diaphragm is obtained after vacuum drying for 12 hours at 60 ℃, and the diaphragm surface coating contains FeS 2 The amount of intercalated and coated montmorillonite composite material was 1mg/cm 2 And the composite separator is applied to a lithium-sulfur battery.
Example 3
The difference from example 1 is FeS formed between montmorillonite layers and on the surface 2 The amounts of (3) are different, specifically:
2g of montmorillonite is added into 100mL of deionized water, stirred and dispersed uniformly to obtain a suspension, and 30mmol of FeSO is added into the suspension 4 ·7H 2 Stirring for 2h at 60 ℃ after O, then adding 30mmol of sodium thiosulfate and 15mmol of elemental sulfur, stirring for 1h at room temperature, transferring the mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 200 ℃, naturally cooling, filtering to recover a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying at 80 ℃ for 12h to obtain FeS 2 Intercalated and coated montmorillonite composites. Adding the composite material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent in a mass ratio of 9:1, fully stirring into a viscous slurry, coating the slurry on one side surface of a commercial polypropylene lithium sulfur battery diaphragm by adopting a simple blade coating mode, and vacuum drying at 60 ℃ for 12 hours to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS 2 The amount of intercalated and coated montmorillonite composite material was 0.2mg/cm 2 And the composite separator is applied to a lithium-sulfur battery.
Comparative example 1
The difference compared to example 1 is that FeS in the composite material 2 Only exists between montmorillonite layers, specifically:
2g of montmorillonite is added into 100mL of deionized water, stirred and dispersed uniformly to obtain a suspension, and 20mmol of FeSO is added into the suspension 4 ·7H 2 Stirring at 60deg.C for 2 hr, filtering, and repeatedly washing filter cake with deionized waterAnd drying the washing liquid at 105 ℃ after no sulfate ions exist, so as to obtain the montmorillonite subjected to ferrous ion exchange. Dispersing the montmorillonite subjected to ferrous ion exchange in 100mL of deionized water, adding 20mmol of sodium thiosulfate and 10mmol of elemental sulfur, stirring at room temperature for 1h, transferring the mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24h, naturally cooling, filtering to recover a filter cake, washing the filter cake with deionized water for 3 times, and vacuum drying at 80 ℃ for 12h to obtain FeS 2 An intercalated montmorillonite composite. Above FeS 2 Adding the intercalated montmorillonite composite material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to the mass ratio of 9:1, fully stirring into a viscous slurry, coating the slurry on one side surface of a commercial polypropylene lithium sulfur battery diaphragm by adopting a simple blade coating mode, and vacuum drying for 12 hours at 60 ℃ to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS 2 The amount of intercalated montmorillonite composite material was 1.5mg/cm 2 And the composite separator is applied to a lithium-sulfur battery.
Comparative example 2
The difference compared to example 1 is that FeS in the composite material 2 The preparation method mainly exists on the surface of montmorillonite, and specifically comprises the following steps:
2g of montmorillonite is added into 100mL of deionized water, stirred and dispersed uniformly to obtain a suspension, and 20mmol of FeSO is added into the suspension 4 ·7H 2 After O,20mmol of sodium thiosulfate and 10mmol of elemental sulfur, transferring the mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, naturally cooling, filtering to recover a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying at 80 ℃ for 12 hours to obtain FeS 2 Coated montmorillonite composite material. Above FeS 2 Adding the coated montmorillonite composite material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to the mass ratio of 9:1, fully stirring into a viscous slurry, coating the slurry on one side surface of a commercial polypropylene lithium sulfur battery diaphragm by adopting a simple blade coating mode, and vacuum drying for 12 hours at 60 ℃ to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS 2 CoatingThe amount of montmorillonite composite material was 0.8mg/cm 2 And the composite separator is applied to a lithium-sulfur battery.
Comparative example 3
The difference compared with example 1 is that montmorillonite and FeS are used 2 After physical mixing of the particles, the commercial battery separator is subjected to surface coating, specifically:
combining pure montmorillonite with pure FeS 2 Mixing the particles in a mass ratio of 1:1.2, and fully and uniformly grinding to obtain montmorillonite and FeS 2 And (3) a mixture. Adding the mixture and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to the mass ratio of 9:1, fully stirring into a viscous slurry, coating the slurry on one side surface of a commercial polypropylene lithium sulfur battery diaphragm by adopting a simple blade coating mode, and vacuum drying at 60 ℃ for 12 hours to obtain montmorillonite/FeS 2 Composite separator coated with mixture, the surface of which is coated with montmorillonite/FeS-containing film 2 The amount of the mixture was 0.5mg/cm 2 And the composite separator is applied to a lithium-sulfur battery.
Comparative example 4
The difference compared with example 1 is that the surface coating modification of the lithium sulfur battery separator is not performed, specifically:
and directly adopting an unmodified lithium sulfur battery diaphragm to assemble a battery for testing the charge and discharge performance.
The separators of example 1 and comparative examples 1 to 4 were used in lithium sulfur batteries for performance test, and the test results were as follows:
FeS prepared in example 1 was used 2 The charge-discharge cycle performance and the multiplying power performance of the lithium sulfur battery assembled by the composite diaphragm coated by the intercalated and coated montmorillonite composite material are respectively shown in fig. 5 and 6, the discharge specific capacity of the battery can reach 1156mAh/g after 100 times of circulation under the current density of 0.2C, the capacity retention rate reaches 88%, the discharge specific capacity of the battery can still be kept about 508mAh/g under the high current density of 5C, and the battery shows excellent cycle stability and multiplying power performance.
FeS prepared by comparative example 1 2 Assembled composite separator coated with intercalated montmorillonite composite materialThe charge-discharge cycle performance and the rate capability of the lithium-sulfur battery are respectively shown in fig. 5 and 6, the discharge specific capacity of the battery is 830mAh/g after the battery is cycled for 100 times under the current density of 0.2C, the capacity retention rate is 65%, the battery can keep stable cycle under the current density of below 4C, and the discharge specific capacity under the current density of 4C is about 496mAh/g. The battery cycle stability and rate performance were reduced compared to the battery of example 1.
FeS prepared by comparative example 2 2 The charge-discharge cycle performance and the multiplying power performance of the lithium sulfur battery assembled by the composite diaphragm coated by the coated montmorillonite composite material are respectively shown in fig. 5 and 6, the specific discharge capacity of the battery is 1065mAh/g after 100 times of circulation under the current density of 0.2C, the capacity retention rate is 79%, the battery can keep stable circulation under the current density of below 3C, and the specific discharge capacity under the current density of 3C is about 580mAh/g. The battery cycle stability and rate performance were reduced compared to the battery of example 1.
montmorillonite/FeS prepared in comparative example 3 2 The charge-discharge cycle performance and the multiplying power performance of the lithium-sulfur battery assembled by the composite diaphragm coated by the mixture are respectively shown in fig. 5 and 6, the specific discharge capacity of the battery after 100 times of circulation is only 764mAh/g under the current density of 0.2C, the capacity retention rate is 62%, the battery can keep stable circulation under the current density of less than 3C, and the specific discharge capacity under the current density of 3C is about 536mAh/g. The battery cycle stability and rate performance were greatly reduced compared to the battery of example 1.
The charge-discharge cycle performance and the rate capability of the lithium sulfur battery directly assembled by adopting the unmodified separator in comparative example 4 are respectively shown in fig. 5 and 6, the specific discharge capacity of the battery after 100 times of cycles is only 568mAh/g under the current density of 0.2C, the capacity retention rate is 56%, the battery can keep stable cycle under the current density of less than 2C, and the specific discharge capacity under the current density of 2C is about 603mAh/g. The battery cycle stability and rate performance were greatly reduced compared to the battery of example 1.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (8)

1. A composite material comprising a transition metal sulfide intercalated and coated montmorillonite; the chemical formula of the transition metal sulfide is MS 2 M comprises any one or more of Fe, cu, mo, ti, co, ni, mn, nb, zr, W, re and Ta;
in the composite material, nano transition metal sulfide particles are intercalated between montmorillonite layers, and transition metal sulfide microcrystals are coated on the surface of montmorillonite;
the mass ratio of the transition metal sulfide to the montmorillonite is (0.5-20): 1.
2. A method of preparing the composite material of claim 1, comprising the steps of: adding transition metal salt into montmorillonite suspension, stirring at 50-70deg.C for more than 2 hr, adding sulfur source, and performing hydrothermal reaction to obtain the final product.
3. The method of claim 2, wherein the hydrothermal reaction is carried out at a temperature of 160-240 ℃.
4. The method of claim 2, wherein the hydrothermal reaction time is 18-30 hours.
5. The lithium-sulfur battery composite diaphragm is characterized by comprising a base material; the surface of the substrate is coated with a coating; the coating comprising the composite of claim 1.
6. The lithium sulfur battery composite separator according to claim 5, wherein the coating contains the composite material with a mass of 0.1-2mg/cm 2 。
7. A method for preparing the lithium-sulfur battery composite separator according to any one of claims 5 to 6, comprising the steps of: mixing the composite material with a binder and a solvent to obtain slurry; and coating the slurry on the surface of a substrate, and drying to obtain the lithium-sulfur battery composite diaphragm.
8. Use of the composite material of claim 1 and/or the lithium-sulfur battery composite separator of any one of claims 5-6 in a lithium-sulfur battery.
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