CN114368788A - Composite material and battery composite diaphragm - Google Patents

Composite material and battery composite diaphragm Download PDF

Info

Publication number
CN114368788A
CN114368788A CN202111569146.4A CN202111569146A CN114368788A CN 114368788 A CN114368788 A CN 114368788A CN 202111569146 A CN202111569146 A CN 202111569146A CN 114368788 A CN114368788 A CN 114368788A
Authority
CN
China
Prior art keywords
battery
composite material
composite
lithium
montmorillonite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111569146.4A
Other languages
Chinese (zh)
Other versions
CN114368788B (en
Inventor
庞浩
吴炼
洪培萍
赵一芳
高树曦
廖兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemical Engineering of Guangdong Academy of Sciences
Original Assignee
Institute of Chemical Engineering of Guangdong Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Engineering of Guangdong Academy of Sciences filed Critical Institute of Chemical Engineering of Guangdong Academy of Sciences
Priority to CN202111569146.4A priority Critical patent/CN114368788B/en
Publication of CN114368788A publication Critical patent/CN114368788A/en
Application granted granted Critical
Publication of CN114368788B publication Critical patent/CN114368788B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Abstract

The invention discloses a composite material and a battery composite diaphragm. A composite material comprising a transition metal sulfide intercalation and coated montmorillonite; the chemical formula of the transition metal sulfide is MS2M includes any one or more of Fe, Cu, Mo, Ti, Co, Ni, Mn, Nb, Zr, W, Re, and Ta. A battery composite separator includes a substrate; a coating is coated on the surface of the base material; the coating comprises a composite material. The composite material provided by the invention is montmorilloniteThe strong adsorption effect on lithium polysulfide and the catalytic effect of transition metal sulfide are organically combined, so that adsorption and catalytic synergistic effects are formed by utilizing adsorption and catalytic active sites inside and outside the composite material, the adsorption and conversion processes of polysulfide in the charging and discharging processes of the lithium-sulfur battery are strengthened, the shuttle effect of polysulfide is effectively inhibited, and the cycle stability of the lithium-sulfur battery is greatly improved.

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 puts higher requirements on the energy density of secondary batteries. The lithium-sulfur battery has extremely high theoretical energy density (2600Wh kg)-1) And has been a focus and hot spot of research in the field of secondary batteries. However, the problems of lithium polysulfide shuttling effect and slow redox reaction kinetics still remain key problems preventing large-scale commercial application of lithium sulfur batteries. Research has shown that the strategy of "adsorption + catalysis" is an effective way to solve the above-mentioned key problems of lithium sulfur batteries. The "adsorption + catalysis" strategy mainly comprises: (1) heteroatom doping of carbon materials (porous carbon, carbon nanotubes, graphene, etc.); (2) introducing an electric catalyst such as metal oxygen/sulfur/nitride into a nonpolar carbon material; (3) the metal oxide/sulfur/nitride electric catalyst is introduced into the polar materials such as MOFs, MXene and the like. Therefore, on the basis of anchoring lithium polysulfide through physical/chemical adsorption, a catalytic active site is introduced into the material to promote the rapid conversion of the lithium polysulfide anchored on the surface of the material, so that the accumulation of the lithium polysulfide in the electrolyte is avoided, and the occurrence of a shuttle effect is greatly inhibited.
The natural montmorillonite clay mineral material has a special two-dimensional layered structure, extremely strong lithium polysulfide adsorption capacity and good thermal stability, chemical stability and mechanical stability, and 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 functional protective layer and a dispersed polysufide for extended cycle life of lithium sulfur batteries, j.mater.chem.a,2015,3,9461-9467.) report that a surface-modified composite diaphragm prepared by coating montmorillonite on the surface of a lithium sulfur battery diaphragm can effectively adsorb and anchor lithium polysulfide on the positive electrode side of the lithium sulfur battery, thereby effectively inhibiting the 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 conversion of lithium polysulfide, so that it is difficult to realize its application in high energy density lithium sulfur batteries. The lithium-sulfur battery diaphragm modified by the surface coating in the prior art has insufficient adsorption or catalytic action on lithium polysulfide, and the surface coating is easy to block the pore 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 prior diaphragm is difficult to realize the application of the prior diaphragm in a high-energy density lithium-sulfur battery due to the shuttle effect of lithium polysulfide in the prior art, one object of the invention is to provide a composite material, and the other object of the invention is to provide a battery composite diaphragm.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a composite material comprising a transition metal sulfide intercalation and coated montmorillonite; the chemical formula of the transition metal sulfide is MS2M includes any one or more of Fe, Cu, Mo, Ti, Co, Ni, Mn, Nb, Zr, W, Re, and Ta.
Preferably, in such a composite, the transition metal sulfide has the formula MS2M comprises any one or more of Fe, Cu, Mn, Zr, Co and Ni; further preferably, M includes any one or more of Fe, Cu, Mn, Zr, and Ni; still further preferably, M includes any one or more of Fe, Cu and Mn; more preferably, M is Fe.
Further preferably, in the composite material, the montmorillonite interlamination layer is provided with nanometer transition metal sulfide particles, and the surface of the montmorillonite is coated with transition metal sulfide microcrystals.
Preferably, in the composite material, the mass ratio of the transition metal sulfide to the montmorillonite is (0.5-20): 1; further preferably, 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: adding transition metal salt into the montmorillonite suspension, adding a sulfur source, and carrying out hydrothermal reaction to obtain the composite material.
Preferably, in the preparation method of the composite material, transition metal salt is added into montmorillonite suspension, and after sufficient cation exchange treatment, a sulfur source is added for hydrothermal reaction to obtain the composite material; preferably, the composite material is obtained by adding transition metal salt into the montmorillonite suspension, stirring for more than 2h, adding a sulfur source, and carrying out hydrothermal reaction.
Preferably, in the preparation method of the composite material, the montmorillonite suspension is added with the transition metal salt and then stirred for more than 2 hours at the temperature of 50-70 ℃; more preferably, the montmorillonite suspension is added with transition metal salt and then stirred for more than 2 hours at the temperature of 55-65 ℃; still more preferably, the montmorillonite suspension is stirred at 60 ℃ for more than 2 hours after the transition metal salt is added.
Preferably, in the preparation method of the composite material, the sulfur source is added and then stirred at room temperature; further preferably, the stirring time at room temperature is 0.5-1.5 h; still more preferably, the stirring time at room temperature is 0.8-1.2 h; more preferably, the stirring time at room temperature is 1 hour.
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 more preferably, the temperature of the hydrothermal reaction is 190-210 ℃; more preferably, the hydrothermal reaction temperature is 200 ℃.
Preferably, in the preparation method of the composite material, the hydrothermal reaction time is 18-30 h; further preferably, the time of the hydrothermal reaction is 20-26 h; still more preferably, the time of the hydrothermal reaction is 23-25 h; 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 0.5-6 wt%; further preferably, the mass concentration of the montmorillonite suspension is 1-4 wt%; still more preferably, the mass concentration of the montmorillonite suspension is 1.5-3 wt%; still more preferably, the mass concentration of the montmorillonite suspension is 2 wt%.
Preferably, in the preparation method of the composite material, the transition metal salt is ferrous salt, and the ferrous salt is FeSO4·7H2O。
Preferably, in the preparation method of the composite material, the mass ratio of the montmorillonite to the transition metal salt is 1 g: (5-15) mmol; further preferably, the mass ratio of montmorillonite to transition metal salt is 1 g: (8-12) mmol; still further preferably, the mass ratio of montmorillonite to transition metal salt is 1 g: 10 mmol.
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 salt 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 preferably, the molar mass ratio of the transition metal salt to the thiosulfate is 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 the transition metal salt to the elemental sulfur is 1: 0.5.
preferably, the preparation method of the composite material further comprises 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 by deionized water for 2-6 times.
The invention also provides a battery composite diaphragm, which comprises a base material; a coating is coated on the surface of the base material; the coating comprises the composite material.
Preferably, the battery composite separator is a lithium-sulfur battery composite separator.
Preferably, the coating of the composite diaphragm of the battery contains the composite material with the mass of 0.1-2mg/cm2(ii) a Further preferably, the coating contains the composite material in an amount of 0.4 to 1.6mg/cm by mass2。
Preferably, the base material of the battery composite diaphragm 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 base material, and drying to obtain the battery composite diaphragm.
Preferably, in the method for preparing the battery composite diaphragm, 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 method for preparing the battery composite separator, the solvent comprises at least one of Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and Dimethylsulfoxide (DMSO); further preferably, the solvent is N-methylpyrrolidone (NMP).
Preferably, in the preparation method of the battery composite diaphragm, the mass ratio of the composite material to the binder is (6-12): 1; further preferably, the mass ratio of the composite material to the binder is (7-11): 1; still further preferably, the mass ratio of the composite material to the binder is (8-10): 1; more preferably, the mass ratio of the composite material to the binder is 9: 1.
preferably, in the preparation method of the battery composite separator, the drying is performed under vacuum conditions.
Preferably, in the preparation method of the battery composite diaphragm, the drying temperature is 50-70 ℃; further preferably, the drying temperature is 55-65 ℃; still more preferably, the drying temperature is 60 ℃.
Preferably, in the preparation method of the battery composite diaphragm, the drying time is 10-14 h; further preferably, the drying time is 11-13 h; still more preferably, the drying time is 12 h.
The invention also provides application of the composite material and/or the battery composite diaphragm in a lithium-sulfur battery.
The invention has the beneficial effects that:
the composite material provided by the invention comprises a transition metal sulfide intercalation layer and coated montmorillonite, and the strong adsorption effect of the montmorillonite on lithium polysulfide and the catalytic effect of the transition metal sulfide are organically combined, 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 adsorption and conversion processes of polysulfide are enhanced in the charging and discharging processes of the lithium-sulfur battery, the shuttle effect of the polysulfide is effectively inhibited, and the cycle stability of the lithium-sulfur battery is greatly improved.
According to the invention, a high-speed lithium ion transmission channel structure is constructed between montmorillonite layers by utilizing the intercalation effect of transition metal sulfide on montmorillonite, so that the lithium ion transmission performance of the lithium-sulfur battery diaphragm is effectively improved, and the rate capability of the lithium-sulfur battery is greatly improved.
According to the invention, a simple hydrothermal synthesis method is adopted, a crystal in-situ growth technology is utilized, nano transition metal sulfide particles are synthesized in situ between montmorillonite layers, transition metal sulfide microcrystals are generated on the surface of the montmorillonite, and the prepared composite material has a composite structure of transition metal sulfide intercalation and coating of the montmorillonite, so that the montmorillonite and transition metal sulfide are organically combined, the composite material has adsorption and catalytic synergistic effects on polysulfide, the shuttle effect is effectively inhibited, and the cycle stability of the lithium-sulfur battery is promoted to be improved.
Compared with the lithium-sulfur battery diaphragm modified by montmorillonite or transition metal sulfide alone in the prior art, the composite material prepared by the invention has the following remarkable improvement: on one hand, the catalytic action of the transition metal sulfide is introduced on the basis of the strong chemical adsorption action of the montmorillonite, so that the adsorption and catalysis synergistic effect is realized on polysulfide generated in the charging and discharging process of the lithium-sulfur battery, the electrochemical reaction kinetic process of the lithium-sulfur battery is greatly promoted, the accumulation of the polysulfide in electrolyte is avoided, and the influence of the shuttle effect of the 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 coating montmorillonite composite material, so that the high-speed migration of lithium ions in the charging and discharging process of the battery is greatly promoted, and the rate capability of the battery is greatly improved.
Compared with the prior art, the cycle stability and rate capability of the lithium-sulfur battery assembled by the composite lithium-sulfur battery diaphragm prepared by the invention are obviously improved.
Drawings
FIG. 1 shows FeS obtained in example 12SEM images of intercalated and coated montmorillonite composites.
FIG. 2 shows FeS obtained in example 12TEM images of intercalated and coated montmorillonite composites.
Fig. 3 is a surface SEM image of the battery composite separator prepared in example 1.
Fig. 4 is an SEM image of a lithium sulfur battery separator that was not surface-coated and modified.
Fig. 5 is a graph showing the charge and discharge cycle stability of the assembled lithium sulfur batteries of examples and comparative examples.
Fig. 6 is a graph of 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 apparatuses used in the examples and comparative examples were obtained from conventional commercial sources or may be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
Adding 2g of montmorillonite intoAdding into 100mL deionized water, stirring and dispersing uniformly to obtain a suspension, and adding 20mmol of FeSO into the suspension4·7H2Stirring for 2h at the temperature of 60 ℃ after O, then adding 20mmol of sodium thiosulfate and 10mmol of sulfur, stirring for 1h at room temperature, transferring all mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at the temperature of 200 ℃, naturally cooling, filtering and recovering a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying for 12h at the temperature of 80 ℃ to obtain FeS2An intercalated and coated montmorillonite composite material having a topographical structure as shown in figures 1 and 2. Adding the composite material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to a mass ratio of 9:1, fully stirring to form 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 drying in vacuum at 60 ℃ for 12 hours to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS2The amount of intercalated and coated montmorillonite composite material is 0.5mg/cm2And the composite diaphragm is applied to the lithium-sulfur battery. The surface SEM image of the composite membrane is shown in fig. 3. SEM images of lithium sulfur battery separator without surface coating modification are shown in fig. 4.
As shown in FIG. 1, a large amount of FeS with the particle size of 200-300nm is coated on the surface of the montmorillonite2Microcrystalline, and a large amount of FeS is clearly seen between the montmorillonite sheets2The ultrafine nanoparticles of (2) are present. As shown in fig. 2, FeS between montmorillonite layers2The particle size of the nano particles is not more than 10 nm. As shown in FIG. 3, it can be clearly seen that the surface of the battery composite separator prepared by the invention is modified with a layer of FeS2The intercalated and coated 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, which was not surface-coated and modified, had a through-hole structure and a uniform pore distribution.
Example 2
The difference from example 1 is that FeS is formed between and on the surface of the montmorillonite2The amount of (A) is different, specifically:
2g of montmorillonite was added to 100mL of deionizationStirring and dispersing the mixture evenly in water to obtain a suspension, and adding 10mmol of FeSO into the suspension4·7H2Stirring for 2h at the temperature of 60 ℃ after O, then adding 10mmol of sodium thiosulfate and 5mmol of sulfur, stirring for 1h at room temperature, transferring all mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at the temperature of 200 ℃, naturally cooling, filtering and recovering a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying for 12h at the temperature of 80 ℃ to obtain FeS2Intercalated and coated montmorillonite composites. Adding the composite material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to a mass ratio of 9:1, fully stirring to form 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 drying in vacuum at 60 ℃ for 12 hours to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS2The amount of the intercalated and coated montmorillonite composite material is 1mg/cm2And the composite diaphragm is applied to the lithium-sulfur battery.
Example 3
The difference from example 1 is that FeS is formed between and on the surface of the montmorillonite2The amount of (A) is different, specifically:
adding 2g of montmorillonite into 100mL of deionized water, stirring and uniformly dispersing to obtain a suspension, and adding 30mmol of FeSO into the suspension4·7H2Stirring for 2h at the temperature of 60 ℃ after O, then adding 30mmol of sodium thiosulfate and 15mmol of sulfur, stirring for 1h at room temperature, transferring all mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at the temperature of 200 ℃, naturally cooling, filtering and recovering a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying for 12h at the temperature of 80 ℃ to obtain FeS2Intercalated and coated montmorillonite composites. Adding the composite material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to a mass ratio of 9:1, fully stirring to form 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 drying in vacuum at 60 ℃ for 12 hours to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS2Intercalated and coatedThe montmorillonite composite material amount is 0.2mg/cm2And the composite diaphragm is applied to the lithium-sulfur battery.
Comparative example 1
Compared with the example 1, the difference is that FeS in the composite material2Only exists between the montmorillonite layers, specifically:
adding 2g of montmorillonite into 100mL of deionized water, stirring and uniformly dispersing to obtain a suspension, and adding 20mmol of FeSO into the suspension4·7H2And O, stirring for 2 hours at the temperature of 60 ℃, filtering, repeatedly washing a filter cake by deionized water until no sulfate ions exist in a washing liquid, and drying at 105 ℃ 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 sulfur, stirring for 1h at room temperature, transferring all mixed solution into a 150mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 200 ℃, naturally cooling, filtering and recovering a filter cake, washing the filter cake with deionized water for 3 times, and carrying out vacuum drying for 12h at 80 ℃ to obtain FeS2An intercalated montmorillonite composite material. The above FeS2Adding the intercalated montmorillonite 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 to form 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 drying in vacuum at 60 ℃ for 12 hours to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS2The amount of intercalated montmorillonite composite material is 1.5mg/cm2And the composite diaphragm is applied to the lithium-sulfur battery.
Comparative example 2
Compared with the example 1, the difference is that FeS in the composite material2Mainly exists on the surface of montmorillonite, and specifically comprises the following components:
adding 2g of montmorillonite into 100mL of deionized water, stirring and uniformly dispersing to obtain a suspension, and adding 20mmol of FeSO into the suspension4·7H2O, 20mmol of sodium thiosulfate and 10mmol of elemental sulfur, transferring all mixed solution into a 150mL hydrothermal reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 2Naturally cooling for 4h, filtering and recovering a filter cake, washing the filter cake for 3 times by using deionized water, and performing vacuum drying at 80 ℃ for 12h to obtain FeS2A coated montmorillonite composite material. The above FeS2Adding the coated montmorillonite composite material and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to a mass ratio of 9:1, fully stirring to form 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 drying in vacuum at 60 ℃ for 12 hours to obtain the battery composite diaphragm, wherein the surface coating of the diaphragm contains FeS2The amount of the coated montmorillonite composite material was 0.8mg/cm2And the composite diaphragm is applied to the lithium-sulfur battery.
Comparative example 3
The difference from example 1 is that montmorillonite and FeS were mixed2After the particles are physically mixed, the surface of a commercial battery diaphragm is coated, and the method specifically comprises the following steps:
mixing pure montmorillonite with pure FeS2Mixing the granules at a mass ratio of 1:1.2, and grinding thoroughly to obtain montmorillonite and FeS2And (3) mixing. Adding the mixture and PVDF (polyvinylidene fluoride) into a certain volume of NMP (N-methyl pyrrolidone) solvent according to a mass ratio of 9:1, fully stirring to form 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 drying in vacuum at 60 ℃ for 12 hours to obtain montmorillonite/FeS2Composite separator coated with mixture, the surface coating of the separator containing montmorillonite/FeS2The amount of the mixture was 0.5mg/cm2And the composite diaphragm is applied to the lithium-sulfur battery.
Comparative example 4
Compared with the example 1, the difference is that the surface coating modification is not carried out on the lithium-sulfur battery diaphragm, and specifically comprises the following steps:
and directly assembling the battery by adopting the unmodified lithium-sulfur battery diaphragm to test the charge and discharge performance.
The separators of example 1 and comparative examples 1 to 4 were subjected to performance tests in a lithium sulfur battery, and the test results were as follows:
preparation of example 1Prepared FeS2The charge-discharge cycle performance and the rate capability of the lithium-sulfur battery assembled by the intercalation and the composite diaphragm coated by the coated montmorillonite composite material are respectively shown in fig. 5 and fig. 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 battery can still maintain the discharge specific capacity of about 508mAh/g under the high current density of 5C, and the battery shows excellent cycle stability and rate capability.
FeS prepared in comparative example 1 was used2The charge-discharge cycle performance and the rate capability of the lithium-sulfur battery assembled by the composite membrane coated by the intercalated montmorillonite composite material are respectively shown in fig. 5 and fig. 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 be stably cycled under the current density of below 4C, and the discharge specific capacity is about 496mAh/g under the current density of 4C. The cycle stability and rate performance of the battery were reduced compared to the battery of example 1.
FeS prepared by comparative example 22The charge-discharge cycle performance and the rate performance of the lithium-sulfur battery assembled by the composite membrane coated with the coated montmorillonite composite material are respectively shown in fig. 5 and fig. 6, the discharge specific capacity of the battery is 1065mAh/g after the battery is cycled for 100 times under the current density of 0.2C, the capacity retention rate is 79%, the battery can be stably cycled under the current density of less than 3C, and the discharge specific capacity is about 580mAh/g under the current density of 3C. The cycle stability and rate performance of the battery were reduced compared to the battery of example 1.
montmorillonite/FeS prepared using comparative example 32The charge-discharge cycle performance and the rate performance of the lithium-sulfur battery assembled by the composite diaphragm coated by the mixture are respectively shown in fig. 5 and fig. 6, the discharge specific capacity of the battery is only 764mAh/g after the battery is cycled for 100 times under the current density of 0.2C, the capacity retention rate is 62%, the battery can only keep stable cycle under the current density of less than 3C, and the discharge specific capacity of the battery under the current density of 3C is about 536 mAh/g. The cycling stability and rate capability of the battery are greatly reduced compared with the battery of example 1.
The charge-discharge cycle performance and the rate performance of the lithium-sulfur battery directly assembled by the unmodified diaphragm in the comparative example 4 are respectively shown in fig. 5 and fig. 6, the discharge specific capacity of the battery is only 568mAh/g after the battery is cycled for 100 times under the current density of 0.2C, the capacity retention rate is 56%, the battery can only keep stable cycling under the current density of below 2C, and the discharge specific capacity is about 603mAh/g under the current density of 2C. The cycling stability and rate capability of the battery are greatly reduced compared with the battery of example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A composite material comprising a transition metal sulfide intercalation and coated montmorillonite; the chemical formula of the transition metal sulfide is MS2M includes any one or more of Fe, Cu, Mo, Ti, Co, Ni, Mn, Nb, Zr, W, Re, and Ta.
2. The composite material according to claim 1, wherein the mass ratio of the transition metal sulfide to the montmorillonite is (0.5-20): 1.
3. A method for preparing a composite material according to any one of claims 1-2, comprising the steps of: adding transition metal salt into the montmorillonite suspension, adding a sulfur source, and carrying out hydrothermal reaction to obtain the composite material.
4. The method as claimed in claim 3, wherein the hydrothermal reaction is carried out at a temperature of 160-240 ℃.
5. The method for preparing the composite material according to claim 3, wherein the hydrothermal reaction time is 18-30 h.
6. A battery composite separator, comprising a substrate; the surface of the base material is coated with a coating; the coating comprising the composite material of any one of claims 1-2.
7. The battery composite separator according to claim 6, wherein said battery composite separator is a lithium-sulfur battery composite separator.
8. The battery composite separator of claim 6, wherein the coating comprises a composite material in an amount of 0.1-2mg/cm by mass2。
9. A method of making a battery composite separator as defined in any one of claims 6 to 8, 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 base material, and drying to obtain the battery composite diaphragm.
10. Use of the composite material according to any one of claims 1 to 2 and/or the battery composite separator according to any one of claims 6 to 8 in a lithium-sulphur battery.
CN202111569146.4A 2021-12-21 2021-12-21 Composite material and battery composite diaphragm Active CN114368788B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111569146.4A CN114368788B (en) 2021-12-21 2021-12-21 Composite material and battery composite diaphragm

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111569146.4A CN114368788B (en) 2021-12-21 2021-12-21 Composite material and battery composite diaphragm

Publications (2)

Publication Number Publication Date
CN114368788A true CN114368788A (en) 2022-04-19
CN114368788B CN114368788B (en) 2023-12-05

Family

ID=81139386

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111569146.4A Active CN114368788B (en) 2021-12-21 2021-12-21 Composite material and battery composite diaphragm

Country Status (1)

Country Link
CN (1) CN114368788B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104891514A (en) * 2015-05-05 2015-09-09 陕西科技大学 Method for preparing bismuth sulfide/montmorillonite composite material by hydrothermal method
CN109244334A (en) * 2018-10-30 2019-01-18 安徽新衡新材料科技有限公司 A kind of preparation method of lithium-sulfur cell and its diaphragm and the diaphragm
CN109786628A (en) * 2019-03-20 2019-05-21 广西师范大学 A kind of preparation method and applications of cobalt nickel bimetal sulfide/carbon paper composite
CN111916640A (en) * 2020-09-11 2020-11-10 合肥工业大学 Lithium sulfur battery WS2/CNTs modified diaphragm and preparation method thereof
CN113381121A (en) * 2021-06-11 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of tungsten oxide/clay mineral nano material modified diaphragm for lithium-sulfur battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104891514A (en) * 2015-05-05 2015-09-09 陕西科技大学 Method for preparing bismuth sulfide/montmorillonite composite material by hydrothermal method
CN109244334A (en) * 2018-10-30 2019-01-18 安徽新衡新材料科技有限公司 A kind of preparation method of lithium-sulfur cell and its diaphragm and the diaphragm
CN109786628A (en) * 2019-03-20 2019-05-21 广西师范大学 A kind of preparation method and applications of cobalt nickel bimetal sulfide/carbon paper composite
CN111916640A (en) * 2020-09-11 2020-11-10 合肥工业大学 Lithium sulfur battery WS2/CNTs modified diaphragm and preparation method thereof
CN113381121A (en) * 2021-06-11 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of tungsten oxide/clay mineral nano material modified diaphragm for lithium-sulfur battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAILI WU ET AL.: "Cobalt and nickel bimetallic sulfide nanoparticles immobilized on montmorillonite demonstrating peroxidase-like activity for H2O2 detection", 《NEW J. CHEM.》, pages 18749 - 18758 *

Also Published As

Publication number Publication date
CN114368788B (en) 2023-12-05

Similar Documents

Publication Publication Date Title
Hao et al. Novel MoSe2/MoO2 heterostructure as an effective sulfur host for high-performance lithium/sulfur batteries
Qu et al. Nitrogen-doped porous “green carbon” derived from shrimp shell: Combined effects of pore sizes and nitrogen doping on the performance of lithium sulfur battery
Shen et al. Metal-organic frameworks (MOFs) and their derivative as electrode materials for lithium-ion batteries
Liu et al. Nano-sized cobalt oxide/mesoporous carbon sphere composites as negative electrode material for lithium-ion batteries
Jin et al. Co-N/KB porous hybrid derived from ZIF 67/KB as a separator modification material for lithium-sulfur batteries
Guo et al. A mixed microporous/low-range mesoporous composite with high sulfur loading from hierarchically-structured carbon for lithium sulfur batteries
Trukawka et al. Hollow carbon spheres loaded with uniform dispersion of copper oxide nanoparticles for anode in lithium-ion batteries
Wu et al. Urchin-like NiCo 2 S 4 infused sulfur as cathode for lithium–sulfur battery
Zhang et al. Bio-inspired construction of electrocatalyst decorated hierarchical porous carbon nanoreactors with enhanced mass transfer ability towards rapid polysulfide redox reactions
Wang et al. Advanced preparation and application of transition metal selenides in lithium–sulfur batteries: a review
CN112138668A (en) Polysulfide redox catalyst and modified diaphragm for lithium sulfur battery
CN102163711A (en) Method for preparing lithium ion battery negative material by utilizing mesoporous carbon supported nano particles
Zhang et al. Impact of micro-/mesoporous carbonaceous structure on electrochemical performance of sulfur
CN115072696B (en) Co-NCNT@HC hierarchical porous carbon material, and preparation method and application thereof
CN116190649A (en) MoO grows on mesoporous hollow carbon sphere surface in situ 2 Nanosheet composite material
KR20190118506A (en) Method for manufacturing iron phosphide
CN114368788B (en) Composite material and battery composite diaphragm
CN114639828B (en) Multi-sheet flower-like network structure silicon-carbon composite material and preparation method and application thereof
CN114649635A (en) Preparation method and application of bimetal nitride multifunctional diaphragm
Dan et al. Cobalt-Carbon nanotubes supported on V2O3 nanorods as sulfur hosts for High-performance Lithium-Sulfur batteries
Duan et al. Enhancing the polysulfide redox conversion by a heterogeneous CoP-Co3S4 electrocatalyst for Li-S batteries
CN114551802A (en) Preparation method and application of carbon nanorod composite material
WO2018195837A1 (en) Metal-sulfur battery and preparation method therefor
CN108899493B (en) Nano sulfur/metal sulfide composite material, preparation method thereof and application of nano sulfur/metal sulfide composite material as electrode material
CN113540428A (en) 3DOM graphene carbon supported monodisperse NiO nanocrystalline material, preparation and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant