CN111403658A - Preparation method of diaphragm with electrocatalysis function and application of diaphragm in lithium-sulfur battery - Google Patents
Preparation method of diaphragm with electrocatalysis function and application of diaphragm in lithium-sulfur battery Download PDFInfo
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- CN111403658A CN111403658A CN202010143776.4A CN202010143776A CN111403658A CN 111403658 A CN111403658 A CN 111403658A CN 202010143776 A CN202010143776 A CN 202010143776A CN 111403658 A CN111403658 A CN 111403658A
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- 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
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- 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
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Abstract
The invention belongs to the technical field of lithium-sulfur batteries, and relates to a diaphragm with an electrocatalysis function, and a preparation method and application thereof. The diaphragm is composed of a commercial polymer diaphragm substrate and an electrocatalytic function modification layer coated on one side surface of the diaphragm substrate, wherein: the electrocatalytic function modifying layer comprises a binder, a conductive agent and an electrocatalyst; the electrocatalyst is graphene and heteroatom-doped MoS2A three-dimensional porous composite of components. The three-dimensional porous structure constructed by the graphene can adsorb a large amount of lithium polysulfide dissolved in the electrolyte through physical action; heteroatom doped MoS2Has rich interface defects, polarity and electrocatalytic activity, and can be used for high efficiencyThe chemical adsorption of lithium polysulfide and the catalysis of the electrochemical conversion of the lithium polysulfide inhibit the shuttle effect of the lithium-sulfur battery, and improve the reversible capacity and the cycling stability of the high-sulfur-capacity lithium-sulfur battery.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage batteries, and particularly relates to a diaphragm with an electrocatalytic function, a preparation method of the diaphragm and application of the diaphragm in a lithium-sulfur battery.
Background
Lithium sulfur batteries are one of lithium secondary battery systems that are highly desired in the scientific and industrial fields. The lithium-sulfur secondary battery takes metal lithium as a negative electrode and elemental sulfur as a positive electrode, and the theoretical specific capacity of the lithium-sulfur secondary battery is 1675mAhg-1Theoretical energy density is 2600Whkg-1The actual energy density can reach as high as 400Whkg-1And the cost is low and the environment is friendly while the specific energy and the specific work are high. However, the lithium-sulfur secondary battery has the defects of low utilization rate of sulfur active substances, poor electrochemical reversibility, fast capacity fading and the like, and is still a key bottleneck for restricting the development of the lithium-sulfur battery at present.
For the lithium-sulfur secondary battery, the sulfur positive electrode material has the following main common technical problems that (1) elemental sulfur and discharge product lithium sulfide L i2Low intrinsic conductivity of S to reduce the utilization rate of active material, (2) intermediate product lithium polysulfide L i formed by elemental sulfur in the process of charging and discharging2S8、Li2S6And L i2S4The electrolyte is easy to dissolve, so that active substances are lost; (3) slow rate of electrochemical reaction of lithium polysulfideAnd low electrochemical activity; (4) under the action of concentration gradient, lithium polysulfide dissolved in electrolyte passes through a diaphragm to be directly contacted with a metal lithium cathode to form a shuttle effect, so that poor cycle performance and high self-discharge rate are caused; (5) during the charging and discharging process of elemental sulfur, larger volume expansion and contraction effects (volume increase is over 80%) are generated, and the physical structure of the electrode is damaged, so that the electrochemical reversibility is poor.
In order to overcome the defects and improve the reversible capacity and the cycle performance of the sulfur anode, the scheme adopted at present mainly comprises the following steps: the method comprises the following steps of sulfur anode compositing, lithium cathode protection, barrier layer adding, diaphragm modification and electrolyte and binder modification. The diaphragm is modified, namely the modified material is coated on one side of the surface of the diaphragm substrate, so that the scheme for effectively improving the performance of the battery is provided. At present, researchers at home and abroad try carbon modified materials such as porous carbon, carbon nanotubes and graphene in different angles. The general characteristics of the carbon modified materials are as follows: the high conductivity of the carbonaceous material can enhance electron conduction; the adsorption effect of the carbonaceous material can relieve the dissolution and diffusion problems of lithium polysulfide. However, the nonpolar carbon material can adsorb polar lithium polysulfide only by weak physical action, and the sulfur fixing effect is limited. Particularly, when the sulfur loading is high, the electrochemical conversion rate of lithium polysulfide is slow, the lithium polysulfide is enriched in a sulfur positive electrode area, and a large concentration gradient is generated, and the lithium polysulfide can easily diffuse through a diaphragm under the action of high concentration difference to generate a shuttle flying effect. Therefore, the current strategy mainly comprising adsorption or 'blocking' of lithium polysulfide is difficult to fundamentally improve the problem of flying shuttle of lithium polysulfide. The structural properties of the membrane finishing material still need to be strongly improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a diaphragm with an electrocatalytic function, a preparation method thereof and application thereof in a lithium-sulfur battery. The diaphragm is composed of a commercial polymer diaphragm substrate and an electrocatalytic function modification layer coated on one side surface of the diaphragm substrate, wherein: the electrocatalytic function modifying layer comprises a binder, a conductive agent and an electrocatalyst; the electrocatalyst is graphene and heteroAtom-doped MoS2A three-dimensional porous composite of components. The preparation method comprises the following steps: firstly, uniformly mixing graphene, a molybdenum source, a sulfur source and a precursor containing a doping element in an aqueous solution, and growing heteroatom-doped MoS on the surface of the graphene in situ by a hydrothermal method2Nanosheets, and simultaneously carrying out three-dimensional structure assembly; and then uniformly coating the binder, the conductive agent and the electrocatalyst on the surface of one side of the diaphragm substrate to prepare the lithium-sulfur battery diaphragm with the electrocatalysis function.
The invention is realized by the following technical scheme:
a diaphragm with electrocatalysis function is characterized in that: the electrocatalytic functional membrane consists of a commercial polymer membrane substrate and an electrocatalytic functional modification layer coated on one side surface of the membrane substrate.
The diaphragm with the electrocatalysis function comprises an electrocatalysis function modification layer, wherein the thickness of the electrocatalysis function modification layer is 10-100 mu m, and the mass ratio of the binder to the conductive agent to the electrocatalysis is 0.5-1:0.5-3: 6-9.
The membrane with the electrocatalysis function is prepared by mixing graphene and heteroatom-doped MoS2Assembled three-dimensional porous composite, MoS2The doped hetero atom is one or more of O, N, P, F, Se, Co, Ni, Fe and other elements.
The diaphragm with the electrocatalysis function is prepared by using one or more of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), Polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), acrylonitrile multipolymer (L A132/L A133), gelatin and other binders as the binders.
The conductive agent of the diaphragm with the electrocatalysis function is any one or more of conductive carbon materials such as acetylene black, carbon fiber, carbon nano tube, Ketjen black, conductive carbon black and the like.
The diaphragm with electrocatalysis function of the invention is characterized in that: the diaphragm substrate is any one of a ceramic diaphragm, a polyethylene diaphragm (PE), a polypropylene diaphragm (PP), a polyester film (PET), a polyamide film (PA), a polyimide film (PI), Celgard2500, Celgard2400, Celgard2340, a cellulose diaphragm, spandex and an aramid film.
A preparation method of a diaphragm with electrocatalysis function is characterized in that:
the preparation method comprises the following steps: firstly, uniformly mixing graphene, a molybdenum source, a sulfur source and a precursor containing a doping element in an aqueous solution, and growing heteroatom-doped MoS on the surface of the graphene in situ by a hydrothermal method2Nanosheets, and simultaneously carrying out three-dimensional structure assembly; and then uniformly coating the binder, the conductive agent and the electrocatalyst on the surface of one side of the diaphragm substrate to prepare the lithium-sulfur battery diaphragm with the electrocatalysis function.
The preparation method of the diaphragm with the electrocatalysis function comprises the following steps:
(1) preparing graphene by using crystalline flake graphite as a raw material through an improved hummer method;
(2) will be (NH)4)6Mo7O24·4H2Adding O, thiourea and a precursor containing a doping element into the aqueous solution of the graphene, and continuously stirring;
(3) transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 150-220 ℃ for 18-24h, naturally cooling to room temperature, washing with deionized water, carrying out suction filtration, and freeze-drying the obtained solid precipitate for 12-24h to obtain heteroatom-doped MoS2A graphene composite material;
(4) the resulting heteroatom-doped MoS2Grinding the graphene composite material into powder, uniformly mixing the powder with a conductive agent and a binder in proportion, and stirring at a high speed to obtain coating slurry;
(5) and uniformly coating the coating slurry on one side surface of the commercial polymer diaphragm by using a doctor blade coating method, and drying at 40-70 ℃ for 12-24 h.
In the preparation method of the diaphragm with the electrocatalytic function, the precursor containing the doping element in the step (2) is NH4F、NaH2PO2、Na2SeO3、Co(NO3)2、Ni(NO3)2And Fe (NO)3)3And one or more of the elements.
The preparation method of the diaphragm with electrocatalytic function of the invention is (NH) in the step (2)4)6Mo7O24·4H2The mass ratio of the O, the thiourea and the precursor containing the doping elements is 1:14-20: 0.01-0.10.
The preparation method of the diaphragm with electrocatalytic function of the invention is (NH) in the step (2)4)6Mo7O24·4H2The mass ratio of the O to the graphene is 0.5-1.5: 1.
According to the preparation method of the diaphragm with the electrocatalysis function, the mass ratio of the binder, the conductive carbon material and the three-dimensional porous composite material in the step (4) is 0.5-1:0.5-3: 6-9.
The application of the diaphragm with electrocatalysis function in the lithium-sulfur battery is characterized in that: the lithium-sulfur battery comprises a high-sulfur-loading sulfur/carbon composite material positive electrode, a metal lithium negative electrode, electrolyte and a diaphragm with an electrocatalytic function.
The diaphragm with the electrocatalysis function is applied to the lithium-sulfur battery, and one side of the functional modification layer in the diaphragm with the electrocatalysis function faces to the sulfur/carbon composite positive electrode material.
The diaphragm with the electrocatalytic function is applied to the lithium-sulfur battery, the high-sulfur-loading sulfur/carbon composite material positive electrode material is composed of sublimed sulfur and a conductive carbon material, and the mass fraction of the sublimed sulfur in the composite material is 70-90 wt.%.
The invention relates to the use of a separator having an electrocatalytic function in a lithium-sulfur battery, said high-sulfur-loading sulfur/carbon composite positive electrode
Compared with the prior art, the technical scheme of the invention has the following technical effects:
(1) the heteroatom-doped molybdenum disulfide adopted by the membrane functional modification layer material with the electrocatalysis function can be used as an electrocatalyst, so that more catalytic active sites are provided, the electrochemical reaction rate is improved, the membrane functional modification layer material has a catalytic effect on the conversion of polysulfide, and the utilization rate of active substance sulfur is improved.
(2) The membrane functional modification layer material with the electrocatalysis function has a chemical adsorption effect on polysulfide generated in a sulfur positive electrode area in a circulation process, and a three-dimensional porous structure formed by doping graphene and heteroatom with molybdenum disulfide has a physical adsorption effect on dissolved polysulfide, so that a shuttle effect in a lithium-sulfur battery is effectively inhibited.
(3) The diaphragm with the electrocatalysis function has certain mechanical strength and flexibility, can relieve the volume expansion of an electrode material in the charging and discharging process, effectively prevent the damage of the electrode material structure, and can prolong the cycle life of a battery.
(4) The lithium-sulfur battery assembled by the diaphragm with the electrocatalysis function has the advantages that the cycle stability and the rate capability are greatly improved, the preparation process of the functional diaphragm is simple, the operation is easy, and the industrial production is facilitated.
Drawings
FIG. 1 is a schematic representation of O-doped MoS prepared in example 1 of the present invention2And a charge-discharge curve diagram of the lithium-sulfur battery with the graphene @ PP diaphragm at 0.2C.
FIG. 2 is a graph of O-doped MoS prepared in example 1 of the present invention2And the cycle performance of the lithium-sulfur battery with the graphene @ PP membrane at 0.2 ℃ is compared with that of the lithium-sulfur battery with the graphene @ PP membrane.
FIG. 3 is an O-doped MoS prepared in example 1 of the present invention2And the cycle performance of the lithium-sulfur battery with the graphene @ PP membrane at 1C is compared.
Detailed Description
Example 1
(1) Weighing 2.0g of sublimed sulfur and 0.5g of Ketjen black, placing the sublimed sulfur and the Ketjen black in a mortar, fully grinding and mixing the sublimed sulfur and the Ketjen black, transferring the obtained sulfur/carbon mixture into a glass tube, vacuumizing, sealing the glass tube, performing heat treatment for 10 hours in a muffle furnace at 300 ℃ to obtain a sulfur/carbon composite material, mixing the prepared S/C composite material, conductive carbon black SuperP and a binder L A133 in a penicillin bottle according to the mass ratio of 9:0.5:0.5, taking deionized water and absolute ethyl alcohol as dispersing agents, performing magnetic stirring to uniformly mix the slurry, coating the coating slurry on the surface of a pre-cut aluminum foil by using a scraper coating method to prepare a sulfur electrode plate, and drying for 24 hours in a vacuum drying box at 60 ℃ for later use.
(2) O-doped MoS2Preparation of graphene composite material: slowly adding 2g of flake graphite, 1g of sodium nitrate and 6g of potassium permanganate into a beaker filled with 46ml of concentrated sulfuric acid in sequence, stirring for 2 hours in an ice-water mixed bath, transferring the beaker into a 35 ℃ constant-temperature water bath, continuously stirring for 0.5 hour, slowly adding 92ml of ultrapure water, raising the temperature of a reaction solution to 98 ℃, maintaining for 15 minutes, diluting the reaction solution to 280ml with warm water, and adding 10ml of 30% H2O2And (4) reducing the redundant potassium permanganate and manganese dioxide by using the solution. And after the reduction is finished, the reaction solution is bright yellow, then is subjected to suction filtration or centrifugation, is washed by a 5% HCl solution, is washed to be neutral by ultrapure water, and is ultrasonically dispersed in the ultrapure water to obtain the graphene aqueous solution. 155mg (NH) are weighed4)6Mo7O24·4H2Adding O and 285mg thiourea into a graphene aqueous solution with the concentration of 70m L being 2 g/L, continuously stirring, transferring the obtained mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 200 ℃ for 18h, naturally cooling to room temperature, washing with deionized water, carrying out suction filtration, and carrying out vacuum drying on the obtained solid precipitate for 24h to obtain O-doped MoS2A graphene composite material.
(3) O-doped MoS2Preparation of a/graphene @ PP composite diaphragm: taking dry O-doped MoS2Grinding the graphene composite material into powder, uniformly mixing the powder with conductive carbon black SuperP and a binder PVDF according to the mass ratio of 9:0.5:0.5, taking an N-methylpyrrolidone (NMP) solution as a dispersing agent, and stirring at a high speed to obtain coating slurry. Coating the coating slurry on one side surface of a polypropylene diaphragm (PP) by using a scraper coating method, and drying at 60 ℃ for 24 hours to obtain MoS2A graphene @ PP composite membrane.
(4) O-doped MoS2Application of/graphene @ PP composite diaphragm in lithium-sulfur batteryThe following steps are used: the prepared high-sulfur-loading sulfur/carbon electrode plate is used as a positive electrode, and the prepared MoS is prepared2The preparation method comprises the steps of dissolving lithium bis (trifluoromethane) sulfonyl imide (L iTFSI) with 1.0M electrolyte in a mixed solution of 1, 3-dioxolane (DO L) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, wherein the/graphene @ PP composite diaphragm is a battery diaphragm, a metal lithium sheet is a negative electrode, and anhydrous L iNO with the mass fraction of 2 wt% is added3In the absence of water and anaerobic (H)20<0.5ppm，O2<0.5ppm) glove box, assembling CR2025 type button batteries according to corresponding sequence, testing the charge and discharge performance of the assembled button batteries at room temperature by adopting L and CT2001A battery testing system and CH1760E electrochemical workstation, as shown in figure 1, the lithium-sulfur battery has two typical discharge platforms, the high voltage platform and the low voltage platform are generally about 2.3V and 2.1V, under the current density of 0.2C, the first discharge specific capacity of the battery can reach 1252.6mAh/g, after 100 cycles, the discharge specific capacity is kept at 916.5mAh/g, and the capacity retention rate is 73.2%.
Example 2
(1) P-doped MoS2Preparation of graphene composite material: the graphene aqueous solution prepared in the step (2) of example 1 was taken. 155mg (NH) are weighed4)6Mo7O24·4H2O, 285mg thiourea and 52mg NaH2PO2Adding the mixture into a graphene aqueous solution with the concentration of 70m L of 1-3 g/L, continuously stirring, transferring the obtained mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 200 ℃ for 18h, naturally cooling to room temperature, washing with deionized water, carrying out suction filtration, and carrying out vacuum drying on the obtained solid precipitate for 24h to obtain P-doped MoS2A graphene composite material.
(2) P-doped MoS2Preparation of a/graphene @ PP composite diaphragm: taking dry P-doped MoS2Grinding the graphene composite material into powder, uniformly mixing the powder with conductive carbon black SuperP and a binder PVDF according to the mass ratio of 9:0.5:0.5, taking an N-methylpyrrolidone (NMP) solution as a dispersing agent, and stirring at a high speed to obtain coating slurry. Coating the coating slurry on one side surface of a polypropylene diaphragm (PP) by using a scraper coating method, and drying at 60 ℃ for 24 hours to obtain MoS2Graphene@ PP composite diaphragm.
(3) P-doped MoS2The application of the/graphene @ PP composite diaphragm in the lithium-sulfur battery is as follows: the prepared MoS was used as the positive electrode with the high sulfur-loaded sulfur/carbon electrode sheet prepared in the step (1) of example 1 as the positive electrode2The preparation method comprises the steps of dissolving lithium bis (trifluoromethane) sulfonyl imide (L iTFSI) with 1.0M electrolyte in a mixed solution of 1, 3-dioxolane (DO L) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, wherein the/graphene @ PP composite diaphragm is a battery diaphragm, a metal lithium sheet is a negative electrode, and anhydrous L iNO with the mass fraction of 2 wt% is added3In the absence of water and anaerobic (H)20<0.5ppm，O2<0.5ppm) in a glove box, CR2025 type button cells were assembled in the corresponding order the charge and discharge performance of the assembled button cells was tested at room temperature using L and ct2001A battery test system and CH1760E electrochemical workstation.
Example 3
(1) Co-doped MoS2Preparation of graphene composite material: the graphene aqueous solution prepared in the step (2) of example 1 was taken. 155mg (NH) are weighed4)6Mo7O24·4H2O, 285mg thiourea and 130mg Co (NO)3)2Adding the mixed solution into a graphene aqueous solution with the concentration of 70m L of 1-3 g/L, continuously stirring, transferring the obtained mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 200 ℃ for 18h, naturally cooling to room temperature, washing with deionized water, carrying out suction filtration, and carrying out vacuum drying on the obtained solid precipitate for 24h to obtain Co-doped MoS2A graphene composite material.
(2) Co-doped MoS2Preparation of a/graphene @ PP composite diaphragm: taking dried Co-doped MoS2Grinding the graphene composite material into powder, uniformly mixing the powder with conductive carbon black SuperP and a binder PVDF according to the mass ratio of 9:0.5:0.5, taking an N-methylpyrrolidone (NMP) solution as a dispersing agent, and stirring at a high speed to obtain coating slurry. Coating the coating slurry on one side surface of a polypropylene diaphragm (PP) by using a scraper coating method, and drying at 60 ℃ for 24 hours to obtain MoS2A graphene @ PP composite membrane.
(3) Co-doped MoS2The application of the/graphene @ PP composite diaphragm in the lithium-sulfur battery is as follows: to be provided withThe high sulfur-loaded sulfur/carbon electrode sheet prepared in step (1) of example 1 was used as a positive electrode, and MoS prepared as described above was used2The preparation method comprises the steps of dissolving lithium bis (trifluoromethane) sulfonyl imide (L iTFSI) with 1.0M electrolyte in a mixed solution of 1, 3-dioxolane (DO L) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, wherein the/graphene @ PP composite diaphragm is a battery diaphragm, a metal lithium sheet is a negative electrode, and anhydrous L iNO with the mass fraction of 2 wt% is added3In the absence of water and anaerobic (H)20<0.5ppm，O2<0.5ppm) in a glove box, CR2025 type button cells were assembled in the corresponding order the charge and discharge performance of the assembled button cells was tested at room temperature using L and ct2001A battery test system and CH1760E electrochemical workstation.
Comparative example 1
(1) Preparing the graphene aerogel: and (3) taking the graphene aqueous solution prepared in the step (2) in the example 1, transferring the graphene aqueous solution to a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 200 ℃ for 18h, naturally cooling to room temperature, washing with deionized water, carrying out suction filtration, and carrying out vacuum drying on the obtained solid precipitate for 24h to obtain the graphene aerogel.
(2) Preparing a graphene @ PP diaphragm: grinding the dried graphene aerogel into powder, uniformly mixing the powder with conductive carbon black SuperP and a binder PVDF according to the mass ratio of 9:0.5:0.5, taking an N-methylpyrrolidone (NMP) solution as a dispersing agent, and stirring at a high speed to obtain coating slurry. Coating the coating slurry on one side surface of a polypropylene diaphragm (PP) by using a scraper coating method, and drying at 60 ℃ for 24h to obtain the graphene @ PP diaphragm.
(3) The application of the graphene @ PP diaphragm in the lithium-sulfur battery is that the sulfur electrode plate prepared in the step (1) in the embodiment 1 is used as a positive electrode, the graphene @ PP diaphragm prepared in the embodiment is used as a battery diaphragm, the metal lithium plate is used as a negative electrode, 1.0M lithium bistrifluoromethanesulfonylimide (L iTFSI) electrolyte is dissolved in a mixed solution of 1, 3-dioxolane (DO L) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, and anhydrous L iNO with the mass fraction of 2 wt% is added3In the absence of water and anaerobic (H)20<0.5ppm，O2<0.5ppm) glove box was assembled with CR2025 type button cells in the corresponding order, using L and ct2001A cell testing system and CH1760E electrochemical workstation at room temperatureThe charge and discharge performance of the assembled button cell is tested, and the charge and discharge termination voltage range is 1.5-2.6V.
Comparative example 2
Taking the sulfur electrode plate prepared in the step (1) in the example 1 as a positive electrode, a polypropylene diaphragm (PP) as a battery diaphragm, a metal lithium plate as a negative electrode and 1.0M lithium bistrifluoromethanesulfonimide (L iTFSI) as an electrolyte, dissolving the lithium bistrifluoromethanesulfonimide (L iTFSI) in a mixed solution of 1, 3-dioxolane (DO L) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, and adding 2 wt% of anhydrous L iNO3In the absence of water and anaerobic (H)20<0.5ppm，O2<0.5ppm) was assembled in a glove box in the corresponding order, the charge and discharge performance of the assembled button cell was tested at room temperature using L and CT2001A battery test system and CH1760E electrochemical workstation, with a charge and discharge end voltage range of 1.5-2.6V.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A membrane having electrocatalytic properties, characterized by: the electrocatalytic functional membrane consists of a commercial polymer membrane substrate and an electrocatalytic functional modification layer coated on one side surface of the membrane substrate.
2. The membrane with electrocatalytic function as set forth in claim 1, wherein: the electrocatalytic function modification layer comprises a binder, a conductive agent and an electrocatalyst, the thickness of the electrocatalytic function modification layer is 10-100 mu m, and the mass ratio of the binder to the conductive agent to the electrocatalyst is 0.5-1:0.5-3: 6-9.
3. Electrocatalytic function as claimed in claim 2The separator of (2), characterized in that: the electrocatalyst is MoS doped with graphene and heteroatom2Assembled three-dimensional porous composite, MoS2The doped hetero atom is one or more of O, N, P, F, Se, Co, Ni, Fe and other elements; the binder is one or more of polyvinylidene fluoride, polyethylene oxide, polytetrafluoroethylene, carboxymethyl cellulose, styrene butadiene rubber, acrylonitrile multipolymer and gelatin binder; the conductive agent is any one or more of conductive carbon materials such as acetylene black, carbon fibers, carbon nanotubes, Ketjen black, conductive carbon black and the like.
4. The membrane with electrocatalytic function as set forth in claim 1, wherein: the diaphragm substrate is any one of a ceramic diaphragm, a polyethylene diaphragm, a polypropylene diaphragm, a polyester film, a polyamide film, a polyimide film, Celgard2500, Celgard2400, Celgard2340, a cellulose diaphragm, spandex and an aramid film.
5. A method for preparing the separator having an electrocatalytic function as set forth in claim 1, wherein: the method comprises the following steps: firstly, uniformly mixing graphene, a molybdenum source, a sulfur source and a precursor containing a doping element in an aqueous solution, and growing heteroatom-doped MoS on the surface of the graphene in situ by a hydrothermal method2Nanosheets, and simultaneously carrying out three-dimensional structure assembly; and then uniformly coating the binder, the conductive agent and the electrocatalyst on the surface of one side of the diaphragm substrate to prepare the lithium-sulfur battery diaphragm with the electrocatalysis function.
6. The method for producing a separator having an electrocatalytic function as set forth in claim 5, wherein: the preparation method specifically comprises the following steps:
(1) preparing graphene by using crystalline flake graphite as a raw material through an improved hummer method;
(2) will be (NH)4)6Mo7O24·4H2Adding O, thiourea and a precursor containing a doping element into the aqueous solution of the graphene, and continuously stirring;
(3) transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 150-220 ℃ for 18-24h, naturally cooling to room temperature, washing with deionized water, carrying out suction filtration, and freeze-drying the obtained solid precipitate for 12-24h to obtain heteroatom-doped MoS2A graphene composite material;
(4) the resulting heteroatom-doped MoS2Grinding the graphene composite material into powder, uniformly mixing the powder with a conductive agent and a binder in proportion, and stirring at a high speed to obtain coating slurry;
(5) and uniformly coating the coating slurry on one side surface of the commercial polymer diaphragm by using a doctor blade coating method, and drying at 40-70 ℃ for 12-24 h.
7. The method for producing a separator having an electrocatalytic function as set forth in claim 6, wherein: the precursor containing the doping element in the step (2) is NH4F、NaH2PO2、Na2SeO3、Co(NO3)2、Ni(NO3)2And Fe (NO)3)3One or more of the elements, the (NH)4)6Mo7O24·4H2The mass ratio of O, thiourea and the precursor containing the doping elements is 1:14-20: 0.01-0.10; (NH) in step (2)4)6Mo7O24·4H2The mass ratio of O to graphene is 0.5-1.5: 1; the mass ratio of the binder, the conductive carbon material and the three-dimensional porous composite material in the step (4) is 0.5-1:0.5-3: 6-9.
8. The application of a diaphragm with electrocatalytic function in a lithium-sulfur battery is characterized in that: the lithium-sulfur battery comprises a high-sulfur-loading sulfur/carbon composite material positive electrode, a metal lithium negative electrode, electrolyte and a diaphragm with an electrocatalytic function.
9. Use of a separator having electrocatalytic function according to claim 8 in a lithium-sulfur battery, characterized in that: one side of the functional modification layer in the diaphragm with the electrocatalysis function faces to the sulfur/carbon composite anode material.
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