CN109671949A - A kind of MXene base flexible compound negative electrode material and preparation method thereof - Google Patents

A kind of MXene base flexible compound negative electrode material and preparation method thereof Download PDF

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CN109671949A
CN109671949A CN201811516704.9A CN201811516704A CN109671949A CN 109671949 A CN109671949 A CN 109671949A CN 201811516704 A CN201811516704 A CN 201811516704A CN 109671949 A CN109671949 A CN 109671949A
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mxene
negative electrode
metal sulfide
expanded graphite
preparation
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邱从交
赵东辉
周鹏伟
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Fujian Xfh Battery Material Co Ltd
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Fujian Xfh Battery Material Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention discloses a kind of MXene base flexible compound negative electrode material and preparation method thereof, transient metal sulfide is supported on the two-dimensional layered structure of MXene material by the present invention by hydro-thermal method, overcome the reuniting effect of MXene material and prevent collapsing for layer structure, while improving the energy density of composite material；MXene material with high conductivity is born the responsibility three-dimensional conductive network skeleton, enhance the electric conductivity and mechanical strength of composite material, the volume expansion of transition metal polysulfide material during the charging process is buffered, while allowing material that there is good charge and discharge cycles stability.The composite material and expanded graphite are combined to the high flexibility negative electrode material for preparing a kind of self-supporting, in charge and discharge process, hydrophilic MXene material has stronger compatibility to polysulfide, it can be further improved the chemical property and capacitive deionization performance of composite negative pole material, and eliminate the sulfide of transient metal sulfide generation, the shuttle effect of polysulfide is limited, the service life of negative electrode material is improved.

Description

A kind of MXene base flexible compound negative electrode material and preparation method thereof
Technical field
The present invention relates to negative electrode material field technology, refer in particular to a kind of MXene base flexible compound negative electrode material and its Preparation method.
Background technique
Flexible battery is the critical component of wearable, foldable smart machine, and the backwardness of current flexible energy storage technology is Be unable to satisfy can portable flexible electronic equipment development demand.Therefore, low cost prepare it is frivolous, have both flexibility and it is high performance soft Property lithium ion battery material rapidly becomes the hot spot of research, and has a vast market foreground.
The cathode of the preparation method of traditional lithium cell cathode material and not applicable flexible lithium ion battery, currently, flexible The research of negative electrode material is concentrated mainly on high with carbon nanotube, graphene and active carbon cloth grade height conductive material, preparation cost And it is difficult to large-scale production.
The lower cost of transient metal sulfide theoretical capacity with higher becomes the active material of Recent study.But For such material in electrochemical reaction process, electrode material volume change is serious, easily causes electrode dusting, to reduce battery appearance Amount and service life.Meanwhile transient metal sulfide material reacts with lithium and can produce the more sulphur midbody products for being dissolved in electrolyte, is formed Shuttle effect, causes capacity to further decrease.
MXenes material is New Two Dimensional transition metal carbon/nitride of discovered in recent years, the high ratio with class graphene Surface area, very high bending strength, the electronic conductivity and high power charging-discharging electrochemical stability of superelevation, because its is excellent Electric property, hydrophily and unique lamellar morphologies make it have huge applications potentiality in terms of high magnification.Layer Shape structure and surface functional group abundant by MXene have very strong active force to polysulfide, it can be achieved that high-sulfur carrying capacity and fast Ion transmission, effectively prevents the shuttle effect of polysulfide.
With the development of science and technology, the flexible negative electrode material of the high-energy of low cost is the side of lithium ion battery in future development To, but current flexible negative electrode material is difficult to have both high capacity and high-intensitive flexibility.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide a kind of MXene base is soft Property composite negative pole material and preparation method thereof, can effectively solve existing flexibility negative electrode material be difficult to high-intensitive flexibility and The problem of high capacity is taken into account.
To achieve the above object, the present invention is using following technical solution:
A kind of preparation method of MXene base flexible compound negative electrode material, includes following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained is compound Object is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion liquid；
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, successively filter expanded graphite dispersion liquid, The compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal vulcanization Object compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；
(5) roll-forming: Sandwich film obtained in step (4) is prepared by simple roll-forming with a thickness of 100 ~400 μm of flexible compound negative electrode material.
As a preferred embodiment, the transient metal sulfide is MoS2、SnS2、CoS2、Ni2S3At least one of, Weight percentage is 5%-20%；The MXene material is the Ti that HF selective etching obtains3C2Tx、Ti2CTx、Ti3CNTx、 Cr2At least one of CTx, wherein Tx is-OH functional group or/and-F functional group.
As a preferred embodiment, the transition metal element is at least one of titanium, molybdenum, cobalt, nickel and tin, described The metal salt of transition metal element refer to the nitrate of transition metal, carbonate, sulfate, chloride it is one or more.
As a preferred embodiment, the sulphur source is vulcanized sodium, thiocarbamide, Ammonium Persulfate 98.5, at least one in thioacetamide Kind.
As a preferred embodiment, the molar ratio of the transient metal sulfide and the sulphur source is (0.2~1.0): 1。
As a preferred embodiment, the reaction temperature of the hydro-thermal reaction is 100 DEG C~200 DEG C, and the reaction time is for 24 hours ~48h collects solid product after cooling, is washed with deionized water and dehydrated alcohol alternate repetition, obtain being supported with transition metal The MXene/ transient metal sulfide composite material of sulfide.
As a preferred embodiment, MXene/ transient metal sulfide suspension is prepared in the step (2), MXene/ mistake The mass percent for crossing metal sulfide compound is 25%~50%, and mixing speed is 1000~2000rpm, mixing time 2 ~5h；The power of ultrasonic disperse is 750W, and ultrasonic time is 1~6h.
As a preferred embodiment, expanded graphite dispersion liquid is prepared in the step (3), expanded graphite in the dispersion liquid Mass fraction be 25%~50%, the expanded graphite be using fix carbon content greater than 98% natural flake graphite as raw material Through obtained by extruding, granularity is 100~250 mesh, and swelling volume is more than 250mL/g.
As a preferred embodiment, in the preparation of rapid (4) sandwich sandwich mixture, the expanded graphite Mass ratio with MXene- transient metal sulfide is (0.2~1.5): 1.
A kind of MXene base flexible compound negative electrode material, using a kind of aforementioned MXene base flexible compound negative electrode material Preparation method is made.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically, by above-mentioned technical proposal Known to:
Transient metal sulfide with higher energy density is supported on the two-dimensional layer of MXene material by hydro-thermal method by the present invention In shape structure, make MXene material is ingenious to overcome reuniting effect and prevent collapsing for layer structure, while improving the energy of composite material Metric density；The MXene material of high conductivity is born the responsibility three-dimensional conductive network skeleton, and the electric conductivity of composite material is greatly improved And mechanical strength, the volume expansion of buffering transition metal polysulfide material during the charging process allow material to have good fill Discharge cycles stability.The composite material and expanded graphite are combined to the high flexibility negative electrode material for preparing a kind of self-supporting, filled In discharge process, the hydrophily of MXene material and the compatibility to polysulfide can be further improved the electricity of composite negative pole material Chemical property and capacitive deionization performance, and the sulfide of transient metal sulfide generation is eliminated, limit wearing for polysulfide Shuttle effect improves the service life of negative electrode material.The method of the present invention preparation process is simple, easy to operate, and production cost is low, for amount It produces and application is laid a good foundation.
Detailed description of the invention
Fig. 1 is preparation flow schematic diagram of the invention；
Fig. 2 is the cycle performance of the embodiment of the present invention 1.
Specific embodiment
Present invention discloses a kind of preparation methods of MXene base flexible compound negative electrode material, include following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；The transient metal sulfide is MoS2、SnS2、CoS2、Ni2S3At least one of, weight percentage 5%-20%； The MXene material is the Ti that HF selective etching obtains3C2Tx、Ti2CTx、Ti3CNTx、Cr2At least one of CTx, wherein Tx For-OH functional group or/and-F functional group.The transition metal element is at least one of titanium, molybdenum, cobalt, nickel and tin, described The metal salt of transition metal element refer to the nitrate of transition metal, carbonate, sulfate, chloride it is one or more.Institute Stating sulphur source is at least one of vulcanized sodium, thiocarbamide, Ammonium Persulfate 98.5, thioacetamide.The transient metal sulfide with it is described Sulphur source molar ratio be (0.2~1.0): 1.The reaction temperature of the hydro-thermal reaction is 100 DEG C~200 DEG C, and the reaction time is For 24 hours~48h collects solid product after cooling, is washed with deionized water and dehydrated alcohol alternate repetition, obtains being supported with transition gold Belong to the MXene/ transient metal sulfide composite material of sulfide.
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained Compound is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；MXene/ transition Metal sulfide suspension is prepared, and the mass percent of MXene/ transient metal sulfide compound is 25%~50%, stirring speed Degree is 1000~2000rpm, and mixing time is 2~5h；The power of ultrasonic disperse is 750W, and ultrasonic time is 1~6h.
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion Liquid；The mass fraction of expanded graphite is 25%~50% in the dispersion liquid, and the expanded graphite is to fix carbon content and be greater than 98% natural flake graphite is raw material through obtained by extruding, granularity is 100~250 mesh, and swelling volume is more than 250mL/g.
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, expanded graphite dispersion is successively filtered Liquid, the compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal Sulfide compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；The expanded graphite and The mass ratio of MXene- transient metal sulfide is (0.2~1.5): 1.
(5) roll-forming: by Sandwich film obtained in step (4) by simple roll-forming prepare with a thickness of 100~400 μm of flexible compound negative electrode material.
The invention also discloses a kind of MXene base flexible compound negative electrode materials, flexible using a kind of aforementioned MXene base The preparation method of composite negative pole material is made.
With multiple embodiments, invention is further described in detail below:
Embodiment 1:
A kind of preparation method of MXene base flexible compound negative electrode material, includes following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；The transient metal sulfide is MoS2, weight percentage 5%；The MXene material is that HF selective etching obtains Ti3C2Tx, wherein Tx is-OH functional group.The transition metal element is titanium, and the metal salt of the transition metal element is Refer to the nitrate of transition metal.The sulphur source is vulcanized sodium.The transient metal sulfide and the molar ratio of the sulphur source are 0.2:1.The reaction temperature of the hydro-thermal reaction is 100 DEG C, and the reaction time is for 24 hours, to collect solid product after cooling, spend from Sub- water and the washing of dehydrated alcohol alternate repetition, the MXene/ transient metal sulfide for obtaining being supported with transient metal sulfide are compound Material.
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained Compound is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；MXene/ transition Metal sulfide suspension is prepared, and the mass percent of MXene/ transient metal sulfide compound is 25%, and mixing speed is 1000rpm, mixing time 2h；The power of ultrasonic disperse is 750W, ultrasonic time 1h.
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion Liquid；The mass fraction of expanded graphite is 25% in the dispersion liquid, and the expanded graphite is to fix carbon content greater than 98% Natural flake graphite is raw material through obtained by extruding, granularity is 100 mesh, and swelling volume is more than 250mL/g.
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, expanded graphite dispersion is successively filtered Liquid, the compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal Sulfide compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；The expanded graphite and The mass ratio of MXene- transient metal sulfide is 0.2:1.
(5) roll-forming: by Sandwich film obtained in step (4) by simple roll-forming prepare with a thickness of 100 μm of flexible compound negative electrode material.
The invention also discloses a kind of MXene base flexible compound negative electrode materials, flexible using a kind of aforementioned MXene base The preparation method of composite negative pole material is made.
The test of cycle performance is carried out to MXene base flexible compound negative electrode material made from the present embodiment, as shown in Fig. 2, With being continuously increased for cycle-index, charge specific capacity is maintained at 550mAh/g, and specific discharge capacity maintains the left side 600 mAh/g The right side, cycle performance are excellent.
Embodiment 2:
A kind of preparation method of MXene base flexible compound negative electrode material, includes following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；The transient metal sulfide is SnS2, weight percentage 20%；The MXene material is that HF selective etching obtains Ti2CTx, wherein Tx is-F functional group.The transition metal element is molybdenum, and the metal salt of the transition metal element refers to The carbonate of transition metal.The sulphur source is thiocarbamide.The molar ratio of the transient metal sulfide and the sulphur source is 1.0: 1.The reaction temperature of the hydro-thermal reaction is 200 DEG C, reaction time 48h, collects solid product after cooling, with deionized water and The washing of dehydrated alcohol alternate repetition, obtains the MXene/ transient metal sulfide composite material for being supported with transient metal sulfide.
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained Compound is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；MXene/ transition Metal sulfide suspension is prepared, and the mass percent of MXene/ transient metal sulfide compound is 50%, and mixing speed is 2000rpm, mixing time 5h；The power of ultrasonic disperse is 750W, ultrasonic time 6h.
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion Liquid；The mass fraction of expanded graphite is 50% in the dispersion liquid, and the expanded graphite is to fix carbon content greater than 98% Natural flake graphite is raw material through obtained by extruding, granularity is 250 mesh, and swelling volume is more than 250mL/g.
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, expanded graphite dispersion is successively filtered Liquid, the compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal Sulfide compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；The expanded graphite and The mass ratio of MXene- transient metal sulfide is 1.5:1.
(5) roll-forming: by Sandwich film obtained in step (4) by simple roll-forming prepare with a thickness of 400 μm of flexible compound negative electrode material.
The invention also discloses a kind of MXene base flexible compound negative electrode materials, flexible using a kind of aforementioned MXene base The preparation method of composite negative pole material is made.
Embodiment 3:
A kind of preparation method of MXene base flexible compound negative electrode material, includes following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；The transient metal sulfide is CoS2, weight percentage 15%；The MXene material is that HF selective etching obtains Ti3CNTx, wherein Tx is-OH functional group and-F functional group.The transition metal element is cobalt, the transition metal element Metal salt refer to the sulfate of transition metal.The sulphur source is Ammonium Persulfate 98.5.The transient metal sulfide and the sulphur The molar ratio in source is 0.6:1.The reaction temperature of the hydro-thermal reaction is 150 DEG C, reaction time 36h, collects solid after cooling Product is washed with deionized water and dehydrated alcohol alternate repetition, obtains the MXene/ transition gold for being supported with transient metal sulfide Belong to sulfide composite material.
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained Compound is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；MXene/ transition Metal sulfide suspension is prepared, and the mass percent of MXene/ transient metal sulfide compound is 40%, and mixing speed is 1500rpm, mixing time 3h；The power of ultrasonic disperse is 750W, ultrasonic time 4h.
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion Liquid；The mass fraction of expanded graphite is 35% in the dispersion liquid, and the expanded graphite is to fix carbon content greater than 98% Natural flake graphite is raw material through obtained by extruding, granularity is 200 mesh, and swelling volume is more than 250mL/g.
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, expanded graphite dispersion is successively filtered Liquid, the compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal Sulfide compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；The expanded graphite and The mass ratio of MXene- transient metal sulfide is 1:1.
(5) roll-forming: by Sandwich film obtained in step (4) by simple roll-forming prepare with a thickness of 300 μm of flexible compound negative electrode material.
The invention also discloses a kind of MXene base flexible compound negative electrode materials, flexible using a kind of aforementioned MXene base The preparation method of composite negative pole material is made.
Embodiment 4:
A kind of preparation method of MXene base flexible compound negative electrode material, includes following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；The transient metal sulfide is Ni2S3, weight percentage 8%；The MXene material is that HF selective etching obtains Cr2CTx, wherein Tx is-OH functional group.The transition metal element is nickel, and the metal salt of the transition metal element is Refer to the chloride of transition metal.The sulphur source is thioacetamide.Mole of the transient metal sulfide and the sulphur source Than for 0.4:1.The reaction temperature of the hydro-thermal reaction is 120 DEG C, reaction time 30h, collects solid product after cooling, is used Deionized water and the washing of dehydrated alcohol alternate repetition, obtain the MXene/ transient metal sulfide for being supported with transient metal sulfide Composite material.
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained Compound is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；MXene/ transition Metal sulfide suspension is prepared, and the mass percent of MXene/ transient metal sulfide compound is 45%, and mixing speed is 1200rpm, mixing time 3h；The power of ultrasonic disperse is 750W, ultrasonic time 4h.
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion Liquid；The mass fraction of expanded graphite is 40% in the dispersion liquid, and the expanded graphite is to fix carbon content greater than 98% Natural flake graphite is raw material through obtained by extruding, granularity is 180 mesh, and swelling volume is more than 250mL/g.
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, expanded graphite dispersion is successively filtered Liquid, the compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal Sulfide compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；The expanded graphite and The mass ratio of MXene- transient metal sulfide is 0.5:1.
(5) roll-forming: by Sandwich film obtained in step (4) by simple roll-forming prepare with a thickness of 150 μm of flexible compound negative electrode material.
The invention also discloses a kind of MXene base flexible compound negative electrode materials, flexible using a kind of aforementioned MXene base The preparation method of composite negative pole material is made.
Embodiment 5:
A kind of preparation method of MXene base flexible compound negative electrode material, includes following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；The transient metal sulfide is MoS2And SnS2, weight percentage 18%；The MXene material is that HF selection is carved Lose obtained Ti3C2Tx and Ti2CTx, wherein Tx is-OH functional group and-F functional group.The transition metal element is tin, described The metal salt of transition metal element refer to the nitrate and carbonate of transition metal.The sulphur source is vulcanized sodium and thiocarbamide.Institute The molar ratio for stating transient metal sulfide and the sulphur source is 0.7:1.The reaction temperature of the hydro-thermal reaction is 140 DEG C, instead It is 43h between seasonable, collects solid product after cooling, washed, be supported with deionized water and dehydrated alcohol alternate repetition Cross the MXene/ transient metal sulfide composite material of metal sulfide.
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained Compound is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；MXene/ transition Metal sulfide suspension is prepared, and the mass percent of MXene/ transient metal sulfide compound is 38%, and mixing speed is 1700rpm, mixing time 3h；The power of ultrasonic disperse is 750W, ultrasonic time 2h.
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion Liquid；The mass fraction of expanded graphite is 38% in the dispersion liquid, and the expanded graphite is to fix carbon content greater than 98% Natural flake graphite is raw material through obtained by extruding, granularity is 190 mesh, and swelling volume is more than 250mL/g.
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, expanded graphite dispersion is successively filtered Liquid, the compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal Sulfide compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；The expanded graphite and The mass ratio of MXene- transient metal sulfide is 0.9:1.
(5) roll-forming: by Sandwich film obtained in step (4) by simple roll-forming prepare with a thickness of 250 μm of flexible compound negative electrode material.
The invention also discloses a kind of MXene base flexible compound negative electrode materials, flexible using a kind of aforementioned MXene base The preparation method of composite negative pole material is made.
Embodiment 6:
A kind of preparation method of MXene base flexible compound negative electrode material, includes following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；The transient metal sulfide is MoS2、SnS2And CoS2, weight percentage 22%；The MXene material is HF choosing Select the Ti that etching obtains3C2Tx、Ti2CTx、Ti3CNTx and Cr2CTx, wherein Tx is-OH functional group and-F functional group.The transition Metallic element is titanium, molybdenum and cobalt, and the metal salt of the transition metal element refers to the nitrate of transition metal, carbonate, sulphur Hydrochlorate and chloride.The sulphur source is vulcanized sodium, thiocarbamide, Ammonium Persulfate 98.5 and thioacetamide.The transient metal sulfide with The molar ratio of the sulphur source is 0.7:1.The reaction temperature of the hydro-thermal reaction is 170 DEG C, reaction time 28h, after cooling Solid product is collected, is washed with deionized water and dehydrated alcohol alternate repetition, obtains being supported with transient metal sulfide MXene/ transient metal sulfide composite material.
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained Compound is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；MXene/ transition Metal sulfide suspension is prepared, and the mass percent of MXene/ transient metal sulfide compound is 46%, and mixing speed is 1600rpm, mixing time 4h；The power of ultrasonic disperse is 750W, ultrasonic time 5h.
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion Liquid；The mass fraction of expanded graphite is 48% in the dispersion liquid, and the expanded graphite is to fix carbon content greater than 98% Natural flake graphite is raw material through obtained by extruding, granularity is 240 mesh, and swelling volume is more than 250mL/g.
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, expanded graphite dispersion is successively filtered Liquid, the compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal Sulfide compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；The expanded graphite and The mass ratio of MXene- transient metal sulfide is 1.4:1.
(5) roll-forming: by Sandwich film obtained in step (4) by simple roll-forming prepare with a thickness of 380 μm of flexible compound negative electrode material.
The invention also discloses a kind of MXene base flexible compound negative electrode materials, flexible using a kind of aforementioned MXene base The preparation method of composite negative pole material is made.
Design focal point of the invention is: the present invention is vulcanized the transition metal with higher energy density by hydro-thermal method Object is supported on the two-dimensional layered structure of MXene material, makes MXene material is ingenious to overcome reuniting effect and prevent layer structure It collapses, while improving the energy density of composite material；The MXene material of high conductivity is born the responsibility three-dimensional conductive network skeleton, greatly Amplitude improves the electric conductivity and mechanical strength of composite material, the body of buffering transition metal polysulfide material during the charging process Product expansion, allows material to have good charge and discharge cycles stability.The composite material and expanded graphite are combined and prepare one kind certainly The high flexibility negative electrode material of support, in charge and discharge process, the hydrophily of MXene material and the compatibility to polysulfide, energy The chemical property and capacitive deionization performance of composite negative pole material are further increased, and eliminates transient metal sulfide generation Sulfide limits the shuttle effect of polysulfide, improves the service life of negative electrode material.The method of the present invention preparation process letter Single, easy to operate, production cost is low, lays a good foundation for volume production and application.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention, Therefore any subtle modifications, equivalent variations and modifications to the above embodiments according to the technical essence of the invention, still Belong in the range of technical solution of the present invention.

Claims (10)

1. a kind of preparation method of MXene base flexible compound negative electrode material, it is characterised in that: include following steps:
(1) prepared by MXene/ transient metal sulfide: the metal salt of transition metal element and sulphur source being mixed, MXene is added Material, alkaline solution obtain mixed solution, in a high pressure reaction kettle hydro-thermal reaction, and it is multiple to obtain MXene/ transient metal sulfide Close object；
(2) MXene/ transient metal sulfide suspension is prepared: the MXene/ transient metal sulfide that step (1) is obtained is compound Object is add to deionized water, high-speed stirred uniformly after re-ultrasonic dispersion, be configured to suspension, it is spare；
(3) expanded graphite dispersion liquid is prepared: expanded graphite is evenly dispersed in deionized water, obtain expanded graphite dispersion liquid；
(4) preparation of sandwich sandwich mixture: by the method for vacuum filtration, successively filter expanded graphite dispersion liquid, The compound suspension of MXene/ transient metal sulfide, expanded graphite dispersion liquid form expanded graphite/MXene- transition metal vulcanization Object compound/expanded graphite Sandwich film, film are dried at normal temperatures and pressures；
(5) roll-forming: Sandwich film obtained in step (4) is prepared by simple roll-forming with a thickness of 100 ~400 μm of flexible compound negative electrode material.
2. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: The transient metal sulfide is MoS2、SnS2、CoS2、Ni2S3At least one of, weight percentage 5%-20%；It is described MXene material is the Ti that HF selective etching obtains3C2Tx、Ti2CTx、Ti3CNTx、Cr2At least one of CTx, wherein Tx be- OH functional group or/and-F functional group.
3. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: The transition metal element is at least one of titanium, molybdenum, cobalt, nickel and tin, and the metal salt of the transition metal element refers to The nitrate of transition metal, carbonate, sulfate, chloride it is one or more.
4. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: The sulphur source is at least one of vulcanized sodium, thiocarbamide, Ammonium Persulfate 98.5, thioacetamide.
5. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: The molar ratio of the transient metal sulfide and the sulphur source is (0.2~1.0): 1.
6. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: The reaction temperature of the hydro-thermal reaction is 100 DEG C~200 DEG C, and the reaction time is for 24 hours~48h, collects solid product after cooling, It is washed with deionized water and dehydrated alcohol alternate repetition, obtains the MXene/ transition metal vulcanization for being supported with transient metal sulfide Object composite material.
7. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: MXene/ transient metal sulfide suspension is prepared in the step (2), the quality of MXene/ transient metal sulfide compound Percentage is 25%~50%, and mixing speed is 1000~2000rpm, and mixing time is 2~5h；The power of ultrasonic disperse is 750W, ultrasonic time are 1~6h.
8. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: Expanded graphite dispersion liquid is prepared in the step (3), and the mass fraction of expanded graphite is 25%~50% in the dispersion liquid, described Expanded graphite be to fix natural flake graphite of the carbon content greater than 98% be raw material through obtained by extruding, granularity is 100~250 Mesh, swelling volume are more than 250mL/g.
9. a kind of preparation method of MXene base flexible compound negative electrode material according to claim 1, it is characterised in that: In the preparation of rapid (4) sandwich sandwich mixture, the expanded graphite and MXene- transient metal sulfide Mass ratio is (0.2~1.5): 1.
10. a kind of MXene base flexible compound negative electrode material, it is characterised in that: described in any item using such as claim 1-9 A kind of preparation method of MXene base flexible compound negative electrode material is obtained.
CN201811516704.9A 2018-12-12 2018-12-12 A kind of MXene base flexible compound negative electrode material and preparation method thereof Pending CN109671949A (en)

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