CN106532015A - MoS2 inserted-layer Ti3C2 lithium ion battery negative electrode material and preparation method thereof - Google Patents

MoS2 inserted-layer Ti3C2 lithium ion battery negative electrode material and preparation method thereof Download PDF

Info

Publication number
CN106532015A
CN106532015A CN201611226367.0A CN201611226367A CN106532015A CN 106532015 A CN106532015 A CN 106532015A CN 201611226367 A CN201611226367 A CN 201611226367A CN 106532015 A CN106532015 A CN 106532015A
Authority
CN
China
Prior art keywords
mos
solution
lithium ion
ion battery
intercalation
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
CN201611226367.0A
Other languages
Chinese (zh)
Other versions
CN106532015B (en
Inventor
郭瑞松
郑梅
王宝玉
刘志超
李福运
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.)
Tianjin University
Original Assignee
Tianjin University
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 Tianjin University filed Critical Tianjin University
Priority to CN201611226367.0A priority Critical patent/CN106532015B/en
Publication of CN106532015A publication Critical patent/CN106532015A/en
Application granted granted Critical
Publication of CN106532015B publication Critical patent/CN106532015B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • H01M4/58—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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 MoS2 inserted-layer Ti3C2 lithium ion battery negative electrode material and a preparation method thereof. A MoS2 inserted-layer Ti3C2 composite material is prepared by taking titanium aluminum carbide as a main raw material and employing different molybdenum sources and sulfur sources, and the mass percent of MoS2 after combination accounts for 1-50%. The initial discharge specific capacity of the MoS2 inserted-layer Ti3C2 lithium ion battery negative electrode material is 604.2mAh/g under 50mA/g, the capacity of a product is 153.3mAh/g under 500mA/g after circulation of 50 times, the interlayer distance is 1.2346 nanometers, the capacity is obviously improved, the interlayer distance is remarkably extended, and the preparation method is a modified method which is simple in process and low in cost, and is suitable for industrial production.

Description

Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of molybdenum bisuphide (MoS2) intercalation titanium carbide (Ti3C2) open conduction negative material and preparation method thereof.
Background technology
Non-renewable energy resources crisis in global range so that sustainable energy is extensively favored.Lithium ion battery is made For safely and efficiently new forms of energy, every field is widely used in.But with the progress of science and technology, electronic equipment, automobile etc. The fast-developing performance to battery is put forward higher requirement, and is badly in need of finding or preparing more preferable electrode material to improve battery Combination property.
In numerous negative materials, transition metal carbide or nitride receive increasing pass in recent years Note.This kind of material be by hf etching MAX (wherein M represents transition metal, and A is the 3rd main group or the 4th major element, X represents carbon or nitrogen) " A " element layer in former phase and get, the product for obtaining consists of Mn+1XnTx(n values are 1,2 or 3, T be introduce during etching～F and the～surface functional group such as OH), because itself and Graphene have a similar structure, therefore quilt Referred to as MXene.It has advantages below (but being not limited only to these advantages)：(1) specific surface area is high, can effectively with electrolysis Matter is contacted, and carries out the transmission of electronics and ion；(2) good conductivity, the layer structure of two dimension are conducive to electronics and ion in interlayer Quick transmission；(3) with hydrophilic so that electrode can be conducive to the diffusion of ion by electrolyte moistening.Therefore, MXene It is a kind of very promising lithium ion battery negative material.
Have at present more than a 70 kinds of MXene material, wherein carbon titanium compound because synthetic method is simple, low cost, performance it is excellent Different the features such as, gets more and more people's extensive concerning.Carbon titanium compound has some concrete materials, wherein Ti3C2It is that Recent study is most A kind of MXene materials, it has specific surface area big, little lithium ion diffusional resistance, good cycling stability, lithographic technique maturation etc. Advantage.But Ti3C2After little, the de- lithium of interlamellar spacing is there is as other MXene, lamella is piled up again, is lacked between layers Weary connection, electronics are the shortcomings of the direction diffusion rate perpendicular to layer is slow.Therefore, in order to promote Ti3C2Material applies to electricity Chi Zhong, then need to take measures to solve the above problems, further improve Ti3C2The performance of material.
For the problems referred to above, different researchers by method the improves MXene materials such as intercalation, layering, surface be modified itself Defect.Wherein intercalation is most technology of applying at present, and effect is best.Many scholars adopt low-dimensional material with carbon element intercalation Ti3C2, Such as Xie et al. is attempted with CNT intercalation Ti3C2, the chemical property of composite is improve, but due to CNT Self-capacity is low, with its intercalation Ti3C2The capacity of the composite for obtaining is relatively low, it is impossible to meet lithium ion cell high-capacity Require [Xie X, Zhao M Q, Anasori B, et al.Nano Energy, 2016,26:513～523.].Also scholar adopts With transition metal oxide intercalation MXene, such as Cu2O[Zhang H,Dong H,Zhang X,et al.Electrochimica Acta,2016,202:24～31], but these molecules are often graininess, granularity is big, it is difficult to It is inserted into interlayer.So be badly in need of finding and can stably support lamella into MXene interlayers and significantly improve MXene material capacities Material improves the chemical property of MXene.
MoS2Have the advantages that capacity height, specific surface area are big, by MoS2It is inserted into Ti3C2Interlayer, be conducive to support Ti3C2 Lamella, forms open conductive three dimensional structure, promotes lithium ion quickly to transmit in interlayer, and prevents Ti3C2After the de- lithium of lamella again Pile up.The composite is made up of thin lamella, and specific surface area is big, is conducive to electrode to contact with electrolyte, shorten lithium from The transmission range of son.MoS2It is connected to Ti3C2Levels, formed linear contact lay, improve Ti3C2Electronics perpendicular to layer direction is led Electrically.MoS2When electrode material is individually used for, with the deintercalation of lithium ion, volume significant changes, capacity significantly can decay. MoS2It is inserted into Ti3C2Interlayer after, the space of interlayer is conducive to alleviating MoS2Change in volume, reduce MoS2In discharge and recharge Capacitance loss and degree of polarization in journey.By sulphur source and molybdenum source and Ti3C2Ultrasound, is conducive to sulphur source and molybdenum source molecule to enter together Ti3C2Interlayer, the two generates MoS in Coating combination2.The MoS obtained by this in situ synthesis2Can be with Ti3C2Closely connect Touch, be conducive to electric transmission therebetween.
By literature search, the present invention is directed to MoS2Intercalation Ti3C2Improve chemical property and be not yet disclosed and reported.
The content of the invention
The purpose of the present invention, is to prepare MoS using hydro-thermal method2The Ti of intercalation3C2Negative material, to improve Ti3C2Electricity Chemical property.Prepare with excellent chemical property there is provided a kind of employing process is simple, method of modifying with low cost Lithium ion battery negative material.
Ti3C2The major defect of negative material is that interlamellar spacing is less, and after de- lithium, lamella is piled up again, and lithium ion is in interlayer Transmission is difficult；And shortage connection, electronics are slow in the direction diffusion rate perpendicular to layer between layers.Use MoS2Intercalation can be propped up Support Ti3C2Lamella, increases its interlamellar spacing, and after preventing lithium ion abjection, lamella is piled up again.MoS2It is connected to Ti3C2Fluctuating plate Layer, defines three-dimensional conductive structure, promotes electronics to transmit in the direction perpendicular to layer, significantly increases Ti3C2Electric conductivity.And MoS2And Ti3C2All have laminar structured, the two three dimensional structure being compounded to form increases contact of the electrode material with electrolyte Area, reduces diffusion length and the electric transmission path of lithium ion.And Ti3C2Layer structure be conducive to buffer MoS2In lithium Change in volume during ion deinsertion, reduces MoS2Capacitance loss and degree of polarization in charge and discharge process.
The present invention is achieved by following technical solution：
(1) prepare Ti3C2：
By Ti3AlC20.05 gram of ratio is added to be distributed in the hydrofluoric acid solution that concentration is 49% according to every milliliter of solution, Stir 24 hours under room temperature, then by mixed solution centrifugation, and precipitate deionized water is rinsed 7～10 times, until The pH value of the solution of flushed precipitate is to 5.5, then the precipitate of acquisition is put in vacuum drying oven in 80 DEG C of dryings 12 hours, Ti is obtained3C2Powder；
(2) synthesize MoS2/Ti3C2Composite：
First add 0.00013～0.01576 gram of ratio to be added in ethanol solution according to every milliliter of solution molybdenum source, treat After being completely dissolved, 0.01428 gram of ratio is added to add the Ti obtained by step (1) according still further to every milliliter of solution3C2Powder, stirring Uniformly；It is last to add 0.00014～0.01359 gram of ratio to add sulphur source according to every milliliter of solution, it is stirred for uniform rear ultrasound Dispersion 1 hour, promotes solution to enter Ti3C2Interlayer；
Again above-mentioned mixed solution is transferred in autoclave, be put in air dry oven at 140～220 DEG C insulation 10～ Carry out hydro-thermal method fabricated in situ within 48 hours, then naturally cool to what is obtained after room temperature, vacuum filtration, and deionized water are rinsed MoS2/Ti3C2Composite, then dry 12 hours in 80 DEG C in vacuum drying oven, 325 mesh sieves are crossed after grinding, MoS is obtained2/ Ti3C2The black powder of composite.
The step (2) uses MoS2Intercalation Ti3C2, form MoS2/Ti3C2Composite.
The molybdenum source of the step (2) is two molybdic acid hydrate sodium, Ammonium Molybdate Tetrahydrate or molybdenum trioxide.
The sulphur source of the step (2) is L～cysteine, thioacetamide or thiourea.
The present invention prepares MoS using hydro-thermal method2The Ti of intercalation3C2Lithium ion battery negative material, with Open architecture With excellent chemical property, it is 604.2 MAhs/g in the lower first discharge specific capacity of 50 milliamperes/gram, under 500 milliamperes/gram Capacity after cycle articles 50 times is 153.3 MAhs/g, and interlamellar spacing is 1.2346 nanometers, and capacity is significantly improved, and interlamellar spacing shows Write increase.Preparation method of the present invention is simple, and material electrochemical performance is excellent, is adapted to industrialized production.
Description of the drawings
Fig. 1 is first charge-discharge curve chart of the comparative example of the present invention under each electric current density；
Fig. 2 is first charge-discharge curve chart of the embodiment of the present invention 4 under each electric current density；
Fig. 3 is first charge-discharge curve chart of the embodiment of the present invention 5 under each electric current density；
Fig. 4 is the embodiment of the present invention 4,5 and cycle performance curve of the comparative example under 500 milliampere/gram electric current densities Figure；
Fig. 5 is the powder diffraction of the embodiment of the present invention 4,5 and comparative example at 5～80 ° of angles；
Fig. 6 is the powder diffraction of the embodiment of the present invention 4,5 and comparative example at 5～12 ° of angles；
Fig. 7 is the powder scanning electron microscope (SEM) photograph of the embodiment of the present invention 4.
Specific embodiment
The present invention is described further with reference to specific embodiment.
Comparative example
With Ti3C2Powder is assembled into button cell using conventional method, then carries out electrochemistry as negative material Can test.
To Ti3C2The battery of dusty material assembling carries out first charge-discharge and cycle performance test.Contrast as can be seen from Figure 1 real The product for applying example is 449.3 MAhs/g in the lower first discharge specific capacity of 50 milliamperes/gram；As shown in Figure 4 under 500 milliamperes/gram Capacity after comparative example's cycle articles 50 times is 71.4 MAhs/g；The interlamellar spacing of Fig. 6 display comparison embodiment products is 0.9659 nanometer.Test result shows no MoS2The Ti of intercalation3C2The capacity of powder body is low and interlamellar spacing is little.
Embodiment 1
(1) by Ti3AlC20.05 gram of ratio is added to be distributed to the hydrofluoric acid solution that concentration is 49% according to every milliliter of solution In, stir 24 hours under room temperature, then by mixed solution centrifugation, and precipitate deionized water is rinsed 7 times, Zhi Daochong The pH value of the solution of washed precipitate is to 5.5, then the precipitate of acquisition is put in vacuum drying oven in 80 DEG C of dryings 12 Hour, Ti is obtained3C2Powder；
(2) first 0.00022 gram of ratio is added to be added in ethanol solution according to every milliliter of solution in two molybdic acid hydrate sodium, Until completely dissolved, 0.01428 gram of ratio is added to add the Ti obtained by step (1) according still further to every milliliter of solution3C2Powder, stirs Mix uniform；It is last to add 0.00022 gram of ratio to add L～cysteine according to every milliliter of solution, it is stirred for uniform rear ultrasound Dispersion 1 hour, promotes solution to enter Ti3C2Interlayer；
Again above-mentioned mixed solution is transferred in autoclave, is incubated to enter for 10 hours in being put into air dry oven at 140 DEG C Water-filling full-boiled process fabricated in situ, then naturally cools to room temperature, vacuum filtration, and deionized water and rinses the MoS for obtaining2/Ti3C2 Composite, then dry 12 hours in 80 DEG C in vacuum drying oven, 325 mesh sieves are crossed after grinding, it is 1% to obtain mass fraction MoS2The Ti of intercalation3C2Composite.
With the MoS2/Ti3C2Composite is assembled into button using conventional method as lithium ion battery negative material Battery.Powder diffraction and the test of surface sweeping Electronic Speculum are carried out to powder body material and first charge-discharge and cycle performance survey are carried out to battery Examination.As a result show Ti3C2Interlamellar spacing increased than comparative example, the chemical property of 1 product of embodiment has been carried It is high.
Embodiment 2
(1) by Ti3AlC20.05 gram of ratio is added to be distributed to the hydrofluoric acid solution that concentration is 49% according to every milliliter of solution In, stir 24 hours under room temperature, then by mixed solution centrifugation, and precipitate deionized water is rinsed 7 times, Zhi Daochong The pH value of the solution of washed precipitate is to 5.5, then the precipitate of acquisition is put in vacuum drying oven in 80 DEG C of dryings 12 Hour, Ti is obtained3C2Powder；
(2) first add 0.00013 gram of ratio to be added in ethanol solution according to every milliliter of solution molybdenum trioxide, treated After CL, 0.01428 gram of ratio is added to add the Ti obtained by step (1) according still further to every milliliter of solution3C2Powder, stirring are equal It is even；It is last to add 0.00014 gram of ratio to add thioacetamide according to every milliliter of solution, it is stirred for uniform rear ultrasonic disperse 1 Hour, promote solution to enter Ti3C2Interlayer；
Again above-mentioned mixed solution is transferred in autoclave, is incubated to enter for 48 hours in being put into air dry oven at 220 DEG C Water-filling full-boiled process fabricated in situ, then naturally cools to room temperature, vacuum filtration, and deionized water and rinses the MoS for obtaining2/Ti3C2 Composite, then dry 12 hours in 80 DEG C in vacuum drying oven, 325 mesh sieves are crossed after grinding, it is 1% to obtain mass fraction MoS2The Ti of intercalation3C2Composite.
With the MoS2/Ti3C2Composite is assembled into button using conventional method as lithium ion battery negative material Battery.Powder diffraction and the test of surface sweeping Electronic Speculum are carried out to powder body material and first charge-discharge and cycle performance survey are carried out to battery Examination.There is MoS in powder diagram2Diffraction maximum, surface sweeping electron microscope show Ti3C2Contain a small amount of MoS between lamella2Nanometer Piece.Cell testing results show that the capacity and interlamellar spacing of 2 product of embodiment all improves, and good cycling stability.
Embodiment 3
(1) by Ti3AlC20.05 gram of ratio is added to be distributed to the hydrofluoric acid solution that concentration is 49% according to every milliliter of solution In, stir 24 hours under room temperature, then by mixed solution centrifugation, and precipitate deionized water is rinsed 7 times, Zhi Daochong The pH value of the solution of washed precipitate is to 5.5, then the precipitate of acquisition is put in vacuum drying oven in 80 DEG C of dryings 12 Hour, Ti is obtained3C2Powder；
(2) first 0.00016 gram of ratio is added to be added in ethanol solution according to every milliliter of solution Ammonium Molybdate Tetrahydrate, Until completely dissolved, 0.01428 gram of ratio is added to add the Ti obtained by step (1) according still further to every milliliter of solution3C2Powder, stirs Mix uniform；It is last to add 0.00014 gram of ratio to add thiourea according to every milliliter of solution, it is stirred for uniform rear ultrasonic disperse 1 little When, promote solution to enter Ti3C2Interlayer；
Again above-mentioned mixed solution is transferred in autoclave, is incubated to enter for 24 hours in being put into air dry oven at 200 DEG C Water-filling full-boiled process fabricated in situ, then naturally cools to room temperature, vacuum filtration, and deionized water and rinses the MoS for obtaining2/Ti3C2 Composite, then dry 12 hours in 80 DEG C in vacuum drying oven, 325 mesh sieves are crossed after grinding, it is 1% to obtain mass fraction MoS2The Ti of intercalation3C2Composite.
With the MoS2/Ti3C2Composite is assembled into button using conventional method as lithium ion battery negative material Battery.Powder diffraction and the test of surface sweeping Electronic Speculum are carried out to powder body material and first charge-discharge and cycle performance survey are carried out to battery Examination.Surface sweeping electron microscope shows Ti3C2MoS between lamella2Pattern is complete, with clearly lamellar structure.Electrochemical property test As a result show that 3 product of embodiment is all significantly improved than the capacity and interlamellar spacing of comparative example, and good cycling stability.
Embodiment 4
The present embodiment is by MoS2Mass fraction is adjusted to 20%, and, with embodiment 3, it is 20% to obtain mass fraction for remaining MoS2The Ti of intercalation3C2Composite.
With the MoS2/Ti3C2Composite is assembled into button using conventional method as lithium ion battery negative material Battery.Powder diffraction and the test of surface sweeping Electronic Speculum are carried out to powder body material and first charge-discharge and cycle performance survey are carried out to battery Examination.The product of embodiment 4 is 503.3 MAhs/g in the lower first discharge specific capacity of 50 milliamperes/gram as can be seen from Figure 2, is compared than real The capacity for applying a product improves 54 MAhs/g；As shown in Figure 4 to 4 cycle articles of embodiment 50 times under 500 milliamperes/gram Capacity afterwards is 153.3 MAhs/g, improves 81.9 MAhs/g than the capacity of comparative example product；Fig. 5 shows real There is MoS in applying 4 product of example2Diffraction maximum；The interlamellar spacing of 4 product of embodiment is 1.2346 nanometers as can be seen from Figure 6, is compared 0.2687 nanometer is increased than the interlamellar spacing of embodiment product.Test result shows the MoS compared with comparative example with 20%2 The Ti of intercalation3C2The capacity of powder body is significantly improved and interlayer is significantly increased.Fig. 7 shows Ti3C2Growth in situ many on lamella MoS2Nanoscale twins, it was demonstrated that MoS can be synthesized by technical scheme proposed by the invention2The Ti of intercalation3C2Composite.
Embodiment 5
The present embodiment is by MoS2Mass fraction is adjusted to 30%, and, with embodiment 3, it is 30% to obtain mass fraction for remaining MoS2The Ti of intercalation3C2Composite.
With the MoS2/Ti3C2Composite is assembled into button using conventional method as lithium ion battery negative material Battery.Powder diffraction and the test of surface sweeping Electronic Speculum are carried out to powder body material and first charge-discharge and cycle performance survey are carried out to battery Examination.5 product of embodiment is 604.2 MAhs/g in the lower first discharge specific capacity of 50 milliamperes/gram as can be seen from Figure 3, is compared than implementing The capacity of example product improves 154.9 MAhs/g；As shown in Figure 4 to 5 cycle articles of embodiment 50 times under 500 milliamperes/gram Capacity afterwards is 153.3 MAhs/g, improves 81.9 MAhs/g than the capacity of comparative example product；Fig. 5 shows real There is MoS in applying 5 product of example2Diffraction maximum；Fig. 6 shows that the interlamellar spacing of 5 product of embodiment is 1.2346 nanometers, compares than implementing The interlamellar spacing of example product increases 0.2687 nanometer.Test result shows the MoS with 30%2The Ti of intercalation3C2The capacity of powder body is bright Aobvious to improve, interlamellar spacing is also significantly increased.
Embodiment 6
The present embodiment is by MoS2Mass fraction is adjusted to 50%, and, with embodiment 3, it is 50% to obtain mass fraction for remaining MoS2The Ti of intercalation3C2Composite.
With the MoS2/Ti3C2Composite is assembled into button using conventional method as lithium ion battery negative material Battery.Powder diffraction and the test of surface sweeping Electronic Speculum are carried out to powder body material and first charge-discharge and cycle performance survey are carried out to battery Examination.As a result show that 6 product of embodiment is increased substantially than the capacity of comparative example.
The method of testing of the present invention is as follows.
With MoS prepared by the present invention2The Ti of intercalation3C2Used as active substance, SuperP is conductive agent to powder, polyvinylidene fluoride Alkene (PVDF) is binding agent, in mass ratio 80：10：10 weigh a certain amount of above-mentioned three kinds of materials.PVDF is dissolved in into N～methyl pyrrole Stirring in pyrrolidone (NMP) forms colloid in 1.5 hours, and SuperP is then added in gained colloid and 2 hours are stirred, Zhi Houjia Enter active substance powder body and continue stirring 3 hours.The slurry for obtaining is coated in into the copper foil surface (slurry of cleaning with adjustable spreader The thickness of material is 100 microns), the Copper Foil for scribbling slurry is positioned in baking oven 60 DEG C of dryings 4 hours, is then dried at 80 DEG C 12 hours.Dried Copper Foil is depressed into into thickness on double roller roll forming machine for 80 microns, diameter about 12 is then gone out from Copper Foil The negative plate of millimeter is standby.
In the present invention, all test batteries adopt 2430 type button cells.Glove box of the battery in high-purity argon gas atmosphere (relative humidity<2%) assembled in.Barrier film used in assembling process is 2400 microporous polypropylene membranes of Celgard, is electrolysed Liquid is 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed liquor (volume ratio of EC and DMC is 1： 1).Lithium piece (non-ferrous metal research in Beijing is manufactured) is adopted for electrode.Upper and lower cover and pad used by assembled battery will thing First with alcohol washes it is clean after be dried.To remove the air and moisture of all thing surface adsorption, before assemble, will All things are placed in more than 4 hours in glove box.The concrete assembling process of battery is：In relative humidity<In 2% glove box first Negative material disk is placed on the central authorities of lower cover with tweezers, adds appropriate electrolyte, be then sequentially placed into barrier film, lithium piece, make Which is placed in middle position, is finally putting into pad compression, covers lid, be assembled into simulated battery.The simulated battery for installing is put into In battery special purpose copper mold, tightened with spanner, make battery be hedged off from the outer world sealing.Interface is sealed with sample sack, what is installed Simulated battery removes glove box.
Battery is filled first using high accuracy battery Performance Test System (new Weir Electronics Co., Ltd. of Shenzhen) Discharge performance, cycle performance etc. test (voltage：0.0001～3.0 volt).Discharge and recharge system is as follows：(1) 2 minutes are stood；(2) it is permanent Current discharge is to 0.0001 volt；(3) 2 minutes are stood；(4) constant current charge is to 3.0 volts.
It is proposed by the present invention that MoS is prepared by hydro-thermal method2The Ti of intercalation3C2Lithium ion battery negative material, by above-mentioned Embodiment is described, and person skilled substantially can be in without departing from present disclosure, spirit and scope to this paper institutes The content stated is modified or suitably changes and combine, and realizes the present invention.Specifically, it is all similar to replace Change and change apparent to those skilled in the art, they are considered as spirit, the scope for being included in the present invention In content.

Claims (4)

1. a kind of MoS2The Ti of intercalation3C2Lithium ion battery negative material, its composite MoS2/Ti3C2In, MoS2Quality hundred It is 1～50% to divide than content, and remaining is Ti3C2。
Above-mentioned MoS2The Ti of intercalation3C2The preparation method of lithium ion battery negative material, with following steps：
(1) prepare Ti3C2：
By Ti3AlC20.05 gram of ratio is added to be distributed in the hydrofluoric acid solution that concentration is 49% according to every milliliter of solution, room temperature Lower stirring 24 hours, then by mixed solution centrifugation, and precipitate deionized water is rinsed 7～10 times, until rinsing The pH value of solution of precipitate is crossed to 5.5, then the precipitate of acquisition is put in vacuum drying oven little in 80 DEG C of dryings 12 When, Ti is obtained3C2Powder；
(2) synthesize MoS2/Ti3C2Composite：
First add 0.00013～0.01576 gram of ratio to be added in ethanol solution according to every milliliter of solution molybdenum source, treat completely After dissolving, 0.01428 gram of ratio is added to add the Ti obtained by step (1) according still further to every milliliter of solution3C2Powder, stirs； It is last to add 0.00014～0.01359 gram of ratio to add sulphur source according to every milliliter of solution, it is stirred for uniform rear ultrasonic disperse 1 Hour, promote solution to enter Ti3C2Interlayer；
Again above-mentioned mixed solution is transferred in autoclave, 10～48 is incubated at 140～220 DEG C in being put into air dry oven little Shi Jinhang hydro-thermal method fabricated in situ, then naturally cools to what is obtained after room temperature, vacuum filtration, and deionized water are rinsed MoS2/Ti3C2Composite, then dry 12 hours in 80 DEG C in vacuum drying oven, 325 mesh sieves are crossed after grinding, MoS is obtained2/ Ti3C2The black powder of composite.
2. MoS according to claim 12The Ti of intercalation3C2Lithium ion battery negative material, it is characterised in that the step (2) use MoS2Intercalation Ti3C2, form MoS2/Ti3C2Composite.
3. MoS according to claim 12The Ti of intercalation3C2Lithium ion battery negative material, it is characterised in that the step (2) molybdenum source is two molybdic acid hydrate sodium, Ammonium Molybdate Tetrahydrate or molybdenum trioxide.
4. MoS according to claim 12The Ti of intercalation3C2Lithium ion battery negative material, it is characterised in that the step (2) sulphur source is L～cysteine, thioacetamide or thiourea.
CN201611226367.0A 2016-12-27 2016-12-27 Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof Expired - Fee Related CN106532015B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611226367.0A CN106532015B (en) 2016-12-27 2016-12-27 Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611226367.0A CN106532015B (en) 2016-12-27 2016-12-27 Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106532015A true CN106532015A (en) 2017-03-22
CN106532015B CN106532015B (en) 2018-12-07

Family

ID=58337591

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611226367.0A Expired - Fee Related CN106532015B (en) 2016-12-27 2016-12-27 Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106532015B (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107660114A (en) * 2017-09-08 2018-02-02 西安工程大学 A kind of preparation method of molybdenum disulfide/MXene lamellar composite absorbing materials
CN107742702A (en) * 2017-09-21 2018-02-27 天津大学 The CNT and tin ash of three-dimensional " upper thread face " structure are modified titanium carbide lithium ion battery negative material and preparation method
CN107799314A (en) * 2017-10-10 2018-03-13 浙江理工大学 Molybdenum disulfide/titanium carbide/carbon composite nano-fiber film and its preparation method and application
CN107887588A (en) * 2017-11-08 2018-04-06 黑龙江科技大学 A kind of preparation method and application of nano-sulfur particles/two-dimensional layer carbonization titanium composite material
CN108735984A (en) * 2018-04-11 2018-11-02 燕山大学 A kind of preparation method of molybdenum disulfide/carbonization titanium composite material
CN109402662A (en) * 2018-12-14 2019-03-01 哈尔滨工业大学 A kind of preparation method of selenizing molybdenum two-dimensional layer carbonization titanium composite material
CN109671949A (en) * 2018-12-12 2019-04-23 福建翔丰华新能源材料有限公司 A kind of MXene base flexible compound negative electrode material and preparation method thereof
CN109830675A (en) * 2019-04-04 2019-05-31 兰州理工大学 MXene/MoS for negative electrode of lithium ion battery2Composite material and preparation method thereof
CN110010862A (en) * 2019-03-15 2019-07-12 辽宁科技大学 A kind of magnesium secondary battery cathode material MXene-Ti3C2/TiS2And preparation method thereof
CN110227525A (en) * 2019-07-04 2019-09-13 清华大学深圳研究生院 A kind of two dimension catalysis material and preparation method thereof and its application method
CN110803702A (en) * 2019-11-01 2020-02-18 河北科技大学 Preparation method of MXene composite material for supercapacitor electrode material and MXene composite material
CN111463018A (en) * 2020-04-08 2020-07-28 桂林理工大学 Titanium tricarboxide/molybdenum disulfide composite film and preparation method and application thereof
CN111777069A (en) * 2020-07-20 2020-10-16 桂林电子科技大学 MXene composite material with stable structure and preparation method and application thereof
CN112054199A (en) * 2020-09-02 2020-12-08 山东大学 MoS for high-performance potassium ion battery2/Ti3C2Preparation method of MXene composite material
CN112326753A (en) * 2020-09-30 2021-02-05 天津科技大学 Preparation method and application of triclosan molecularly imprinted membrane electrochemical sensor
CN113830769A (en) * 2021-09-22 2021-12-24 同济大学 Non-linear nano hybrid material based on vanadium carbide and molybdenum disulfide and preparation method thereof
CN114512653A (en) * 2022-02-22 2022-05-17 广东工业大学 Preparation method of nitrogen-doped MXene-loaded molybdenum disulfide composite material, product and application of product

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868104A (en) * 2015-03-27 2015-08-26 浙江工业大学 Two-dimensional layered titanium carbide/metal ion composite material and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868104A (en) * 2015-03-27 2015-08-26 浙江工业大学 Two-dimensional layered titanium carbide/metal ion composite material and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ADNAN ALI等: ""Effect of surface oxidation on performance of Ti3C2Tx/MO composite as anode materials for lithium ion batteries"", 《INTERNATIONAL CONFERENCE ON BATTERY AND FUEL CELL TECHNOLOGY》 *
JIANMIN LUO等: ""Sn4+ Ion Decorated Highly Conductive Ti3C2 MXene: Promising Lithium-Ion Anodes with Enhanced Volumetric Capacity and Cyclic Performance"", 《ACS NANO》 *
刘志超等: ""碳纳米材料改性二维MXene负极材料"", 《第18届全国固态离子学学术会议暨国际电化学储能技术论坛》 *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107660114A (en) * 2017-09-08 2018-02-02 西安工程大学 A kind of preparation method of molybdenum disulfide/MXene lamellar composite absorbing materials
CN107742702A (en) * 2017-09-21 2018-02-27 天津大学 The CNT and tin ash of three-dimensional " upper thread face " structure are modified titanium carbide lithium ion battery negative material and preparation method
CN107799314A (en) * 2017-10-10 2018-03-13 浙江理工大学 Molybdenum disulfide/titanium carbide/carbon composite nano-fiber film and its preparation method and application
CN107799314B (en) * 2017-10-10 2023-06-06 浙江理工大学 Molybdenum disulfide/titanium carbide/carbon composite nanofiber membrane and preparation method thereof
CN107887588A (en) * 2017-11-08 2018-04-06 黑龙江科技大学 A kind of preparation method and application of nano-sulfur particles/two-dimensional layer carbonization titanium composite material
CN107887588B (en) * 2017-11-08 2020-03-20 黑龙江科技大学 Preparation method and application of nano sulfur particle/two-dimensional layered titanium carbide composite material
CN108735984A (en) * 2018-04-11 2018-11-02 燕山大学 A kind of preparation method of molybdenum disulfide/carbonization titanium composite material
CN109671949A (en) * 2018-12-12 2019-04-23 福建翔丰华新能源材料有限公司 A kind of MXene base flexible compound negative electrode material and preparation method thereof
CN109402662B (en) * 2018-12-14 2020-07-07 哈尔滨工业大学 Preparation method of molybdenum selenide two-dimensional layered titanium carbide composite material
CN109402662A (en) * 2018-12-14 2019-03-01 哈尔滨工业大学 A kind of preparation method of selenizing molybdenum two-dimensional layer carbonization titanium composite material
CN110010862A (en) * 2019-03-15 2019-07-12 辽宁科技大学 A kind of magnesium secondary battery cathode material MXene-Ti3C2/TiS2And preparation method thereof
CN110010862B (en) * 2019-03-15 2022-03-29 辽宁科技大学 MXene-Ti as positive electrode material of magnesium secondary battery3C2/TiS2And method for preparing the same
CN109830675A (en) * 2019-04-04 2019-05-31 兰州理工大学 MXene/MoS for negative electrode of lithium ion battery2Composite material and preparation method thereof
CN109830675B (en) * 2019-04-04 2021-10-08 兰州理工大学 MXene/MoS for lithium ion battery cathode2Method for preparing composite material
CN110227525A (en) * 2019-07-04 2019-09-13 清华大学深圳研究生院 A kind of two dimension catalysis material and preparation method thereof and its application method
CN110803702A (en) * 2019-11-01 2020-02-18 河北科技大学 Preparation method of MXene composite material for supercapacitor electrode material and MXene composite material
CN110803702B (en) * 2019-11-01 2023-03-24 河北科技大学 Preparation method of MXene composite material for supercapacitor electrode material and MXene composite material
CN111463018A (en) * 2020-04-08 2020-07-28 桂林理工大学 Titanium tricarboxide/molybdenum disulfide composite film and preparation method and application thereof
CN111463018B (en) * 2020-04-08 2021-07-09 桂林理工大学 Titanium tricarboxide/molybdenum disulfide composite film and preparation method and application thereof
CN111777069B (en) * 2020-07-20 2022-12-23 桂林电子科技大学 MXene composite material with stable structure and preparation method and application thereof
CN111777069A (en) * 2020-07-20 2020-10-16 桂林电子科技大学 MXene composite material with stable structure and preparation method and application thereof
CN112054199A (en) * 2020-09-02 2020-12-08 山东大学 MoS for high-performance potassium ion battery2/Ti3C2Preparation method of MXene composite material
CN113675408A (en) * 2020-09-02 2021-11-19 山东大学 MoS for high-performance potassium ion battery2/Ti3C2Preparation method of MXene composite material
CN112326753A (en) * 2020-09-30 2021-02-05 天津科技大学 Preparation method and application of triclosan molecularly imprinted membrane electrochemical sensor
CN112326753B (en) * 2020-09-30 2023-06-23 天津科技大学 Preparation method and application of triclosan molecular imprinting membrane electrochemical sensor
CN113830769A (en) * 2021-09-22 2021-12-24 同济大学 Non-linear nano hybrid material based on vanadium carbide and molybdenum disulfide and preparation method thereof
CN113830769B (en) * 2021-09-22 2023-07-04 同济大学 Nonlinear nanometer hybrid material based on vanadium carbide and molybdenum disulfide and preparation method thereof
CN114512653A (en) * 2022-02-22 2022-05-17 广东工业大学 Preparation method of nitrogen-doped MXene-loaded molybdenum disulfide composite material, product and application of product

Also Published As

Publication number Publication date
CN106532015B (en) 2018-12-07

Similar Documents

Publication Publication Date Title
CN106532015B (en) Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof
Cheng et al. One-step controlled synthesis of hierarchical hollow Ni3S2/NiS@ Ni3S4 core/shell submicrospheres for high-performance supercapacitors
Yang et al. Surfactant-dependent flower-and grass-like Zn 0.76 Co 0.24 S/Co 3 S 4 for high-performance all-solid-state asymmetric supercapacitors
CN104183848B (en) Graphene/nickel sulphide nano composite electrode material and preparation method thereof
Zhu et al. Novel carbon coated core-shell heterostructure NiCo2O4@ NiO grown on carbon cloth as flexible lithium-ion battery anodes
Younas et al. Facile one-step microwave-assisted method to synthesize nickel selenide nanosheets for high-performance hybrid supercapacitor
CN102142537A (en) Graphene/MoS2 compound nano material lithium ion battery electrode and preparation method thereof
Ma et al. Fabrication of NiO-ZnO/RGO composite as an anode material for lithium-ion batteries
Che et al. Facile synthesis of three dimensional flower-like Co3O4@ MnO2 core-shell microspheres as high-performance electrode materials for supercapacitors
Wang et al. Hierarchical NiCoP/Co (OH) 2 nanoarrays for high-performance asymmetric hybrid supercapacitors
Zhu et al. Three-dimensional hierarchical porous MnCo2O4@ MnO2 network towards highly reversible lithium storage by unique structure
Liang et al. β-Ni (OH) 2 nanosheets coating on 3D flower-like α-Ni (OH) 2 as high-performance electrodes for asymmetric supercapacitor and Ni/MH battery
Zhang et al. Facile synthesis of Mn2. 1V0. 9O4/rGO: a novel high-rate anode material for lithium-ion batteries
Guo et al. Double layers combined with MXene and in situ grown NiAl-LDH arrays on nickel foam for enhanced asymmetric supercapacitors
Zhao et al. Synthesis of Ni (OH) 2 nanoflakes through a novel ion diffusion method controlled by ion exchange membrane and electrochemical supercapacitive properties
CN113121836B (en) Fe-Co-Ni metal organic framework with nano framework super structure and preparation method and application thereof
Wang et al. Facile preparation of Ni–Mn layered double hydroxide nanosheets/carbon for supercapacitor
Zhang et al. CMK-3/NiCo2S4 nanostructures for high performance asymmetric supercapacitors
Zhou et al. Development of high-utilization honeycomb-like α-Ni (OH) 2 for asymmetric supercapacitors with excellent capacitance
Li et al. Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material
Wang et al. Rational design of Co–Ni layered double hydroxides electrodeposited on Co3O4 nanoneedles derived from 2D metal-organic frameworks for high-performance asymmetric supercapacitors
Gao et al. Facial design and synthesis of Ce doped Co-Ni oxide nanocages with cubic structure for high-performance asymmetric supercapacitors
Zhang et al. Electrodeposition synthesis of reduced graphdiyne oxide/NiCo2S4 hierarchical nanosheet arrays for small size and light weight aqueous asymmetry supercapacitors
Wang et al. One-step growth of Ni2Co (PO4) 2 microspheres for high energy density supercapacitors
Li et al. Design and synthesis of one-dimensional Co 3 O 4/Co 3 V 2 O 8 hybrid nanowires with improved Li-storage properties

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 300350 Haijing garden, Haihe Education Park, Jinnan, Tianjin, 135, Tianjin University.

Applicant after: Tianjin University

Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92

Applicant before: Tianjin University

CB02 Change of applicant information
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20181207

Termination date: 20201227

CF01 Termination of patent right due to non-payment of annual fee