CN106532015B - Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof - Google Patents

Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof Download PDF

Info

Publication number
CN106532015B
CN106532015B CN201611226367.0A CN201611226367A CN106532015B CN 106532015 B CN106532015 B CN 106532015B CN 201611226367 A CN201611226367 A CN 201611226367A CN 106532015 B CN106532015 B CN 106532015B
Authority
CN
China
Prior art keywords
mos
solution
added
lithium ion
gram
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.)
Expired - Fee Related
Application number
CN201611226367.0A
Other languages
Chinese (zh)
Other versions
CN106532015A (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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of molybdenum disulfide hybrid titanium carbide lithium ion battery negative materials and preparation method thereof, using titanium aluminium carbon as main material, using different molybdenum source and sulphur source prepare molybdenum disulfide hybrid carbonization titanium composite material, it is compound after molybdenum disulfide mass percent be 1-50%.The present invention is 604.2 MAhs/g in the lower first discharge specific capacity of 50 milliamperes/gram, capacity after the lower cycle articles of 500 milliamperes/gram 50 times is 153.3 MAhs/g, interlamellar spacing is 1.2346 nanometers, capacity significantly improves, interlamellar spacing significantly increases, it is a kind of simple process, low-cost method of modifying, is suitble to industrialized 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, use molybdenum disulfide (MoS more particularly to a kind of2) intercalation titanium carbide (Ti3C2) open conductive negative electrode material and preparation method thereof.
Background technique
Non-renewable energy resources crisis in global range, so that sustainable energy is favored extensively.Lithium ion battery is made For safe and efficient new energy, it is widely used in every field.But with the development of science and technology electronic equipment, automobile etc. More stringent requirements are proposed for performance of the fast development to battery, is badly in need of finding or prepares better electrode material to improve battery Comprehensive performance.
In numerous negative electrode materials, transition metal carbide or nitride receive more and more passes in recent years Note.This kind of material be by hf etching MAX (wherein M represents transition metal, and A is third main group or the 4th major element, X represents carbon or nitrogen) " A " element layer in former phase and get, obtained product group becomes Mn+1XnTx(n value is 1,2 or 3, T be introduced during etching~F and the~surface functional groups such as OH), because it has similar structure with graphene, thus by Referred to as MXene.It has the following advantages that (but being not limited only to these advantages): (1) specific surface area is high, can effectively with electrolysis Matter contact, carries out the transmission of electronics and ion；(2) good conductivity, two-dimensional layer structure are conducive to electronics and ion in interlayer Quick transmission；(3) there is hydrophily, electrode is soaked by electrolyte, is conducive to the diffusion of ion.Therefore, MXene It is a kind of very promising lithium ion battery negative material.
Have more than 70 kinds of MXene materials at present, wherein carbon titanium compound is because synthetic method is simple, at low cost, performance is excellent The features such as different, gets more and more people's extensive concerning.Carbon titanium compound has several specific substances, wherein Ti3C2It is the most studied in recent years A kind of MXene material, it has small large specific surface area, lithium ion diffusional resistance, good cycling stability, lithographic technique maturation etc. Advantage.But Ti3C2That there is interlamellar spacings as other MXene is small, lamella is accumulated again, lacked between layers after de- lithium Weary connection, electronics are the disadvantages of the direction diffusion rate perpendicular to layer is slow.Therefore, in order to promote Ti3C2Material applies to electricity Chi Zhong then needs to take measures to solve the above problems, further increases Ti3C2The performance of material.
In view of the above-mentioned problems, different researchers improve itself of MXene material by the methods of intercalation, layering, surface modification Defect.Wherein intercalation is to apply most technologies at present, and effect is best.Many scholars use low-dimensional carbon material intercalation Ti3C2, Such as Xie et al. attempts to use carbon nanotube intercalation Ti3C2, the chemical property of composite material is improved, but due to carbon nanotube Self-capacity is low, with its intercalation Ti3C2The capacity of obtained composite material is relatively low, is unable to satisfy lithium ion cell high-capacity It is required that [Xie X, Zhao M Q, Anasori B, et al.Nano Energy, 2016,26:513~523.].Some scholars adopt 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, is difficult It is inserted into interlayer.It is able to enter the stable support lamella of MXene interlayer so being badly in need of finding and significantly improves MXene material capacity The chemical property of substance improvement MXene.
MoS2Have the advantages that capacity height, large specific surface area, 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 prevent Ti3C2After the de- lithium of lamella again Accumulation.The composite material is made of thin lamella, large specific surface area, is conducive to electrode and is contacted with electrolyte, shorten lithium from The transmission range of son.MoS2It is connected to Ti3C2Upper and lower level, formed line contact, improve Ti3C2It is led perpendicular to the electronics in layer direction Electrically.MoS2When being individually used for electrode material, with the deintercalation of lithium ion, volume significant changes, capacity can significantly decay. MoS2It is inserted into Ti3C2Interlayer after, the gap of interlayer be conducive to alleviate MoS2Volume change, reduce MoS2In charge and discharge Capacitance loss and degree of polarization in journey.By sulphur source and molybdenum source and Ti3C2It is ultrasonic together, be conducive to sulphur source and molybdenum source molecule enters Ti3C2Interlayer, the two generate MoS in Coating combination2.The MoS obtained by this in situ synthesis2It can be with Ti3C2Closely connect Touching, is conducive to electron-transport between the two.
By literature search, the present invention is directed to MoS2Intercalation Ti3C2Improvement chemical property, which has not yet been disclosed, to be reported.
Summary of the invention
The purpose of the present invention is to prepare MoS using hydro-thermal method2The Ti of intercalation3C2Negative electrode material, to improve Ti3C2Electricity Chemical property.It provides and a kind of is prepared using simple process, low-cost method of modifying with excellent chemical property Lithium ion battery negative material.
Ti3C2The major defect of negative electrode material is that interlamellar spacing is smaller, and lamella is accumulated again after de- lithium, 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 prop up Support Ti3C2Lamella increases its interlamellar spacing, and lamella is accumulated again after preventing lithium ion from deviating from.MoS2It is connected to Ti3C2Fluctuating plate Layer forms three-dimensional conductive structure, promotes electronics in the direction transmission perpendicular to layer, significantly increases Ti3C2Electric conductivity.And MoS2And Ti3C2All have it is laminar structured, the three-dimensional structure that the two is compounded to form increases contact of the electrode material with electrolyte Area reduces diffusion length and the electron-transport path of lithium ion.And Ti3C2Layer structure be conducive to buffer MoS2In lithium Volume change 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) Ti is prepared3C2:
By Ti3AlC2It is distributed to according to the ratio that every milliliter of solution is added 0.05 gram in the hydrofluoric acid solution that concentration is 49%, It stirs 24 hours, then by mixed solution centrifugation, and sediment deionized water is rinsed 7~10 times at room temperature, until The pH value of the solution of flushed sediment is put into vacuum oven until 5.5, then by the sediment of acquisition in 80 DEG C of dryings 12 hours, Ti is made3C2Powder；
(2) MoS is synthesized2/Ti3C2Composite material:
First molybdenum source is added in ethanol solution according to the ratio that every milliliter of solution is added 0.00013~0.01576 gram, to After being completely dissolved, step (1) resulting Ti is added in the ratio for being added 0.01428 gram according still further to every milliliter of solution3C2Powder, stirring Uniformly；Sulphur source finally is added according to the ratio that every milliliter of solution is added 0.00014~0.01359 gram, ultrasound after being stirred for uniformly Dispersion 1 hour, promotes solution to enter Ti3C2Interlayer；
Above-mentioned mixed solution is transferred in autoclave again, be put into air dry oven at 140~220 DEG C heat preservation 10~ 48 hours progress hydro-thermal method fabricated in situ, then cooled to room temperature, is filtered by vacuum, and obtained after being rinsed with deionized water MoS2/Ti3C2Composite material, then dried 12 hours in 80 DEG C in a vacuum drying oven, 325 meshes are crossed after grinding, obtain MoS2/ Ti3C2The black powder of composite material.
The step (2) uses MoS2Intercalation Ti3C2, form MoS2/Ti3C2Composite material.
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 thiocarbamide.
The present invention prepares MoS using hydro-thermal method2The Ti of intercalation3C2Lithium ion battery negative material has Open architecture It is 604.2 MAhs/g in the lower first discharge specific capacity of 50 milliamperes/gram, under 500 milliamperes/gram with excellent chemical property Capacity after cycle articles 50 times is 153.3 MAhs/g, and interlamellar spacing is 1.2346 nanometers, and capacity significantly improves, and interlamellar spacing is aobvious It writes and increases.Preparation method of the present invention is simple, and material electrochemical performance is excellent, is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is first charge-discharge curve graph of the comparative example of the present invention under each current density；
Fig. 2 is first charge-discharge curve graph of the embodiment of the present invention 4 under each current density；
Fig. 3 is first charge-discharge curve graph of the embodiment of the present invention 5 under each current density；
Fig. 4 is the cycle performance curve of the embodiment of the present invention 4,5 and comparative example under 500 milliampere/gram 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 combined with specific embodiments below.
Comparative example
With Ti3C2Powder is assembled into button cell as negative electrode material, using conventional method, then carries out electrochemistry It can test.
To Ti3C2The battery of dusty material assembling carries out first charge-discharge and cycle performance test.Comparison is real as can be seen from Figure 1 It is 449.3 MAhs/g that the product of example, which is applied, in the lower first discharge specific capacity of 50 milliamperes/gram；As shown in Figure 4 under 500 milliamperes/gram Capacity after comparative example cycle articles 50 times is 71.4 MAhs/g；Fig. 6 shows that the interlamellar spacing of comparative example product is 0.9659 nanometer.Test result shows no MoS2The Ti of intercalation3C2The capacity of powder is low and interlamellar spacing is small.
Embodiment 1
(1) by Ti3AlC2The hydrofluoric acid solution that concentration is 49% is distributed to according to the ratio that every milliliter of solution is added 0.05 gram In, it stirs 24 hours, then by mixed solution centrifugation, and sediment deionized water is rinsed 7 times, Zhi Daochong at room temperature The pH value of the solution of sediment is washed until 5.5, then the sediment of acquisition is put into vacuum oven in 80 DEG C dry 12 Hour, Ti is made3C2Powder；
(2) first two molybdic acid hydrate sodium are added in ethanol solution according to the ratio that every milliliter of solution is added 0.00022 gram, Until completely dissolved, step (1) resulting Ti is added in the ratio for being added 0.01428 gram according still further to every milliliter of solution3C2Powder stirs It mixes uniformly；L~cysteine finally is added according to the ratio that every milliliter of solution is added 0.00022 gram, ultrasound after being stirred for uniformly Dispersion 1 hour, promotes solution to enter Ti3C2Interlayer；
Above-mentioned mixed solution is transferred in autoclave again, be put into air dry oven keep the temperature 10 hours at 140 DEG C into Row hydro-thermal method fabricated in situ, then cooled to room temperature, is filtered by vacuum, and the MoS obtained is rinsed with deionized water2/Ti3C2 Composite material, then dried 12 hours in 80 DEG C in a vacuum drying oven, 325 meshes are crossed after grinding, obtaining mass fraction is 1% MoS2The Ti of intercalation3C2Composite material.
With the MoS2/Ti3C2Composite material is assembled into button as lithium ion battery negative material, using conventional method 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 result shows that Ti3C2Interlamellar spacing increased compared with comparative example, the chemical property of 1 product of embodiment is mentioned It is high.
Embodiment 2
(1) by Ti3AlC2The hydrofluoric acid solution that concentration is 49% is distributed to according to the ratio that every milliliter of solution is added 0.05 gram In, it stirs 24 hours, then by mixed solution centrifugation, and sediment deionized water is rinsed 7 times, Zhi Daochong at room temperature The pH value of the solution of sediment is washed until 5.5, then the sediment of acquisition is put into vacuum oven in 80 DEG C dry 12 Hour, Ti is made3C2Powder；
(2) first molybdenum trioxide is added in ethanol solution according to the ratio that every milliliter of solution is added 0.00013 gram, to complete After fully dissolved, step (1) resulting Ti is added in the ratio for being added 0.01428 gram according still further to every milliliter of solution3C2Powder, stirring are equal It is even；Thioacetamide finally is added according to the ratio that every milliliter of solution is added 0.00014 gram, ultrasonic disperse 1 after being stirred for uniformly Hour, promote solution to enter Ti3C2Interlayer；
Above-mentioned mixed solution is transferred in autoclave again, be put into air dry oven keep the temperature 48 hours at 220 DEG C into Row hydro-thermal method fabricated in situ, then cooled to room temperature, is filtered by vacuum, and the MoS obtained is rinsed with deionized water2/Ti3C2 Composite material, then dried 12 hours in 80 DEG C in a vacuum drying oven, 325 meshes are crossed after grinding, obtaining mass fraction is 1% MoS2The Ti of intercalation3C2Composite material.
With the MoS2/Ti3C2Composite material is assembled into button as lithium ion battery negative material, using conventional method 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 are 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 of 2 product of embodiment and interlamellar spacing all improve, and good cycling stability.
Embodiment 3
(1) by Ti3AlC2The hydrofluoric acid solution that concentration is 49% is distributed to according to the ratio that every milliliter of solution is added 0.05 gram In, it stirs 24 hours, then by mixed solution centrifugation, and sediment deionized water is rinsed 7 times, Zhi Daochong at room temperature The pH value of the solution of sediment is washed until 5.5, then the sediment of acquisition is put into vacuum oven in 80 DEG C dry 12 Hour, Ti is made3C2Powder；
(2) first Ammonium Molybdate Tetrahydrate is added in ethanol solution according to the ratio that every milliliter of solution is added 0.00016 gram, Until completely dissolved, step (1) resulting Ti is added in the ratio for being added 0.01428 gram according still further to every milliliter of solution3C2Powder stirs It mixes uniformly；Thiocarbamide finally is added according to the ratio that every milliliter of solution is added 0.00014 gram, ultrasonic disperse 1 is small after being stirred for uniformly When, promote solution to enter Ti3C2Interlayer；
Above-mentioned mixed solution is transferred in autoclave again, be put into air dry oven keep the temperature 24 hours at 200 DEG C into Row hydro-thermal method fabricated in situ, then cooled to room temperature, is filtered by vacuum, and the MoS obtained is rinsed with deionized water2/Ti3C2 Composite material, then dried 12 hours in 80 DEG C in a vacuum drying oven, 325 meshes are crossed after grinding, obtaining mass fraction is 1% MoS2The Ti of intercalation3C2Composite material.
With the MoS2/Ti3C2Composite material is assembled into button as lithium ion battery negative material, using conventional method 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, has clearly lamellar structure.Electrochemical property test The result shows that 3 product of embodiment is all significantly improved compared with 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, obtaining mass fraction is 20% for remaining MoS2The Ti of intercalation3C2Composite material.
With the MoS2/Ti3C2Composite material is assembled into button as lithium ion battery negative material, using conventional method 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, more real than comparison 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, and the capacity than comparative example product improves 81.9 MAhs/g；Fig. 5 display is real Apply in 4 product of example that there are MoS2Diffraction maximum；The interlamellar spacing of 4 product of embodiment is 1.2346 nanometers as can be seen from Figure 6, is compared Interlamellar spacing than embodiment product increases 0.2687 nanometer.Test result shows the MoS compared with comparative example with 20%2 The Ti of intercalation3C2The capacity of powder significantly improves and interlayer significantly increases.Fig. 7 shows Ti3C2Growth in situ many on lamella MoS2Nanoscale twins, it was demonstrated that the technical solution proposed through the invention can synthesize MoS2The Ti of intercalation3C2Composite material.
Embodiment 5
The present embodiment is by MoS2Mass fraction is adjusted to 30%, and, with embodiment 3, obtaining mass fraction is 30% for remaining MoS2The Ti of intercalation3C2Composite material.
With the MoS2/Ti3C2Composite material is assembled into button as lithium ion battery negative material, using conventional method 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 implemented than comparison 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, and the capacity than comparative example product improves 81.9 MAhs/g；Fig. 5 display is real Apply in 5 product of example that there are MoS2Diffraction maximum；Fig. 6 shows that the interlamellar spacing of 5 product of embodiment is 1.2346 nanometers, implements than comparison The interlamellar spacing of example product increases 0.2687 nanometer.Test result shows the MoS with 30%2The Ti of intercalation3C2The capacity of powder is bright Aobvious to improve, interlamellar spacing also significantly increases.
Embodiment 6
The present embodiment is by MoS2Mass fraction is adjusted to 50%, and, with embodiment 3, obtaining mass fraction is 50% for remaining MoS2The Ti of intercalation3C2Composite material.
With the MoS2/Ti3C2Composite material is assembled into button as lithium ion battery negative material, using conventional method 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 result shows that 6 product of embodiment is increased substantially compared with the capacity of comparative example.
Test method of the invention is as follows.
With MoS prepared by the present invention2The Ti of intercalation3C2For powder as active material, SuperP is conductive agent, polyvinylidene fluoride Alkene (PVDF) is binder, and 80:10:10 in mass ratio weighs a certain amount of above-mentioned three kinds of substances.PVDF is dissolved in N~methyl pyrrole 1.5 hours formation colloids are stirred in pyrrolidone (NMP), and SuperP is then added into gained colloid and are stirred 2 hours, Zhi Houjia Enter active material powder and continues stirring 3 hours.The adjustable spreader of obtained slurry is coated in clean copper foil surface (slurry Material with a thickness of 100 microns), the copper foil for being coated with slurry is placed in 60 DEG C drying 4 hours in baking oven, then at 80 DEG C dry 12 hours.By the copper foil after drying in being depressed on double roller roll forming machine with a thickness of 80 microns, diameter about 12 is then gone out from copper foil The negative electrode tab of millimeter is spare.
All test batteries are all made of 2430 type button cells in the present invention.Glove box of the battery in high-purity argon gas atmosphere It is assembled in (relative humidity < 2%).Diaphragm used in assembling process is 2400 microporous polypropylene membrane of Celgard, electrolysis Liquid is 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed liquor (volume ratio of EC and DMC be 1: 1).Use lithium piece (manufactured by the research of Beijing non-ferrous metal) for electrode.Upper and lower cover used in assembled battery and gasket will things First with alcohol washes it is clean after be dried.It will before assembling battery for the air and moisture for removing all thing adsorptions All things are placed in glove box 4 hours or more.The specific assembling process of battery are as follows: in the glove box of relative humidity < 2% first Negative electrode material disk is placed on tweezers the center of lower cover, suitable electrolyte is added, is then sequentially placed into diaphragm, lithium piece, make It is placed in central location, is finally putting into gasket compression, covers upper cover, be assembled into simulated battery.The simulated battery installed is put into It in battery special purpose copper mold, is tightened with spanner, battery is made to be isolated from the outside world sealing.Interface is sealed with sample sack, what is installed Simulated battery removes glove box.
Battery is filled for the first time 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).Charge and discharge system is as follows: (1) standing 2 minutes；(2) 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 has passed through above-mentioned Embodiment is described, related technical personnel obviously can not depart from the contents of the present invention, in spirit and scope to this paper institute The content stated is modified or appropriate changes and combinations, to realize the present invention.In particular, it should be pointed out that all similar replaces Change and change apparent to those skilled in the art, they are considered as including in spirit of the invention, range In content.

Claims (3)

1. a kind of MoS2The Ti of intercalation3C2Lithium ion battery negative material, which is characterized in that in composite material MoS2/Ti3C2In, MoS2Mass percentage content be 1~50%, remaining is Ti3C2；
Above-mentioned MoS2The Ti of intercalation3C2The preparation method of lithium ion battery negative material has following steps:
(1) Ti is prepared3C2:
By Ti3AlC2It is distributed to according to the ratio that every milliliter of solution is added 0.05 gram in the hydrofluoric acid solution that concentration is 49%, room temperature Lower stirring 24 hours then by mixed solution centrifugation, and sediment deionized water is rinsed 7~10 times, until rinsing The pH value of the solution of sediment is crossed until 5.5, then the sediment of acquisition is put into vacuum oven in 80 DEG C dry 12 small When, Ti is made3C2Powder；
(2) MoS is synthesized2/Ti3C2Composite material:
First molybdenum source is added in ethanol solution according to the ratio that every milliliter of solution is added 0.00013~0.01576 gram, to complete After dissolution, step (1) resulting Ti is added in the ratio for being added 0.01428 gram according still further to every milliliter of solution3C2Powder stirs evenly； Sulphur source finally is added according to the ratio that every milliliter of solution is added 0.00014~0.01359 gram, ultrasonic disperse 1 after being stirred for uniformly Hour, promote solution to enter Ti3C2Interlayer；
Gained mixed solution is transferred in autoclave again, it is small to be put into air dry oven the heat preservation 10~48 at 140~220 DEG C Shi Jinhang hydro-thermal method fabricated in situ, then cooled to room temperature, is filtered by vacuum, and obtained after being rinsed with deionized water MoS2/Ti3C2Composite material, then dried 12 hours in 80 DEG C in a vacuum drying oven, 325 meshes are crossed after grinding, obtain MoS2/ Ti3C2The black powder of composite material.
2. MoS according to claim 12The Ti of intercalation3C2Lithium ion battery negative material, which is characterized in that the step (2) molybdenum source is two molybdic acid hydrate sodium, Ammonium Molybdate Tetrahydrate or molybdenum trioxide.
3. MoS according to claim 12The Ti of intercalation3C2Lithium ion battery negative material, which is characterized in that the step (2) sulphur source is L~cysteine, thioacetamide or thiocarbamide.
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 CN106532015A (en) 2017-03-22
CN106532015B true 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)

Families Citing this family (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
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
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
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
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
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
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
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
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
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
CN114512653B (en) * 2022-02-22 2023-01-06 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
"Effect of surface oxidation on performance of Ti3C2Tx/MO composite as anode materials for lithium ion batteries";Adnan Ali等;《International Conference on Battery and Fuel Cell Technology》;20161209;第6卷;第52页 *
"Sn4+ Ion Decorated Highly Conductive Ti3C2 MXene: Promising Lithium-Ion Anodes with Enhanced Volumetric Capacity and Cyclic Performance";Jianmin Luo等;《ACS NANO》;20160202;第10卷;第2491-2499页 *
"碳纳米材料改性二维MXene负极材料";刘志超等;《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》;20161103;第56页 *

Also Published As

Publication number Publication date
CN106532015A (en) 2017-03-22

Similar Documents

Publication Publication Date Title
CN106532015B (en) Molybdenum disulfide hybrid titanium carbide lithium ion battery negative material and preparation method thereof
Zhang et al. Super long-life all solid-state asymmetric supercapacitor based on NiO nanosheets and α-Fe2O3 nanorods
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
Jiang et al. An easy way for preparing high performance porous silicon powder by acid etching Al–Si alloy powder for lithium ion battery
Jia et al. Formation of ZnCo 2 O 4@ MnO 2 core–shell electrode materials for hybrid supercapacitor
CN104183848B (en) Graphene/nickel sulphide nano composite electrode material and preparation method thereof
Huang et al. Three-dimensional sandwich-structured NiMn2O4@ reduced graphene oxide nanocomposites for highly reversible Li-ion battery anodes
CN110942921B (en) Preparation method of three-dimensional composite aerogel electrode material
Jiang et al. Rod-like porous CoMoO4@ C as excellent anode for high performance lithium ion battery
Kang et al. Bimetallic coordination polymer composites: A new choice of electrode materials for lithium ion batteries
CN106449132B (en) A kind of mesoporous Co3O4Nano wire@NiCo2O4Nanometer sheet is classified nucleocapsid array material, preparation method and application
Ma et al. Fabrication of NiO-ZnO/RGO composite as an 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
Huang et al. Metal‐Organic‐Framework‐Derived MCo2O4 (M= Mn and Zn) Nanosheet Arrays on Carbon Cloth as Integrated Anodes for Energy Storage Applications
CN108046320B (en) Preparation method of supercapacitor electrode material vanadium sulfide nanoflower
CN105788875A (en) Cobaltosic oxide nanowire/reduction-oxidization graphene hydrogel composite material and preparation method and application therefor
CN112239200A (en) Preparation of amorphous phosphate material and application of amorphous phosphate material as electrode material of super capacitor
Zhao et al. Synthesis of Ni (OH) 2 nanoflakes through a novel ion diffusion method controlled by ion exchange membrane and electrochemical supercapacitive properties
Barkhordari et al. Facile synthesis of ZnMn 2 O 4 nanosheets via cathodic electrodeposition: characterization and supercapacitor behavior studies
Zhou et al. Novel ternary transition metal oxide solid solution: mesoporous Ni–Mn–Co–O nanowire arrays as an integrated anode for high-power lithium-ion batteries
CN113121836A (en) Nano-framework-shaped super-structure Fe-Co-Ni metal organic framework and preparation method and application thereof
Zhou et al. Development of high-utilization honeycomb-like α-Ni (OH) 2 for asymmetric supercapacitors with excellent capacitance
CN104167298A (en) Graphene-protein derived carbon supercapcaitor material and preparation method thereof
Han et al. Preparation of carbon cloth supported Sn thin film for structural lithium-ion battery anodes

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