CN107799745A - A kind of molybdenum carbide sulphur composite and preparation method and application - Google Patents
A kind of molybdenum carbide sulphur composite and preparation method and application Download PDFInfo
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Abstract
The present invention relates to lithium sulfur battery anode material technical field, provide a kind of molybdenum carbide sulphur composite and its preparation method and application, the molybdenum carbide sulphur composite includes molybdenum carbide and sulphur simple substance, molybdenum carbide is porous club shaped structure, length is 1~5 μm, a diameter of 30~60nm, sulphur simple substance are doped in the hole of molybdenum carbide, and the mass ratio of molybdenum carbide and sulphur simple substance is 1~9：9~1.Molybdenum carbide sulphur composite provided by the invention has higher specific surface area and electronic conductivity, it is possible to increase the utilization rate of sulphur, alleviates shuttle effect.The lithium-sulfur cell prepared using above-mentioned molybdenum carbide sulphur composite carries out charge-discharge test, and 623~653mAh/g reversible capacity is still maintained after circulating 500 times, takes in and is maintained at more than 70%, has the coulombic efficiency more than 93%, and cycle performance is significantly improved.
Description
Technical field
The present invention relates to lithium sulfur battery anode material technical field, more particularly to a kind of molybdenum carbide sulphur composite and its system
Preparation Method and application.
Background technology
In the last few years, with the fast development of electric car and energy storage device, current commercialized lithium ion battery is very
Difficulty meets the needs of people are to high-energy-density.Lithium-sulfur cell due to high-energy-density, characteristic of low cost, quilt it is believed that
It is one of candidate of next battery eliminator.However, due to the relatively low electronic conductivity of element sulphur, polysulfide is dissolved in electrolyte
In, big Volume Changes cause shuttle effect in cyclic process, and the utilization rate of sulphur is low, and stable circulation is poor, and these all govern lithium
The practical application of sulphur battery.
Such as Ti is used in the prior art4O7With TiN isopolarities conductive materials compound conduct lithium sulphur is carried out as the carrier of sulphur
The positive electrode of battery, but these positive electrodes weak stable circulation that instead results in bound to polysulfide is poor, and do not apply to
In large-scale production.
Therefore, the performances of lithium-sulfur cell are more improved using carbon-sulfur compound in the prior art, by carbon material conduct
The carrier of sulphur, the electrical conductivity of integral composite is improved, while be capable of the free diffusing of physics constraint polysulfide.It is but existing
The interphase interaction of carbon material and polysulfide is weaker in some carbon-sulfur compounds, as circulation is carried out, the increase of cycle-index,
Polysulfide can be still diffused into electrolyte, cause carbon-sulfur compound cycle performance and service life to be met.
The content of the invention
It is an object of the invention to provide a kind of molybdenum carbide sulphur composite and preparation method thereof and in lithium-sulfur cell
Using；Molybdenum carbide sulphur composite provided by the invention has higher specific surface area and electrical conductivity, can effectively alleviate shuttle
Effect, improve the cyclical stability and service life of lithium-sulfur cell.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of molybdenum carbide sulphur composite, molybdenum carbide and sulphur simple substance, the carbon are included in chemical composition
Change molybdenum is porous club shaped structure, and length is 1~5 μm, a diameter of 30~60nm；The sulphur simple substance is doped in the hole of molybdenum carbide
In, the mass ratio of molybdenum carbide and sulphur simple substance is 1~9：9~1.
Present invention also offers the preparation method of above-mentioned molybdenum carbide sulphur composite, comprise the following steps：
1) after mixing molybdenum trioxide raw material, hydrogen peroxide and salpeter solution, hydrothermal treatment obtains bar-shaped molybdenum trioxide；
2) the bar-shaped molybdenum trioxide and carbon matrix precursor material are mixed, dried, reduction reaction is carried out under protective atmosphere
Obtain bar-shaped molybdenum carbide；
3) the bar-shaped molybdenum carbide and sulphur simple substance are mixed, carries out being thermally treated resulting in molybdenum carbide sulphur under protective atmosphere compound
Material.
Preferably, the concentration of the hydrogen peroxide is 0.01~0.35g/mL；The concentration of the salpeter solution be 0.01~
0.7g/mL。
Preferably, the temperature of the hydro-thermal process is 90~200 DEG C, and the time of the hydro-thermal process is 1~72h.
Preferably, the carbon matrix precursor material includes glucose, phenolic resin, aniline, pyrroles, thiophene, sucrose and carboxylic first
One or more kinds of mixtures in base cellulose.
Preferably, the mass ratio of the bar-shaped molybdenum trioxide and carbon matrix precursor material is 1：0.05~200.
Preferably, the protective atmosphere in the step 2) and step 3) independently is N2, Ar, He and H2In one kind or two
The mixed gas of the kind above.
Preferably, the temperature of reduction reaction is 400~1200 DEG C in the step 2), time of reduction reaction for 1~
72h。
Preferably, the temperature of heat treatment is 140~200 DEG C in the step 3), and the time of heat treatment is 10~30h.
Present invention also offers a kind of lithium-sulfur cell, including positive pole, cathode of lithium and electrolyte, the positive pole includes active matter
Matter, the molybdenum carbide sulphur composite that the active material is above-mentioned molybdenum carbide sulphur composite or above-mentioned preparation method obtains.
The invention provides a kind of molybdenum carbide sulphur composite, molybdenum carbide and sulphur simple substance, the carbon are included in chemical composition
Change molybdenum is porous club shaped structure, and length is 1~5 μm, a diameter of 30~60nm；The sulphur simple substance is doped in the hole of molybdenum carbide
In, the mass ratio of molybdenum carbide and sulphur simple substance is 1~9：9~1.Club shaped structure in molybdenum carbide sulphur composite provided by the invention
Molybdenum carbide has higher specific surface area and electronic conductivity, can alleviate volumetric expansion, physics constraint polysulfide, reduce more
The diffusion phenomena of sulfide, improve the utilization rate of sulphur；Higher electronic conductivity can improve electron transport ability, be finally reached
Improve the cyclical stability of lithium-sulfur cell and the purpose of service life.
Molybdenum carbide has very strong suction-operated to the polysulfide of polarity in itself simultaneously, effectively inhibits more vulcanizations
The free diffusing of thing, alleviate shuttle effect.Test result indicates that the length of molybdenum carbide sulphur composite provided by the invention is 1
~5 μm, a diameter of 30~60nm, the specific surface area of composite is 289~352m2/ g, electrical conductivity are 1.1 × 102S·cm-1
~1.02 × 102S·cm-1。
Present invention also offers a kind of preparation method of the molybdenum carbide sulphur composite, this method is easy to operate, is easy to
Implement.
Molybdenum carbide sulphur composite provided by the invention can be applied in lithium-sulfur cell.Test result indicates that with carbonization
Lithium-sulfur cell prepared by molybdenum sulphur composite, at 30 DEG C of constant temperature, in 1.5-3.0V voltage range, is entered with 1C current density
Row charge-discharge test, 623~653mAh/g reversible capacity is still maintained after circulating 500 times, take in and be maintained at more than 70%, tool
93% coulombic efficiency is had more than, shows good cyclical stability.
Brief description of the drawings
Fig. 1 is the SEM figures of molybdenum carbide sulphur composite prepared by the embodiment of the present invention 1；
Fig. 2 is the cycle performance curve map of button lithium-sulfur cell prepared by the embodiment of the present invention 2；
Fig. 3 is the cycle performance curve map of button lithium-sulfur cell prepared by the embodiment of the present invention 4.
Embodiment
The invention provides a kind of molybdenum carbide sulphur composite, and comprising molybdenum carbide and sulphur simple substance, the molybdenum carbide is porous
Club shaped structure, length are 1~5 μm, a diameter of 30~60nm；The sulphur simple substance is doped in the hole of molybdenum carbide, molybdenum carbide with
The mass ratio of sulphur simple substance is 1~9：9~1.
Molybdenum carbide sulphur composite provided by the invention includes molybdenum carbide；In the present invention, the molybdenum carbide is nanometer
Club shaped structure, the length of the carbide nanorods is preferably 1~5 μm, more preferably 2~4 μm；The carbide nanorods are straight
Footpath is preferably 30~60nm, more preferably 40~50nm, most preferably 45nm；Molybdenum carbide in the present invention is answered as molybdenum carbide sulphur
The main body framework structure of condensation material, can play a supportive role.In the present invention, the mass content of the molybdenum carbide be preferably 10~
90%, more preferably 30~60%, most preferably 50%.
In the present invention, the molybdenum carbide has higher specific surface area and electronic conductivity, can alleviate volumetric expansion,
Physics fetters polysulfide, reduces the diffusion phenomena of polysulfide, improves the utilization rate of sulphur；Higher electronic conductivity can carry
High electron transport ability, the final cyclical stability and service life for improving lithium-sulfur cell.Molybdenum carbide is in itself to polarity simultaneously
Polysulfide has very strong suction-operated, effectively inhibits the free diffusing of polysulfide, alleviates shuttle effect.
Molybdenum carbide sulphur composite provided by the invention also includes the sulphur simple substance being doped in bar-shaped molybdenum carbide hole；At this
In invention, the mass content of the sulphur simple substance is preferably 10~90%, more preferably 30~60%, most preferably 50%；At this
In invention, the sulphur simple substance of the certain content is adulterated as the active material of molybdenum carbide sulphur composite, can significantly improve lithium
The high rate performance and cyclical stability of sulphur battery.
The structure of molybdenum carbide sulphur composite provided by the invention is nano bar-shape, and length is 1~5 μm, a diameter of 30~
60nm；The specific surface area of molybdenum carbide sulphur composite provided by the invention is 289~352m2/ g, electrical conductivity are 1.1 × 102~
1.02×102S·cm-1, compared to other existing carbon-sulfur compounds, its specific surface area and electrical conductivity are all significantly improved.
Present invention also offers the preparation method of above-mentioned molybdenum carbide sulphur composite, comprise the following steps：
1) after mixing molybdenum trioxide raw material, hydrogen peroxide and salpeter solution, hydrothermal treatment obtains bar-shaped molybdenum trioxide；
2) the bar-shaped molybdenum trioxide, carbon matrix precursor material and solvent are mixed, reduction reaction is carried out under protective atmosphere
Obtain molybdenum carbide；
3) by the molybdenum carbide with and sulphur simple substance mix, carry out being thermally treated resulting in molybdenum carbide sulphur composite wood under protective atmosphere
Material.
The present invention obtains mixed liquor after mixing molybdenum trioxide raw material, hydrogen peroxide and salpeter solution.The present invention is for three oxygen
The source for changing molybdenum raw material, hydrogen peroxide and salpeter solution does not have particular/special requirement, using commercially available or experiment reagent；Institute of the present invention
It is commercially available non-club shaped structure raw material with molybdenum trioxide；The purpose that hydrogen peroxide and salpeter solution are selected in the present invention is to dissolve
Molybdenum trioxide, the molybdenum carbide of special club shaped structure is prepared.
In the present invention, the concentration of the hydrogen peroxide is preferably 0.01~0.35g/ml, more preferably 0.1~0.25g/
Ml, most preferably 0.15g/ml；The concentration of the salpeter solution is preferably 0.01~0.7g/ml, more preferably 0.1~0.5g/
Ml, most preferably 0.2~0.4g/ml.In the present invention, the volume ratio of the hydrogen peroxide and salpeter solution is preferably 0.1~20：
1, more preferably 0.5~5：1.
In the present invention, the solid-to-liquid ratio (i.e. mass content of the molybdenum trioxide in mixed liquor) of the mixed liquor is preferably
0.001~100, more preferably 0.01~50, most preferably 0.1~20.
In the present invention, the mixing of the molybdenum trioxide raw material, hydrogen peroxide and salpeter solution is preferably entered under agitation
OK, the stirring is preferably magnetic agitation；The speed of the stirring is preferably 10~5000r/min, more preferably 100~
1000r/min, most preferably 200~500r/min；The time of the stirring is preferably 1~72h, more preferably 5~50h, most
Preferably 20~40h.The present invention enables to raw material to be well mixed using the hybrid mode of stirring, promotes club shaped structure three to aoxidize
The formation of molybdenum.
Mixing order of the present invention for molybdenum trioxide raw material, hydrogen peroxide and salpeter solution does not have particular/special requirement, San Zheke
Mixed with random order, the molybdenum trioxide of special appearance can be prepared.The present invention preferably mixes hydrogen peroxide and salpeter solution
Close, add the mixing of molybdenum trioxide raw material, this mixing order can avoid because of the change of nitric acid and hydrogen peroxide order of addition and
The pattern of caused molybdenum trioxide is uncontrollable, it is ensured that obtains bar-shaped molybdenum trioxide.
After obtaining mixed liquor, mixed liquor hydrothermal treatment is obtained bar-shaped molybdenum trioxide by the present invention.In the present invention, it is described
The temperature of hydro-thermal process is preferably 90~200 DEG C, more preferably 120~180 DEG C, most preferably 160 DEG C；The hydro-thermal process
Time is preferably 1~72h, more preferably 12~60h, most preferably 24~32h.The present invention does not have for the equipment of hydro-thermal process
Particular determination, hydro-thermal process is carried out preferably in hydrothermal reaction kettle in embodiments of the present invention.
After hydro-thermal process terminates, the bar-shaped molybdenum trioxide solution that preferred pair of the present invention obtains sequentially is cooled down, separated, done
It is dry, obtain pure bar-shaped molybdenum trioxide；In the present invention, the temperature after the cooling is preferably room temperature, and the present invention is for cold
But mode does not have particular/special requirement, using the conventional type of cooling in this area, in embodiments of the present invention, it is preferred to use from
The mode so cooled down.
In the present invention, the separation includes centrifuging and filtered；The present invention is not special for the technique for centrifuging and filtering
Limit, using the conventional centrifugation in this area and filter method, the separation of solid and liquid of bar-shaped molybdenum trioxide and mixed liquor can be realized i.e.
Can.
In the present invention, the temperature of the drying is preferably 20~120 DEG C, more preferably 50~100 DEG C, most preferably 60
~80 DEG C；The present invention does not have any particular/special requirement to time of the drying, enable to that separation of solid and liquid obtains bar-shaped three
Solution evaporation on molybdenum oxide is clean.
After obtaining bar-shaped molybdenum trioxide, the present invention mixes the bar-shaped molybdenum trioxide and carbon matrix precursor material, is protecting
Reduction reaction is carried out under atmosphere and obtains molybdenum carbide.
In the present invention, the mass ratio of the bar-shaped molybdenum trioxide and carbon matrix precursor material is preferably 1：0.05~200, more
Preferably 1：1~100, most preferably 1：10~50.In the present invention, the carbon matrix precursor material includes glucose, phenolic aldehyde tree
One or more kinds of mixtures in fat, aniline, pyrroles, thiophene, sucrose and carboxymethyl cellulose.In the present invention,
Carbon matrix precursor material obtains molybdenum carbide as reducing agent reduction molybdenum trioxide.
In the present invention, preferably -5~100 DEG C of the temperature of the mixing, more preferably 0~80 DEG C, most preferably 10~
50℃；The mixing is preferably carried out under agitation；The speed of the stirring is preferably 10~5000r/min, more preferably
100~1000r/min, most preferably 200~500r/min；The time of the stirring is preferably 1~48h, more preferably 10~
32h, most preferably 18~24h.
The bar-shaped molybdenum trioxide and carbon matrix precursor material are preferably scattered in solvent and mixed by the present invention, so as to
To more uniform mixture.In the present invention, the concentration of carbon matrix precursor is 0.01mol/L~10mol/L in the mixed liquor.
The solvent preferably includes water and/or organic solvent, and the organic solvent preferably includes ethanol, methanol, acetone, isopropanol, four
One or more kinds of mixtures in hydrogen furans and carbon tetrachloride.After dispersion mixing terminates in a solvent, the present invention is excellent
Obtained mixture is dried to obtain the solid mixed-powder of bar-shaped molybdenum trioxide and carbon matrix precursor material for choosing.In the present invention
In, the temperature of the drying is preferably 20~120 DEG C, more preferably 40~100 DEG C, most preferably 50~70 DEG C.The present invention is right
It is not particularly limited in dry method, using drying mode well known to those skilled in the art；In the present invention, dry
Purpose be to obtain the solid mixed-powder of bar-shaped molybdenum trioxide and carbon matrix precursor material.
Dry after terminating, obtained solid powder is carried out reduction reaction under protective atmosphere and obtains bar-shaped carbonization by the present invention
Molybdenum.In the present invention, the protective atmosphere is preferably N2, Ar, He and H2One or both of more than mixed gas.At this
In invention, the effect of protective atmosphere is to prevent precursor material from being reacted with the oxygen in air.
In the present invention, the temperature of the reduction reaction is preferably 400 DEG C~1200 DEG C, more preferably 500~1000 DEG C,
Most preferably 600~800 DEG C；The time of the reduction reaction is preferably 1~72h, more preferably 12~60h, and most preferably 24
~32h；The reduction reaction is preferably sintered in high temperature furnace.
After reduction reaction terminates, the product system of the invention for preferably obtaining reduction reaction is cooled to room temperature and obtains bar-shaped carbon
Change molybdenum；In the present invention, the mode of the cooling is preferably natural cooling.
After obtaining bar-shaped molybdenum carbide, the present invention mixes the bar-shaped molybdenum carbide and sulphur simple substance, is carried out under protective atmosphere
It is thermally treated resulting in molybdenum carbide sulphur composite.In the present invention, the molybdenum carbide and the mass ratio of sulphur simple substance are preferably 1~9：9
~1, more preferably 1~5：5~1, most preferably 1~2：2~1.In the present invention, the protective atmosphere is preferably N2、Ar、He
And H2One or both of more than mixed gas.
The present invention for molybdenum carbide with and sulphur simple substance mix operate no special restriction, using those skilled in the art
The technical scheme of well known powder mixing；In the present invention, the molybdenum carbide with and the mixing of sulphur simple substance be preferably ball milling
Mixing, the time of the ball milling mixing is 1~72h, more preferably 12~60h, most preferably 24~32h；The speed of the ball milling
Rate is preferably 10~5000r/min, more preferably 100~1000r/min, most preferably 200~500r/min.
In the present invention, the temperature of the heat treatment is preferably 140~200 DEG C, more preferably 150~180 DEG C, most preferably
For 160~170 DEG C；The time of the heat treatment is preferably 1~72h, more preferably 12~60h, most preferably 24~32h.
In the present invention, select above-mentioned heat treatment to be makes forerunner's precursor reactant generate molybdenum carbide to heat, and carbon matrix precursor is carbonized at high temperature
Carbon is generated, these carbon can react with bar-shaped molybdenum trioxide, and generation has porose molybdenum carbide.
Present invention also offers a kind of lithium-sulfur cell, including positive pole, cathode of lithium and electrolyte, the positive pole includes active matter
Matter, acetylene black and PVDF, the active material are above-mentioned molybdenum carbide sulphur composite or the carbon prepared according to above-mentioned preparation method
Change molybdenum sulphur composite.
The present invention is assembled into knob preferably in the glove box of argon gas protection, by negative pole and electrolyte, positive plate of lithium metal
Detain lithium-sulfur cell；The present invention does not have special restriction to the preparation method of the lithium-sulfur cell, ripe using those skilled in the art
The technical scheme for the assembling lithium-sulfur cell known.
In the present invention preferably by molybdenum carbide sulphur composite and acetylene black, PVDF in mass ratio 8：1：1 is mixed, with
1-METHYLPYRROLIDONE is that uniform slurry (solid content 50%) is made in solvent, and coated in suitable depth on aluminium foil, drying
Obtain positive plate.The present invention does not have special restriction to the species of the cathode of lithium and electrolyte, using those skilled in the art
The cathode of lithium and electrolyte of well known lithium-sulfur cell；Electrolyte preferred LiTFSI and LiNO in the present invention3For lithium salts,
DOL and DME is solvent, and two kinds of solvent volume ratios are 1：1, the concentration of lithium salts is 1M LiTFSI, 0.1M LiNO3。
With reference to embodiment to molybdenum carbide sulphur composite provided by the invention and preparation method thereof and in lithium-sulfur cell
In application be described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Mixed liquor (0.3g/ml hydrogen peroxide 20ml, 0.65g/ml salpeter solution 10ml) is prepared, 0.4g molybdenum trioxides are added
Stirred 72 hours into mixed liquor, stir speed (S.S.) 500r/min；Then hydro-thermal process 36 hours under the conditions of 190 DEG C, cooling
To room temperature, after centrifuging, filtering, bar-shaped molybdenum trioxide is dried to obtain at 70 DEG C；
By bar-shaped molybdenum trioxide obtained above and phenolic resin according to mass ratio 2：1 is dispersed in 40ml alcohol solvents,
Stirred 28 hours at 40 DEG C, solid mixed-powder is dried to obtain at 80 DEG C.By solid mixed-powder in N2The high temperature furnace of protection
Middle sintering, with 5 DEG C/min programming rates, 900 DEG C of sintering reaction 18h are risen to, room temperature is naturally cooled to and obtains molybdenum carbide；
By obtained molybdenum carbide and sulphur simple substance according to mass ratio 2：3, ball milling 4 hours in ball mill, product is in N2Protection
High temperature furnace in, 160 DEG C be heat-treated 30 hours, naturally cool to room temperature and obtain molybdenum carbide sulphur composite.
The SEM figures of molybdenum carbide sulphur composite manufactured in the present embodiment are as shown in Figure 1.It will be seen from figure 1 that the present embodiment
The molybdenum carbide sulphur composite of preparation is nano bar-shape structure, long 2 μm, a diameter of 50nm of nanometer rods；Through nitrogen adsorption and four
The specific surface area and electrical conductivity of probe test material, the specific surface area of molybdenum carbide sulphur composite is 352m2/ g, electrical conductivity are
1.02×102S·cm-1。
Embodiment 2
The preparation of lithium-sulfur cell：Molybdenum carbide sulphur composite prepared by embodiment 1 and acetylene black, PVDF in mass ratio 8：
1：1 is mixed, and uniform slurry (solid content 50%) is made by solvent of 1-METHYLPYRROLIDONE, and be coated in aluminium foil
On, drying obtains positive plate, in the glove box of argon gas protection, using lithium metal as negative pole, and 1M LiTFSI, 0.1M LiNO3
(DOL and DME are solvent, volume ratio 1：1) it is electrolyte, is assembled into button lithium-sulfur cell.
Cycle performance is tested：At 30 DEG C of constant temperature, in 1.5~3.0V voltage range, filled with 1C current density
Discharge test, circulate 500 times.
The cycle performance curve of positive electrode is understood as shown in Figure 2, and the reversible of 653mAh/g is still maintained after circulating 500 times
Capacity, and taken in after 1C circulations 500 times and can still be maintained at more than 70%, there is the coulomb effect more than 93%
Rate, there is excellent cyclical stability.
Embodiment 3
Mixed liquor (0.1g/ml hydrogen peroxide 10ml, 0.45g/ml salpeter solution 40ml) is prepared, 0.8g molybdenum trioxides are added
Stirred 36 hours into mixed liquor, stir speed (S.S.) 100r/min；Then hydro-thermal process 24 hours under the conditions of 160 DEG C, cooling
To room temperature, after centrifuging, filtering, bar-shaped molybdenum trioxide is dried to obtain at 60 DEG C；
The bar-shaped molybdenum trioxide by made from is with glucose according to mass ratio 1：1 is dispersed in 30ml water, is stirred at 30 DEG C
20 hours, solid mixed-powder is dried to obtain at 50 DEG C.Solid mixed-powder is placed in the high temperature furnace of argon gas, with 10 DEG C/
Min programming rates, 800 DEG C of sintering reaction 12h are risen to, room temperature is naturally cooled to and obtains molybdenum carbide；
By obtained molybdenum carbide and sulphur simple substance according to mass ratio 3：4, ball milling 8 hours in ball mill, product is protected in argon gas
In the high temperature furnace of shield, 170 DEG C are heat-treated 20 hours, naturally cool to room temperature and obtain molybdenum carbide sulphur composite.
Molybdenum carbide sulphur composite manufactured in the present embodiment is nano bar-shape structure, long 1 μm, nanometer rods it is a diameter of
30nm；Specific surface area and electrical conductivity through nitrogen adsorption and four probe test materials, molybdenum carbide sulphur manufactured in the present embodiment are compound
Material specific surface area is 289m2/ g, electrical conductivity are 1.1 × 102S·cm-1。
Embodiment 4
The molybdenum carbide sulphur composite prepared in embodiment 3 is assembled into button lithium-sulfur cell in the way of embodiment 2.
Cycle performance is tested：At 30 DEG C of constant temperature, in 1.5~3.0V voltage range, filled with 1C current density
Discharge test, circulate 500 times.
The cycle performance curve of positive electrode is understood as shown in Figure 3, and the reversible of 623mAh/g is still maintained after circulating 500 times
Capacity, and taken in after 1C circulations 500 times and can still be maintained at more than 70%, there is the coulomb effect more than 97%
Rate, show excellent cyclical stability.
Embodiment 5
Mixed liquor (0.2g/ml hydrogen peroxide 60ml, 0.35g/ml salpeter solution 10ml) is prepared, 2g molybdenum trioxides are added to
Stirred 5 hours in mixed liquor, stir speed (S.S.) 300r/min；Then hydro-thermal process 12 hours under the conditions of 90 DEG C, are cooled to room
Temperature, after centrifuging, filtering, bar-shaped molybdenum trioxide is dried to obtain at 20 DEG C；
The bar-shaped molybdenum trioxide by made from is with thiophene according to mass ratio 2：1 is dispersed in 80ml carbon tetrachloride solvents, 100
Stirred 5 hours at DEG C, solid mixed-powder is dried to obtain at 20 DEG C.Solid mixed-powder is placed in the high temperature furnace of hydrogen,
With 5 DEG C/min programming rates, 1200 DEG C of sintering reaction 12h are risen to, room temperature is naturally cooled to and obtains molybdenum carbide；
By obtained molybdenum carbide and sulphur simple substance according to mass ratio 1：9, ball milling 48 hours in ball mill, product is protected in hydrogen
In the high temperature furnace of shield, 140 DEG C are heat-treated 24 hours, naturally cool to room temperature and obtain molybdenum carbide sulphur composite.
Molybdenum carbide sulphur composite manufactured in the present embodiment is nano bar-shape structure, long 5 μm, nanometer rods it is a diameter of
60nm；Specific surface area and electrical conductivity through nitrogen adsorption and four probe test materials, molybdenum carbide sulphur manufactured in the present embodiment are compound
Material specific surface area is 320m2/ g, electrical conductivity are 1.05 × 102S·cm-1。
Embodiment 6
The molybdenum carbide sulphur composite prepared in embodiment 5 is assembled into button lithium-sulfur cell in the way of embodiment 2.
Cycle performance is tested：At 30 DEG C of constant temperature, in 1.5~3.0V voltage range, filled with 1C current density
Discharge test, 648 reversible capacity is still maintained after circulation 500 times, and take in and can protect after 1C circulations 500 times
Hold more than 70%, there is the coulombic efficiency more than 97%, show excellent cyclical stability.
Embodiment 7
Mixed liquor (0.2g/ml hydrogen peroxide 18ml, 0.35g/ml salpeter solution 18ml) is prepared, 3g molybdenum trioxides are added to
Stirred 12 hours in mixed liquor, stir speed (S.S.) 500r/min；Then hydro-thermal process 24 hours under the conditions of 120 DEG C, are cooled to
Room temperature, after centrifuging, filtering, bar-shaped molybdenum trioxide is dried to obtain at 120 DEG C；
The bar-shaped molybdenum trioxide by made from is with carboxymethyl cellulose according to mass ratio 1：10 are dispersed in 50ml acetone solvents,
Stirred 48 hours at -5 DEG C, solid mixed-powder is dried to obtain at 120 DEG C.Solid mixed-powder is placed in N2High temperature furnace
In, with 10 DEG C/min programming rates, 600 DEG C of sintering reaction 24h are risen to, room temperature is naturally cooled to and obtains molybdenum carbide；
By obtained molybdenum carbide and sulphur simple substance according to mass ratio 9：1, ball milling 12 hours in ball mill, product is in N2Protection
High temperature furnace in, 200 DEG C be heat-treated 12 hours, naturally cool to room temperature and obtain molybdenum carbide sulphur composite.
Molybdenum carbide sulphur composite manufactured in the present embodiment is nano bar-shape structure, long 3 μm, nanometer rods it is a diameter of
50nm；Specific surface area and electrical conductivity through nitrogen adsorption and four probe test materials, molybdenum carbide sulphur manufactured in the present embodiment are compound
Material specific surface area is 340m2/ g, electrical conductivity are 1.03 × 102S·cm-1。
Embodiment 8
The molybdenum carbide sulphur composite prepared in embodiment 7 is assembled into button lithium-sulfur cell in the way of embodiment 2.
Cycle performance is tested：At 30 DEG C of constant temperature, in 1.5~3.0V voltage range, filled with 1C current density
Discharge test, still maintains 635mAh/g reversible capacity after circulation 500 times, and is taken in after 1C circulations 500 times
More than 70% can be maintained at, there is the coulombic efficiency more than 97%, show excellent cyclical stability.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of molybdenum carbide sulphur composite, it is characterised in that molybdenum carbide and sulphur simple substance, the molybdenum carbide are included in chemical composition
For porous club shaped structure, length is 1~5 μm, a diameter of 30~60nm；The sulphur simple substance is doped in the hole of molybdenum carbide, carbon
The mass ratio for changing molybdenum and sulphur simple substance is 1~9：9~1.
2. the preparation method of molybdenum carbide sulphur composite as claimed in claim 1, comprises the following steps：
1) after mixing molybdenum trioxide raw material, hydrogen peroxide and salpeter solution, hydrothermal treatment obtains bar-shaped molybdenum trioxide；
2) the bar-shaped molybdenum trioxide and carbon matrix precursor material are mixed, dried, reduction reaction is carried out under protective atmosphere and is obtained
Bar-shaped molybdenum carbide；
3) the bar-shaped molybdenum carbide and sulphur simple substance are mixed, carries out being thermally treated resulting in molybdenum carbide sulphur composite wood under protective atmosphere
Material.
3. the preparation method of molybdenum carbide sulphur composite according to claim 2, it is characterised in that the concentration of the hydrogen peroxide
For 0.01~0.35g/mL；The concentration of the salpeter solution is 0.01~0.7g/mL.
4. the preparation method of molybdenum carbide sulphur composite according to Claims 2 or 3, it is characterised in that the hydro-thermal process
Temperature be 90~200 DEG C, the time of the hydro-thermal process is 1~72h.
5. the preparation method of molybdenum carbide sulphur composite according to claim 2, it is characterised in that the carbon matrix precursor material
Including one or more kinds of mixed in glucose, phenolic resin, aniline, pyrroles, thiophene, sucrose and carboxymethyl cellulose
Compound.
6. according to the preparation method of the molybdenum carbide sulphur composite of claim 2 or 5, it is characterised in that bar-shaped three oxygen
The mass ratio for changing molybdenum and carbon matrix precursor material is 1：0.05~200.
7. the preparation method of molybdenum carbide sulphur composite according to claim 2, it is characterised in that the step 2) and step
3) protective atmosphere in independently is N2, Ar, He and H2One or both of more than mixed gas.
8. according to the preparation method of the molybdenum carbide sulphur composite of claim 2 or 7, it is characterised in that in the step 2)
The temperature of reduction reaction is 400~1200 DEG C, and the time of reduction reaction is 1~72h.
9. according to the preparation method of the molybdenum carbide sulphur composite of claim 2 or 7, it is characterised in that in the step 3)
The temperature of heat treatment is 140~200 DEG C, and the time of heat treatment is 10~30h.
10. a kind of lithium-sulfur cell, including positive pole, cathode of lithium and electrolyte, the positive pole include active material, acetylene black and
PVDF, it is characterised in that the active material is for molybdenum carbide sulphur composite described in claim 1 or according to claim 2
The molybdenum carbide sulphur composite that preparation method described in~9 any one obtains.
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| CN114914426A (en) * | 2022-05-30 | 2022-08-16 | 大连理工大学 | High-performance sulfur @ carbon/molybdenum carbide composite material and preparation method thereof |
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