CN109546139A - A kind of metal sulfide/carbon composite, preparation method and its application in cell negative electrode material - Google Patents
A kind of metal sulfide/carbon composite, preparation method and its application in cell negative electrode material Download PDFInfo
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- H—ELECTRICITY
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
A kind of metal sulfide/carbon composite, preparation method and its application in cell negative electrode material, are related to battery electrode material preparation technical field.The metal sulfide for using stalk to obtain for precursor preparation/carbon net composite material, in piece is flower-shaped or the nano level metal sulfide uniform load of sheet is in carbon net in structure.As metal sulfide proportion is different in composite material, the form of metal sulfide also shows difference in product.The composite material of this structure has macroion and electronic conductivity, and has outstanding structural stability, is conducive to the high rate performance and cycle life that improve material.Using the metal sulfide/carbon composite as anode material of lithium-ion battery, and it is assembled into battery and is tested, the composite material presents extremely outstanding high current fast charging and discharging performance, and the cycle life of overlength, and high charge-discharge capacity is had both, is the ideal anode material of lithium-ion battery with application prospect.
Description
Technical field
The present invention relates to battery electrode material preparation technical fields, are specifically related to a kind of metal sulfide/carbon composite wood
Material, preparation method and its application in cell negative electrode material.
Background technique
As lithium ion battery is in the extensive use of electric car, the cost and reserves of relevant raw materials are faced with sternness
The problem of.Because of the rich reserves of sodium on earth, take up an area the 2.36% of shell, is more than 1000 times of lithium resource (0.0017%).Phase
The extensive concern of global industry is gradually caused to cheap sodium-ion battery (NIB).And lithium, sodium belong to the first main group, have
Similar physico-chemical property, NIB are the novel energy-storing systems for being currently most hopeful to substitute conventional lithium ion battery.Transition Metal Sulfur
Compound is used as one kind NIB negative electrode material, is very promising candidate negative electrode material because of theoretical discharge specific capacity with higher.
In various metal sulfides, because of molybdenum disulfide (MoS2) material has two-dimensional layered structure, it is Na+Insertion with
Abjection provides good transmission channel, and MoS2It is the sodium of great application prospect with high theoretical specific capacity (670mAh/g)
Ion battery cathode material.But pure MoS2Conductivity is low, and structure easily collapses, reunites during charge/discharge cycle, thus long
Journey cycle performance is bad.Research is found using molybdenum disulfide/carbon (MoS2/ C) composite material can effectively improve pure MoS2It is existing to ask
Topic, is outstanding cell negative electrode material.
In recent years, a variety of MoS2The synthetic method of/C composite negative pole material is developed.For example, being with sodium molybdate and thiocarbamide
Forerunner's hydrothermal synthesis MoS2Material, then by MoS2Material is mixed with carbonaceous organic material (such as glucose) carries out hydro-thermal reaction realization
Carbon coating, finally in Ar/H2(5%) 2h that anneals at 800 DEG C in gaseous mixture has obtained MoS2/ C composite, in 0.67A/g electric current
Under density, 300 circle of circulation can be stablized, discharge capacity is 400mAh/g (Wang J, Luo C, Gao T, et al.Small
2015,11,4,473–481).The carbon coating MoS of this technology synthesis2Composite material, surface coated carbon-coating can bear MoS2Charge and discharge
Electric bulk strain power is limited, thus its cycle life is only capable of obtaining limited promotion.It is with graphene, carbon nanotube, carbon fiber
Carbon carrier grows MoS2To prepare MoS2/ C composite is also a kind of common synthetic route.As Zhao Hailei et al. is adopted
Polyvinylpyrrolidone, thiocarbamide, ammonium molybdate and oxalic acid is added to graphene aqueous solution ultrasonic disperse 1h with hydro-thermal method,
Hydro-thermal reaction 12h at 180 DEG C is cleaned after drying in C2H230min is calcined at 500 DEG C in/Ar gaseous mixture, obtains MoS2/ graphene
Composite material has preferable high rate during charging-discharging, under 5A/g high current density, can recycle 200 circles, capacity is
304mAh/g(Teng Y,Zhao H,Zhang Z,et al.Carbon 2017,119,91-100).This technology preparation
MoS2/ C composite performance has preferable raising, but synthesis cost is expensive, and yield is less.Also have and prepared by carbon source of biomass
MoS2/ C composite, as LiuGuilong et al. by palm silk cleaning, drying and in argon gas 800 DEG C calcine be made palm silk
Carbon disperses in aqueous solution and is added sodium molybdate, thiocarbamide, glucose for palm silk carbon, and for 24 hours, product is into one for 200 DEG C of hydro-thermal reactions
600 DEG C of step calcines 2h in argon atmospher, has finally obtained MoS2/ C composite, as anode material of lithium-ion battery,
Under 0.05A/g current density, discharge capacity 223mAh/g keeps 100 circles.Biomass is often first passed through height by the technical solution
Then temperature carbonization loads MoS as carbon base body and molybdenum source, sulphur source hydro-thermal reaction2, further high-temperature calcination obtains final product
(LiuG,Cui J,Luo R,et al.Applied Surface Science2019,469,854–863).Program step compared with
Various, multiple high temp calcining increases cost, and the carbon-based MoS with load being carbonized2Binding force is limited, long circulating performance and
High rate during charging-discharging is bad.
Metal sulfide/carbon composite that above these types method obtains usually has at high cost, complicated for operation or makees
For the limitations such as cell negative electrode material chemical property is bad, cost, environmental protection cannot be considered in terms of with high-performance, to limit its reality
Using.For this purpose, developing the synthetic method of high-performance metal sulfide/carbon composite green, low cost, metal is vulcanized
The preparation of object/carbon composite scale and its practical application as heavy-duty battery negative electrode material are of great significance.
Summary of the invention
It cannot be combined for metal sulfide/carbon composite existing in the prior art inexpensive, environmental-friendly
The technical issues of preparation route and this two industrialization index important greatly of high electrochemical performance, present invention firstly provides a kind of new
The metal sulfide of clever structure/carbon net composite material has macroion and electronic conductivity and strong structure stability.Meanwhile
The present invention also provides the preparation methods of the composite material, calcine pretreatment process without biomass high-temperature.By the composite material,
Applied to the circulation in anode material of lithium-ion battery, showing extremely outstanding high current fast charging and discharging performance and overlength
Service life, and have both high charge-discharge capacity.
To achieve the goals above, the technical scheme adopted by the invention is as follows:
A kind of metal sulfide/carbon composite proposed by the present invention, is made of metal sulfide and carbon, in structure, is in
Piece is flower-shaped or the nano level metal sulfide uniform load of sheet is in carbon net.With metal sulfide institute accounting in composite material
Weight is different, and the form of metal sulfide also shows difference in product.
In the metal sulfide/carbon composite kind, the metal sulfide is preferably molybdenum disulfide, tungsten disulfide, two
The beneficial effects such as high ionic conductivity, high structural stability can further be reached when cobalt sulfide or zinc sulphide.
A kind of preparation method of metal sulfide/carbon composite proposed by the present invention, stalk is molten by delignification
Liquid activation after be made stalk presoma, then by stalk presoma with prepare the source metal of metal sulfide, sulphur source mixes progress
Hydro-thermal reaction, preparing product by anaerobic high-temperature process can be obtained metal sulfide/carbon composite.
As the optimal technical scheme of preparation method of the invention, specific preparation process is as follows:
1), stalk raw material are crushed, acid reaction liquid is then added and carries out removal of impurities processing, it is molten that delignification is then added
Liquid is activated, and stalk presoma is obtained；Stalk is selected from bagasse, corncob, pomelo peel, rice straw, Wheat Straw；
2) stalk presoma is mixed with source metal, sulphur source solution, carries out hydro-thermal reaction；Source metal is selected from sodium molybdate, tungsten
Sour sodium, cobaltous sulfate, zinc chloride, sulphur source are selected from thiocarbamide, L-cysteine, elemental sulfur；
3) hydro-thermal reaction product is heated under oxygen-free atmosphere, metal sulfide/carbon composite is made；It is compound
The mass fraction of metal sulfide is between 5wt%~95wt%, preferably 30wt%~90wt% in material.
Further preferred technical solution as preparation method of the invention:
The process of Hybrid Heating removal of impurities in acid reaction liquid is added in step 1) and delignification solution Hybrid Heating is added
The process of activation, the unlimited precedence of the two processes；It does not clean at the same time it can also only activate.Preferred steps are that acid is first added
Property reaction solution Hybrid Heating removal of impurities, add delignification solution Hybrid Heating activation.
Acid reaction liquid is the one or several kinds of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, preferably sulfuric acid solution in step 1)；Acid
Property reaction solution concentration be 0.1mol/L~15mol/L, preferably 1mol/L~5mol/L；Delignification solution is hydroxide
The one or several kinds of sodium, potassium hydroxide, hydrogen peroxide, sodium sulfite, sodium hypochlorite, preferably sodium hydroxide solution；It goes wooden
The solutes content of plain solution is 0.1wt%~40wt%, preferably 1wt%~15wt%；Stalk powder and delignification solution
Proportion be 1g:5mL~400mL, preferably 1g:20mL~100mL.
Hybrid mode in step 1) between stalk powder and acid reaction liquid, delignification solution includes that stirring is mixed, super
Sound mixing；The heating temperature that removal of impurities and delignification solution are activated is preferably between 50 DEG C~120 between 10 DEG C~300 DEG C
℃；The time is handled between 30 minutes~3 days, is preferably between 2 hours~20 hours.
It is required to carry out product washing and drying and processing in step 1) and step 2), washing is washed including washing, alcohol.
The pH value of mixed solution is 1~9, preferably 5~8 in step 2)；The temperature of reaction is heated between 140 DEG C~300
DEG C, preferably 160 DEG C~220 DEG C；Reaction time between 30 minutes~3 days, is preferably between 6 hours~24 hours.
Oxygen-free atmosphere includes argon gas, nitrogen, argon gas/hydrogen mixed gas one or several kinds, preferably nitrogen in step 3)；Add
Hot temperature is between 200 DEG C~1000 DEG C, preferably 400 DEG C~800 DEG C；Heating time between 30 minutes~3 days, is preferably between 30 points
Clock~5 hour.
Compared with prior art, beneficial effects of the present invention are shown:
1) it is that forerunner prepares metal sulfide/carbon composite method that, the invention proposes a kind of with stalk, synthesized
The metal sulfide by taking molybdenum disulfide as an example/carbon net composite material in, molybdenum disulfide film clips (are received by what nanometer sheet assembled
Popped rice ball), nanometer sheet is between the carbon net.Molybdenum disulfide is to expand layer structure, and the interlamellar spacing of molybdenum disulfide increases and (reaches 0.98nm),
And the interlamellar spacing of traditional molybdenum disulfide material is only 0.64nm, the composite material of this structure has macroion and electronic conductance
Rate, and metal sulfide and carbon combining power are strong, have outstanding structural stability, are conducive to improve the high rate performance of material and follow
The ring service life is the ideal anode material of lithium-ion battery with application prospect.
2), preparation flow is simple and efficient, environmental-friendly using cheap raw material, and lower production costs solve mesh
The preceding problem for preparing molybdenum disulfide/carbon composite low cost, can not be had both etc. with high electrochemical performance.Preparation of the invention
Method can effectively solve the key that molybdenum disulfide/carbon composite is produced as high-performance anode material of lithium-ion battery magnanimity and ask
Topic.Used raw material is stalk, low in cost, environmental-friendly, can play utilization of waste as resource.With existing based on biology
Matter prepares metal sulfide/carbon composite technology and compares, and preparation flow of the present invention is succinctly original, calcines without biomass high-temperature
Pretreatment process, there is no the carbon-based MoS with load2Binding force limited circumstances occur, and products therefrom pattern, structure are only
Spy, chemical property are outstanding.
3), the application as the composite material in terms of electrochemical energy storage, using the metal sulfide/carbon composite as
Anode material of lithium-ion battery, and be assembled into battery and tested.With reported molybdenum disulfide/carbon compound cathode material in the world
Material is compared, and cyclical stability is outstanding, and high current fast charging and discharging performance is outstanding, can steady-state cycle under 5A/g high current density
8000 circles, specific discharge capacity are up to 194mAh/g, and capacity retention ratio is (preceding 20 circle low current density activation) capacity after activation
80.2%, coulombic efficiency is up to 99.8%.Therefore, which presents extremely outstanding high rate during charging-discharging, Yi Jichao
Long cycle life, and outstanding charge/discharge capacity is had both, it is the ideal sodium-ion battery cathode material with application prospect
Material.
Detailed description of the invention
Fig. 1 a, b are molybdenum disulfide/carbon composite different angle scanning electron microscope (SEM) photographs that embodiment 1 obtains, and Fig. 1 c-f is
The Selected area electron power spectrum image of sample；
Fig. 2 a is molybdenum disulfide/carbon composite X-ray diffraction spectrum that embodiment 1 obtains, and Fig. 2 b is the height of the material
Resolved transmittance electron microscope；
Fig. 3 is that molybdenum disulfide/carbon composite that embodiment 1 obtains is electric in 0.2A/g as anode material of lithium-ion battery
Charging and discharging curve figure under current density；
Fig. 4 is high rate performance of the obtained molybdenum disulfide/carbon composite of embodiment 1 as anode material of lithium-ion battery
Figure；
Fig. 5 is that molybdenum disulfide/carbon composite that embodiment 1 obtains is anode material of lithium-ion battery in 5A/g high current
Cycle performance figure under density；
Fig. 6 a is molybdenum disulfide/carbon composite X-ray diffraction spectrum that embodiment 2 obtains, Fig. 6 b, c be the material not
With the scanning electron microscope (SEM) photograph of angle；
Fig. 7 is molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph that embodiment 3 obtains；
Fig. 8 is molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph that embodiment 4 obtains；
Fig. 9 is molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph that embodiment 5 obtains；
Figure 10 a is that embodiment 6 obtains tungsten disulfide/carbon composite X-ray diffraction spectrum, and Figure 10 b is sweeping for the material
Retouch electron microscope；
Figure 11 a is that embodiment 7 obtains cobalt disulfide/carbon composite X-ray diffraction spectrum, and Figure 11 b is sweeping for the material
Retouch electron microscope.
Specific embodiment
With reference to embodiments with attached drawing to metal sulfide/carbon composite of the invention, preparation method and its in electricity
Application in the negative electrode material of pond, which is made, to be discussed further.
Embodiment 1
A kind of preparation method of molybdenum disulfide/carbon composite, comprises the following steps that
(1) bagasse is pre-processed: 5g bagasse raw material is crushed, addition 250mL concentration is 1mol/L sulfuric acid
Impurity is washed away, heating temperature is 80 DEG C, heating time 2h, washing, filtering, and the concentration for adding 250mL is 10wt% hydrogen-oxygen
Change sodium solution in, heat after mixing, heating temperature be 90 DEG C, heating time 3h, then wash, alcohol is washed, is filtered, is dried,
Obtain bagasse presoma.
(2) by step (1) prepare bagasse presoma take 1g be added 60mL water in disperse, be added 2mmol sodium molybdate and
8mmol thiocarbamide, pH are adjusted to 7, after being uniformly mixed, carry out hydro-thermal reaction, reaction temperature be 200 DEG C, the reaction time be for 24 hours,
Product washing, alcohol are washed, filter, dried.
(3) mixture that step (2) is prepared is placed in tube furnace, is heated under a nitrogen, heating temperature
It is 700 DEG C, heating time 2h, products therefrom is molybdenum disulfide/carbon net composite material.
If Fig. 1 a, b are molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph that the present embodiment obtains, Fig. 1 c-f is sample
Selected area electron power spectrum image.As seen from the figure, for molybdenum disulfide film clips in carbon web frame, diameter is about 300 nanometers by carbon net
Molybdenum disulfide film clips tightly wrap up, and be evenly distributed, be conducive to the structural stability for improving material.It is this implementation such as Fig. 2 a
Molybdenum disulfide/carbon net composite material X-ray diffraction spectrum that example obtains is molybdenum disulfide (the JCPDS 00-024- of hexagonal phase
0513), with standard spectrogram except that (002) crystal face of sample obtained by the present embodiment and the molybdenum disulfide (JCPDS of standard
It 00-024-0513) compares, is deviated to low angle, be 2 θ=9.0 °, d=0.98nm shows the molybdenum disulfide of the present embodiment
(002) crystal face interlamellar spacing increases, and to expand layer structure, is conducive to Na+Quick transmission.Without obvious carbon diffraction maximum, show in product
Carbon is amorphous carbon.It is molybdenum disulfide/carbon net composite material high-resolution-ration transmission electric-lens figure that the present embodiment obtains such as Fig. 2 b, into
It is 0.98nm that one step, which demonstrates molybdenum disulfide interlamellar spacing,.
Sodium-ion battery performance test:
The polyvinylidene fluoride (PVDF) of the resulting molybdenum disulfide of embodiment 1/carbon net composite material and 10wt% are bonded
Agent, the conductive black of 10wt%, methyl pyrrolidone (NMP) are mixed into slurry, are coated on metal copper foil, in 110 DEG C of vacuum
Dry 10h, obtains molybdenum disulfide/carbon net composite electrode in drying box.
CR2025 button cell is assembled using above-mentioned working electrode: being to electrode, glass microfiber with sodium piece
(Whatman, GF/A) is diaphragm, with NaClO4Solution for the propene carbonate (PC) of 1.0mol/L is electrolyte, in argon gas
The assembling of CR2025 battery is completed in the glove box of atmosphere.
Pass through Land CT2001A battery test system (0.01V-3.0V) test loop performance under conditions of 25 DEG C.
Fig. 3 is molybdenum disulfide made from embodiment 1/carbon net composite material charging and discharging curve figure, and Fig. 3 illustrates material
It is 0.01-3.0V in voltage range, current density is the 1st circle under 0.2A/g, and the 2nd circle and the 3rd circle recycle lower charging and discharging curve, first
Circle electric discharge and charge specific capacity are respectively 743mA h/g and 395mA h/g, and first circle coulombic efficiency reaches 53.2%.
Fig. 4 is molybdenum disulfide made from embodiment 1/carbon net composite material high rate performance figure, is shown in Fig. 4 compound
High rate performance of the material under different current densities 0.2,0.5,1,3,5,7,10,15 and 20A/g super-large current, be still able to maintain compared with
High specific discharge capacity shows it with excellent electrochemistry.
In addition, after being again restored to low current 0.2A/g after excess current densities 20A/g is tested, reversible specific volume
Amount remains to be restored to proper mass specific capacity, and specific capacity does not decay significantly in the circulation of 10 circles under each current density,
Show molybdenum disulfide/excellent invertibity of carbon net composite material and high rate performance.
Fig. 5 is molybdenum disulfide/carbon net composite material high current cycle performance figure prepared by the embodiment of the present invention 1, in Fig. 5
Molybdenum disulfide/carbon net composite material is shown as sodium-ion battery cathode, circulation can be stablized under 5A/g high current density
8000 circles (cyclic activation process of preceding 20 circle under 0.2A/g low current density is completed in the battery), and hold after 8000 circle circulations
Amount still reaches 194mA h/g, is 80.2% of capacity after activation, coulombic efficiency is up to 99.8%.Sufficiently presenting the material has
Many structural stabilities, the cycle life of overlength and high specific discharge capacity are that a kind of outstanding high-performance sodium-ion battery is negative
Pole material.
Embodiment 2
A kind of preparation method of molybdenum disulfide/carbon composite, comprises the following steps that
(1) bagasse is pre-processed: 5g bagasse raw material is crushed, addition 250mL concentration is 1mol/L sulfuric acid
Impurity is washed away, heating temperature is 80 DEG C, heating time 2h, washing, filtering, and the concentration for adding 250mL is 10wt% hydrogen-oxygen
Change sodium solution in, heat after mixing, heating temperature be 90 DEG C, heating time 3h, then wash, alcohol is washed, is filtered, is dried,
Obtain bagasse presoma.
(2) by step (1) prepare bagasse presoma take 1g be added 60mL water in disperse, be added 1mmol sodium molybdate and
4mmol thiocarbamide, pH are adjusted to 7, after being uniformly mixed, carry out hydro-thermal reaction, reaction temperature be 200 DEG C, the reaction time be for 24 hours,
Product washing, alcohol are washed, filter, dried.
(3) mixture that step (2) is prepared is placed in tube furnace, is heated under a nitrogen, heating temperature
It is 700 DEG C, heating time 2h, products therefrom is molybdenum disulfide/carbon composite.
If Fig. 6 a is hexagonal phase for molybdenum disulfide/carbon net composite material X-ray diffraction spectrum that the present embodiment obtains
Molybdenum disulfide (JCPDS 00-024-0513), with standard spectrogram except that the present embodiment obtained by sample (002) crystal face with
The molybdenum disulfide (JCPDS 00-024-0513) of standard is compared, and is deviated to low angle, is 2 θ=8.8 °, and d=1.05nm shows
Molybdenum disulfide (002) the crystal face interlamellar spacing of the present embodiment increases (up to 1.05nm), to expand layer structure, is conducive to Na+It is quick
Transmission.Such as Fig. 6 b-c, the molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph obtained for the present embodiment.As seen from the figure, curing
For molybdenum sheet in carbon net, carbon net tightly wraps up the curing molybdenum sheet that diameter is about 200nm, and is evenly distributed, and is conducive to improve
The structural stability of material.
Embodiment 3
A kind of preparation method of molybdenum disulfide/carbon composite, comprises the following steps that
(1) corncob is pre-processed: 5g corncob raw material is crushed, the concentration that 300mL is added is 5wt% hydrogen-oxygen
Change potassium solution in, heat after mixing, heating temperature be 100 DEG C, heating time 2h, then wash, alcohol is washed, is filtered, is dried,
Obtain corncob presoma.
(2) it takes 1.5g to be added in 60mL water corncob presoma prepared by step (1) to disperse, add 2mmol molybdic acid
Sodium, 8mmol L-cysteine, pH is adjusted to 6, after being uniformly mixed, carries out hydro-thermal reaction, reaction temperature is 160 DEG C, reaction
Time is for 24 hours, product washing, alcohol to be washed, filter, dried.
(3) mixture that step (2) is prepared is placed in tube furnace, is heated under argon gas, heating temperature
It is 500 DEG C, heating time 5h, products therefrom is molybdenum disulfide/carbon net composite material.
Fig. 7 is molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph that the present embodiment obtains, and is molybdenum disulfide/carbon net
Composite construction.
Embodiment 4
A kind of preparation method of molybdenum disulfide/carbon composite, comprises the following steps that
(1) pomelo peel is pre-processed: 5g pomelo peel raw material is crushed, addition 250mL concentration is 2mol/L hydrochloric acid
Impurity is washed away, heating temperature is 100 DEG C, heating time 5h, washing, filtering, and the concentration for adding 500mL is 12wt% peroxide
Change hydrogen solution in, heat after mixing, heating temperature be 120 DEG C, heating time 3h, then wash, alcohol is washed, is filtered, is dried,
Obtain pomelo peel presoma.
(2) it takes 0.5g to be added in 60mL water pomelo peel presoma prepared by step (1) to disperse, 1mmol sodium molybdate is added
With 4mmolL- cysteine, pH is adjusted to 8, after being uniformly mixed, carries out hydro-thermal reaction, reaction temperature is 220 DEG C, when reaction
Between be 8h, product washing, alcohol are washed, filter, are dried.
(3) mixture that step (2) is prepared is placed in tube furnace, under argon gas/hydrogen mixed gas at heating
Reason, heating temperature are 800 DEG C, heating time 1h, and products therefrom is molybdenum disulfide/carbon net composite material.
Fig. 8 is molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph that the present embodiment obtains, and is molybdenum disulfide/carbon net
Composite construction.
Embodiment 5
A kind of preparation method of molybdenum disulfide/carbon composite, comprises the following steps that
(1) Wheat Straw is pre-processed: 5g Wheat Straw raw material is crushed, addition 250mL concentration is 3mol/L nitric acid
Impurity is washed away, heating temperature is 90 DEG C, heating time 3h, washing, filtering, and the concentration for adding 100mL is 15wt% sulfurous
In acid sodium solution, heat after mixing, heating temperature be 110 DEG C, heating time 10h, then wash, alcohol is washed, is filtered, is dried
It is dry, obtain Wheat Straw presoma.
(2) by step (1) prepare Wheat Straw presoma take 2g be added 120mL water in disperse, be added 2mmol sodium molybdate and
8mmol thiocarbamide, pH are adjusted to 5, after being uniformly mixed, carry out hydro-thermal reaction, and reaction temperature is 210 DEG C, reaction time 10h,
Product washing, alcohol are washed, filter, dried.
(3) mixture that step (2) is prepared is placed in tube furnace, is heated under a nitrogen, heating temperature
It is 1000 DEG C, heating time 1h, products therefrom is molybdenum disulfide/carbon net composite material.
Fig. 9 is molybdenum disulfide/carbon composite scanning electron microscope (SEM) photograph that the present embodiment obtains, and is molybdenum disulfide/carbon net
Composite construction.
Embodiment 6
A kind of preparation method of tungsten disulfide/carbon composite, the specific steps are as follows:
(1) bagasse is pre-processed: 5g bagasse raw material is crushed, addition 250mL concentration is 4mol/L phosphoric acid
Impurity is washed away, heating temperature is 80 DEG C, heating time 2h, washing, filtering, and the concentration for adding 250mL is 10wt% hydrogen-oxygen
Change sodium solution in, heat after mixing, heating temperature be 90 DEG C, heating time 3h, then wash, alcohol is washed, is filtered, is dried,
Obtain bagasse presoma.
(2) by step (1) prepare bagasse presoma take 1g be added 60mL water in disperse, be added 1mmol sodium tungstate and
4mmol thiocarbamide, pH are adjusted to 7, after being uniformly mixed, carry out hydro-thermal reaction, and reaction temperature is 190 DEG C, reaction time 20h,
Product washing, alcohol are washed, filter, dried.
(3) mixture that step (2) is prepared is placed in tube furnace, is heated under a nitrogen, heating temperature
It is 500 DEG C, heating time 5h, products therefrom is tungsten disulfide/carbon net composite material.
Such as Figure 10 a-b, the respectively obtained tungsten disulfide/carbon net composite material X-ray diffraction spectrum of the present embodiment, and
Scanning electron microscope (SEM) photograph.Diffraction spectra analysis shows, the present embodiment product be hexagonal phase tungsten disulfide (JCPDS 01-087-2417),
Carbon is amorphous carbon.By Figure 10 b it is found that the present embodiment product is tungsten disulfide/carbon net composite material.
Embodiment 7
A kind of preparation method of cobalt disulfide/carbon composite, the specific steps are as follows:
(1) corncob is pre-processed: 5g corncob raw material is crushed, addition 250mL concentration is 5mol/L sulfuric acid
Impurity is washed away, heating temperature is 80 DEG C, heating time 3h, washing, filtering, and the concentration for adding 250mL is 10wt% hydrogen-oxygen
Change potassium solution in, heat after mixing, heating temperature be 100 DEG C, heating time 5h, then wash, alcohol is washed, is filtered, is dried,
Obtain corncob presoma.
(2) by step (1) prepare corncob presoma take 1g be added 60mL water in disperse, be added 1mmol cobaltous sulfate and
4mmolL- cysteine, pH are adjusted to 7, after being uniformly mixed, carry out hydro-thermal reaction, and reaction temperature is 190 DEG C, the reaction time
For 24 hours, product washing, alcohol to be washed, filter, dried.
(3) mixture that step (2) is prepared is placed in tube furnace, is heated under a nitrogen, heating temperature
It is 750 DEG C, heating time 2h, products therefrom is cobalt disulfide/carbon composite.
Such as Figure 11 a-b, the respectively obtained cobalt disulfide/carbon net composite material X-ray diffraction spectrum of the present embodiment, and
Scanning electron microscope (SEM) photograph.Diffraction spectra analysis shows, the present embodiment product be cubic phase cobalt disulfide (JCPDS 03-06503322),
Carbon is amorphous carbon.By Figure 11 b it is found that the present embodiment product is cobalt disulfide/carbon net composite material.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (10)
1. a kind of metal sulfide/carbon composite, is made of metal sulfide and carbon, which is characterized in that in piece is flower-shaped or piece
The nano level metal sulfide uniform load of shape is in carbon net.
2. metal sulfide/carbon composite as described in claim 1, which is characterized in that the metal sulfide is preferably
Molybdenum disulfide, tungsten disulfide, cobalt disulfide or zinc sulphide.
3. a kind of method for preparing metal sulfide/carbon composite as claimed in claim 1 or 2, which is characterized in that by stalk
Stalk presoma is made after activating by delignification solution, then by stalk presoma and the metal for preparing metal sulfide
Source, sulphur source mixing carry out hydro-thermal reaction, and preparing product by anaerobic high-temperature process can be obtained metal sulfide/carbon composite wood
Material.
4. preparation method as claimed in claim 3, which is characterized in that steps are as follows:
1), stalk raw material are crushed, then be added acid reaction liquid carry out removal of impurities processing, then be added delignification solution into
Row is activated, and obtains stalk presoma；Stalk is selected from bagasse, corncob, pomelo peel, rice straw, Wheat Straw；
2) stalk presoma is mixed with source metal, sulphur source solution, carries out hydro-thermal reaction；Source metal is selected from sodium molybdate, wolframic acid
Sodium, cobaltous sulfate, zinc chloride, sulphur source are selected from thiocarbamide, L-cysteine, elemental sulfur；
3) hydro-thermal reaction product is heated under oxygen-free atmosphere, metal sulfide/carbon composite is made；Composite material
The mass fraction of middle metal sulfide is between 5wt%~95wt%, preferably 30wt%~90wt%.
5. preparation method as claimed in claim 4, which is characterized in that acid reaction liquid is hydrochloric acid, nitric acid, sulphur in step 1)
The one or several kinds of acid, phosphoric acid, preferably sulfuric acid solution；The concentration of acid reaction liquid is 0.1mol/L~15mol/L, preferably
1mol/L~5mol/L；Delignification solution be sodium hydroxide, potassium hydroxide, hydrogen peroxide, sodium sulfite, sodium hypochlorite one
Kind is several, preferably sodium hydroxide solution；The solutes content of delignification solution is 0.1wt%~40wt%, preferably
1wt%~15wt%；The proportion of stalk powder and delignification solution is 1g:5mL~400mL, preferably 1g:20mL~
100mL。
6. preparation method as claimed in claim 4, which is characterized in that stalk powder and acid reaction liquid in step 1) remove wood
Hybrid mode between quality solution includes stirring mixed, ultrasonic mixing；The heating temperature that removal of impurities and delignification solution are activated
Degree is preferably between 50 DEG C~120 DEG C between 10 DEG C~300 DEG C；Handle the time between 30 minutes~3 days, be preferably between 2 hours~
20 hours.
7. preparation method as claimed in claim 4, which is characterized in that be required to wash product in step 1) and step 2)
It washs and drying and processing, washing is washed including washing, alcohol.
8. preparation method as claimed in claim 4, which is characterized in that the pH value of mixed solution is 1~9 in step 2), preferably
It is 5~8；The temperature of reaction is heated between 140 DEG C~300 DEG C, preferably 160 DEG C~220 DEG C；Reaction time is between 30 minutes~3
It, is preferably between 6 hours~24 hours.
9. preparation method as claimed in claim 4, which is characterized in that oxygen-free atmosphere includes argon gas, nitrogen, argon in step 3)
Gas/hydrogen mixed gas one or several kinds, preferably nitrogen；Heating temperature is between 200 DEG C~1000 DEG C, preferably 400 DEG C~800
℃；Heating time between 30 minutes~3 days, is preferably between 30 minutes~5 hours.
10. a kind of metal sulfide/carbon composite answering in anode material of lithium-ion battery as claimed in claim 1 or 2
With.
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