CN109273679A - A kind of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material and preparation method and purposes - Google Patents
A kind of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material and preparation method and purposes Download PDFInfo
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- CN109273679A CN109273679A CN201810991939.7A CN201810991939A CN109273679A CN 109273679 A CN109273679 A CN 109273679A CN 201810991939 A CN201810991939 A CN 201810991939A CN 109273679 A CN109273679 A CN 109273679A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/58—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
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
A kind of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material and preparation method and purposes, comprising: the first step is raw material with sodium molybdate and thioacetamide, by 160-200 DEG C of hydro-thermal method, grows MoS on blistered water hyacinth biomass carbon surface2Nano-chip arrays；Second step, 80-100 DEG C of immersion method is in MoS2One layer of DOPA amine polymer is coated on nano-chip arrays；Third step is carbonized the dopamine of polymerization to form carbon coating layer to get carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure is arrived by 500-800 DEG C of high-temperature calcination under inert atmosphere.Operation of the present invention is simple, and yield is big, and clad is uniform；When the composite material being related to is as sodium ion negative electrode material, have many advantages, such as at low cost, high reversible charge and discharge capacitance ﹑ long circulation life and excellent high rate performance.
Description
Technical field
The present invention relates to a kind of negative electrode materials of sodium-ion battery, specially carbon coating molybdenum sulfide/water hyacinth biomass carbon
Composite material and preparation method and its purposes.
Background technique
As the energy is largely developed and used to win economic development, environmental pollution and energy shortage is led to problems such as increasingly to dash forward
Out, exploitation and using clean reproducible energy be current social development urgent need.Currently, lithium ion secondary battery is due to height
The advantages that energy density, high power density, long circulation life and higher security performance, be widely used in electronic product,
Electric car is even in aerospace field and environmentally protective chemical energy storage power supply with fastest developing speed.But limited lithium
Resource is unable to satisfy people to the huge demand of lithium ion secondary battery, thus the key solved the problems, such as be to develop it is environmentally protective
And cheap related energy storage technology is to replace lithium-ion energy storage technology.Belong to the sodium of same main group with lithium, it is resourceful, take up an area shell
2.64 % of element reserves, and it is cheap, thus sodium-ion battery increasingly obtains the concern of people, especially extensive
Application in energy storage field.But sodium ion heavier mass and radius (0.102nm) is greatly than lithium ion (0.069nm), this can lead
It causes sodium ion deintercalation in electrode material slow, largely influences the cyclical stability and high rate performance of battery, therefore develop
Suitable electrode material is the critical issue of sodium-ion battery technology development.
Molybdenum sulfide (the MoS of layer structure2) be used as anode material of lithium-ion battery when, specific capacity with higher, ratio
Capacity can reach 500-800mAh g-1.MoS2It is made of single layer or multilayer sulfide, single layer MoS2Upper layer and lower layer are that sulphur is former
Son, intermediate one layer is molybdenum atom, so that there are stronger covalent bonds for interlayer, there is weaker Van der Waals force between layers, more
Layer MoS2By several single layer MoS2Composition, interlamellar spacing is about 0.65nm.Such special structure, is conducive to the insertion of sodium ion,
And bigger space can be provided for its insertion, it avoids leading to volume expansion when insertion sodium, so that keeping the Wen of structure to Ding ﹑ meets sodium
Dinging Xing of the Wen ﹑ that ion quick storage needs possesses required shorter path when larger effective ratio area and ion deinsertion.But
During charge and discharge, MoS2Due to the van der Waals interaction of layer and interlayer, easily hair is reunited, so as to cause electrolyte and activity
Effective contact of substance, so that its reversible capacity is quickly decayed；MoS2Electronic conductivity is not high, and during embedding sodium
The electric conductivity that the Na2O of formation can also deteriorate such electrode material hinders so that high rate performance when it is as cathode is poor
The application in its sodium-ion battery field.
Generally use layer structure MoS2It is compound with Shi Mo Xi ﹑ carbon nanotube, inhibit its reunion, increases its electric conductivity, mention
High sodium ion diffusion rate.At the same time, also to MoS2Surface modification or cladding are carried out, its charge and discharge process is inhibited to generate
The shuttle problem of polysulfide stores up the stability and high rate performance of sodium so as to improve it.Although these methods are to a certain degree
MoS can be improved2As the chemical property of sodium-ion battery electrode, but its reversible capacity and high rate performance etc. are from industry
There is also a distances for change, and it is still necessary to improve.In addition, the preparation cost of these carbon materials such as graphene, carbon nanotube is often high
Expensive, non-renewable material, and the preparation procedure of these carbon materials is relatively complicated, needs a large amount of time and efforts.
Summary of the invention
The purpose of the present invention is to provide carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material and preparation methods and use
On the way, to solve the problems mentioned in the above background technology.
In order to solve the above technical problem, the present invention provides following technical solutions:
A kind of preparation method of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material, comprising the following steps:
1) sodium molybdate is taken to be dissolved in deionized water, under normal temperature conditions, stirring forms colourless solution A；
2) it takes thioacetamide to be dissolved in solution A, forms the solution B of yellow；
3) water intaking cucurbit, peeling are cut into bulk again, after ethanol postincubation, are placed in solution B, are transferred in reaction kettle, 160-
200 DEG C hydro-thermal reaction 12-24 hours, wash, it is dry, obtain MoS2/ water hyacinth biomass carbon composite material；
4) Dopamine hydrochloride is weighed, dissolution forms solution in deionized water, then by the resulting MoS of step 3)2/ water hyacinth
Biomass carbon composite material impregnates wherein, and the generation in 12-24 hours of 80-100 DEG C of water-bath polymerization reaction polymerize dopamine, then stands,
Wash drying；The MoS2Content is 60-70%；
5) it will be calcined 2-6 hours at composite material obtained by step 4) under an inert atmosphere 500-800 DEG C, obtain carbon coating vulcanization
Molybdenum/water hyacinth biomass carbon composite material of core-shell structure.
Wherein, in the step 1), the concentration of sodium molybdate in deionized water is 0.7mmol ml-1-3.0 mmol ml-1。
In the step 2), the concentration of thioacetamide in deionized water is 2.0mmol ml-1-8.0 mmol ml-1。
In the step 4), for the temperature of hydro-thermal reaction at 160 DEG C -200 DEG C, the reaction time is 12-24 h；The concentration of dopamine is
2.5mg mL-1-5mg mL-1.It is high pure nitrogen or argon gas, calcining temperature under the inert atmosphere of high temperature cabonization in the step 5)
Degree is 500-800 DEG C, and calcination temperature is 2-6 hours.
The present invention also provides a kind of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material preparation method is resulting
Biomass carbon composite material is more with hydrochloric acid using sodium molybdate, thioacetamide as raw material that is, using water hyacinth biomass carbon as substrate
Bar amine is polymer monomer preparation.The carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure, MoS2Content is
60-70%.
The present invention also provides a kind of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material preparation method is resulting
The purposes of biomass carbon composite material, i.e., it is the resulting carbon coating molybdenum sulfide of step 5)/water hyacinth biomass carbon core-shell structure is multiple
Condensation material is prepared into cell size, and the slurry is uniformly applied in the nickel foam cut, dry, is stamped and formed out electrode slice,
Inert atmosphere glove box is to electrode assembling button sodium-ion battery with sodium piece.
Wherein, the preparation process of the cell size: carbon coating molybdenum sulfide/water hyacinth biomass carbon core-shell structure is compound
Material, conductive agent acetylene black, binder Kynoar (PVDF) are more uniform than ground and mixed by 80:10:10 mass, are then added
N-methyl-2-pyrrolidone (NMP) solvent, is uniformly mixed.Battery diaphragm uses whatman glass fibre, and electrolyte is adopted
It is with 1mol L-1NaClO4For solute, the ethylene carbonate (EC) that volume ratio is 1:1 is molten with dimethyl carbonate (DMC)
Agent, and 5.0wt. % fluorinated ethylene carbonate is added, cathode uses sodium piece, and the assembling process of battery is all full of height
Pure argon and water oxygen content are completed in the glove box lower than 0.1ppm.
Assembled button sodium-ion battery is stood carries out constant current charge-discharge test afterwards for 24 hours, and charging/discharging voltage range is
0.01-3.0V recycles its charge and discharge cycles stability and multiplying power property in 25 ± 1 DEG C of environment.
Compared with prior art, biological material is cheap in some the Nature, renewable, environmental pollution is small, source
The unique texture that extensive and different biological materials itself have can be prepared by simple process with flourishing hole
The carbon skeleton of gap structure, so that it is in MoS2Modification application in have very big potentiality.Therefore, the present invention by with
Water hyacinth biomass carbon is skeleton, and the carbon coating MoS for the carbon coating layer building that carbonization is formed is polymerize with dopamine2/ water hyacinth is raw
Substance carbon composite material of core-shell structure, obtains high specific capacity and excellent cyclical stability and high rate performance is before there is development in pole
Scape.Advantage of the invention is as follows.
(1) biomass carbon used keeps water hyacinth in the Nature distinctive blistered, is not necessarily to constructed by any template,
The method combined with Shui Re ﹑ water-bath with calcining in preparation prepares carbon coating molybdenum sulfide/water hyacinth biomass composite, at
This is cheap, and preparation process is simple, it is easy to accomplish large production.Mutually tied with composite material construction method and hydro-thermal with immersion method
It closes, easy industrialized production, without being related to vapour deposition process complicated for operation.
(2) carbon coating molybdenum sulfide/water hyacinth biomass composite prepared by, has core-shell structure, and carbon coating layer is
2-10nm thickness, the electric conductivity for being conducive to improve material are asked with effective shuttle for inhibiting polysulfide in charge and discharge process with dissolution
Topic.And the composite material, using water hyacinth biomass carbon as skeleton, polymer is clad, molybdenum sulfide is constructed by active material
Carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure, not single carbon coating structure.
(3) carbon coating molybdenum sulfide/water hyacinth biomass composite prepared by is carried by carbon of water hyacinth biomass carbon
Body, which easily obtains, is from a wealth of sources, processing is convenient, reduces the cost of electrode material.And it is interior for using biomass carbon
Core, the shell that polymer carbonization obtains are worked along both lines the volume change for alleviating sulfide in embedding removing sodium ion, and molybdenum sulfide is overcome
The dissolution of the polysulfide present in charge and discharge process and shuttle problem, and single carbon coating layer is difficult to reach its effect.
(4) carbon coating molybdenum sulfide/water hyacinth biomass composite prepared by, MoS2Nano-chip arrays are grown in water calabash
On reed biomass carbon skeleton, the characteristic of hard carbon and soft carbon is had both, is improved by the carbon coating layer that dopamine polymer carbonization is obtained
The electric conductivity of electrode and the dissolution of polysulfide is generated during inhibiting cycle charge-discharge to overcome special capacity fade fast
Disadvantage, realizing has height ratio capacity, long circulation life, excellent times of forthright, anode material of lithium-ion battery.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the carbon coating molybdenum sulfide/water hyacinth biomass composite XRD spectra prepared in embodiment 1；
Fig. 2 and 3 is the molybdenum sulfide/water hyacinth biomass composite different multiples SEM figure prepared in embodiment 1；
Figure 4 and 5 are the carbon coating molybdenum sulfide/water hyacinth biomass composite different multiples SEM figure prepared in embodiment 1；
Fig. 6 is that carbon coating molybdenum sulfide/water hyacinth biomass composite preparation circulating battery stability is prepared in embodiment 1
Energy；
Fig. 7 is that carbon coating molybdenum sulfide/water hyacinth biomass composite battery high rate performance is prepared in embodiment 1.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Fig. 1-5 is please referred to, the present invention provides a kind of technical solution:
A kind of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material, using water hyacinth biomass carbon as substrate, with sodium molybdate,
Thioacetamide is raw material, is prepared by polymer monomer of Dopamine hydrochloride.
Embodiment 1:
(1) sodium molybdate of 0.15g is taken to be dissolved in the deionized water of 60mL, under normal temperature conditions, stirring forms colourless
Solution A；
(2) it takes the thioacetamide dispersing and dissolving of 0.25g in solution A, forms the solution B of yellow；
(3) the peeling water hyacinth for taking 0.3g, is cut into bulk, after ethanol postincubation, is placed in solution B and stirs, is transferred to reaction kettle
In the middle, 200 DEG C of hydro-thermal reactions for 24 hours, are washed, dry, obtain MoS2/ water hyacinth biomass carbon composite material；
(4) Dopamine hydrochloride for weighing 0.15g, is dissolved in the deionized water of 60mL and forms solution, then by MoS2/ water calabash
Reed biomass carbon composite material impregnates wherein, and 80 DEG C of water-bath polymerization reactions for 24 hours, wash drying；
(5) above-mentioned dopamine is polymerize MoS2/ water hyacinth biomass carbon composite material is under inert gas argon gas, 600 DEG C of high temperature
Carbonization 4 hours, obtains carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure；
(6) resulting carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure is prepared into cell size, battery
The preparation process of slurry: it by carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure, conductive agent acetylene black, glues
Knot agent Kynoar (PVDF) is more uniform than ground and mixed by 80:10:10 mass, and n-methyl-2-pyrrolidone is then added
(NMP) solvent is uniformly mixed.
(7) by slurry, drop coating is dry in the nickel foam cut respectively, strikes out electrode slice as half electricity of button sodium ion
The electrode in pond.The assembling of button sodium ion half-cell: diaphragm uses whatman glass fibre, and electrolyte is with 1mol L-
1NaClO4For solute, the ethylene carbonate (EC) and dimethyl carbonate (DMC) that volume ratio is 1:1 are solvent, and are added
5.0wt.% fluorinated ethylene carbonate, cathode use sodium piece, and the assembling process of battery is all being full of argon gas and water oxygen
Content is completed in the glove box lower than 0.1ppm.
Carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material tests (XRD) by X-ray diffraction spectrum, such as specification
Shown in attached drawing 1, carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure prepared by the present embodiment 1 has spreading out for C
Peak is penetrated, with MoS2Diffraction maximum (JCPDS Card No.17-1492)；As shown in Figure of description 2 and 3, MoS2/ water hyacinth is raw
The SEM picture of substance carbon composite keeps the blistered of water hyacinth biomass carbon self character, and grows one on the surface thereof
Layer MoS2Nano-chip arrays, nanoscale twins thickness 5-10nm.After the polymerization of water-bath dopamine forms carbon coating layer with high temperature cabonization,
As shown in Figure of description 4 and 5, it can be seen that the MoS of blistered biomass carbon surface growth2Nanometer sheet thickens, with a thickness of 10-
15nm forms carbon-coated MoS2- C nuclear shell structure nano chip arrays.According to the reaction of poor quality and thermogravimetric analysis in front and back, it is known that carbon
Coat MoS in molybdenum sulfide/water hyacinth biomass carbon composite material2Content be about 60-70wt.%.
Assembled sodium-ion battery is placed and carries out constant current charge-discharge test afterwards for 24 hours, and charging/discharging voltage section is 3.0V
~0.01V, specific capacity, charge and discharge cycles stabilization energy when circulation measurement is as sodium-ion battery cathode under the conditions of 25 ± 1 DEG C
And multiplying power property.
After being assembled into sodium-ion battery, various electrochemical property tests are carried out.
If Figure of description 6 is the present embodiment in 200mA g-1The stability recycled under current density, for the first time specific capacity
For 729mAh g-1, its discharge capacity still has 477mAh g after 600 circulations-1, 99% or more coulombic efficiency maintenance, table
The composite material of bright the present embodiment has height ratio capacity and excellent cyclical stability in sodium-ion battery field.
As Figure of description 7 show the multiplying power property that button sodium-ion battery manufactured in the present embodiment is run, the material
It shows excellent high rate performance, respectively reaches 542 with specific capacity under 5.0A g-1 current density 0.2,0.5,1.0,2.0,
499,415,328 and 258mAh g-1.When current density resets to 0.2A g-1When, battery capacity returns to 548mAh g-1。
Embodiment 2:
(1) sodium molybdate of 0.3g is taken to be dissolved in the deionized water of 60mL, under normal temperature conditions, stirring forms colourless
Solution A；
(2) it takes the thioacetamide dispersing and dissolving of 0.5g in solution A, forms the solution B of yellow；
(3) water hyacinth of 0.6g is taken, peeling is cut into bulk again, after ethanol postincubation, is placed in solution B and stirs, be transferred to reaction
In kettle, 200 DEG C hydro-thermal reaction 24 hours, wash, it is dry, obtain MoS2/ water hyacinth biomass carbon composite material；
(4) Dopamine hydrochloride for weighing 0.3g, is dissolved in the deionized water of 60mL and forms solution, then by MoS2/ water hyacinth
Biomass carbon composite material impregnates wherein, 80 DEG C water-bath polymerization reaction 12 hours, then stand 12h, wash drying；
(5) MoS for polymerizeing dopamine2/ water hyacinth biomass carbon composite material is under protective atmosphere, 700 DEG C of high temperature cabonizations 3
Hour, obtain carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure；
(6) resulting carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure is prepared into cell size, battery
The preparation process of slurry: it by carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure, conductive agent acetylene black, glues
Knot agent Kynoar (PVDF) is more uniform than ground and mixed by 80:10:10 mass, and n-methyl-2-pyrrolidone is then added
(NMP) solvent is uniformly mixed.
(7) by slurry, drop coating is dry in the nickel foam cut respectively, strikes out electrode slice as half electricity of button sodium ion
The anode in pond.The assembling of button sodium ion half-cell: diaphragm uses whatman glass fibre, and electrolyte is with 1mol L- 1NaClO4For solute, the ethylene carbonate (EC) and dimethyl carbonate (DMC) that volume ratio is 1:1 are solvent, and are added
5.0wt.% fluorinated ethylene carbonate, cathode use sodium piece, and the assembling process of battery is all being full of argon gas and water oxygen
Content is completed in the glove box lower than 0.1ppm.
By carbon coating molybdenum sulfide manufactured in the present embodiment/water hyacinth biomass carbon composite material of core-shell structure be assembled into sodium from
After sub- secondary cell, various electrochemical property tests are carried out.Sodium-ion battery is in 200mA g-1It recycles under current density, puts for the first time
Electric specific capacity is 720mAh g-1, its discharge capacity still has 474mAh g after 600 circulations-1, coulombic efficiency maintenance
99% or more, show that the composite material of the present embodiment has height ratio capacity and excellent stable circulation in sodium-ion battery field
Property.From the high rate performance figure that the present embodiment prepares composite material, in 0.2,0.5,1.0,2.0 and 5.0A g-1Under current density
Specific capacity respectively reaches 540,495,412,325 and 255mAh g-1.When current density resets to 0.2Ag-1When, battery capacity
Return to 545mAh g-1。
Embodiment 3:
(1) sodium molybdate of 0.2g is taken to be dissolved in the deionized water of 60mL, under normal temperature conditions, stirring forms colourless
Solution A；
(2) it takes the thioacetamide dispersing and dissolving of 0.3g in solution A, forms the solution B of yellow；
(3) the peeling water hyacinth of 0.4g is taken, then is cut into bulk, after ethanol postincubation, is placed in solution B and stirs, be transferred to reaction
In kettle, 200 DEG C hydro-thermal reaction 36 hours, wash, it is dry, obtain MoS2/ water hyacinth biomass carbon composite material；
(4) Dopamine hydrochloride for weighing 0.2g, is dissolved in the deionized water of 60mL and forms solution, then by MoS2/ water hyacinth
Biomass carbon composite material impregnate wherein, 80 DEG C water-bath polymerization reaction 18 hours, wash drying；
(5) MoS for polymerizeing dopamine2/ water hyacinth biomass carbon composite material is under protective atmosphere, 800 DEG C of high temperature cabonizations 3
Hour, obtain carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material；
(6) resulting carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material is prepared into cell size, the system of cell size
Standby process: carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure, conductive agent acetylene black, binder is poly- inclined
Vinyl fluoride (PVDF) is more uniform than ground and mixed by 80:10:10 mass, and n-methyl-2-pyrrolidone (NMP) solvent is then added,
It is uniformly mixed.
(7) by slurry, drop coating is dry in the nickel foam cut respectively, strikes out electrode slice as half electricity of button sodium ion
The anode in pond.The assembling of button sodium ion half-cell: diaphragm uses whatman glass fibre, and electrolyte is with 1mol L- 1NaClO4For solute, the ethylene carbonate (EC) and dimethyl carbonate (DMC) that volume ratio is 1:1 are solvent, and are added
5.0wt.% fluorinated ethylene carbonate, cathode use sodium piece, and the assembling process of battery is all being full of argon gas and water oxygen
Content is completed in the glove box lower than 0.1ppm.
By carbon coating molybdenum sulfide manufactured in the present embodiment/water hyacinth biomass carbon composite material of core-shell structure be assembled into sodium from
After sub- secondary cell, various electrochemical property tests are carried out.Sodium-ion battery is in 200mA g-1It recycles under current density, puts for the first time
Electric specific capacity is 725mAh g-1, its discharge capacity still has 478mAh g after 600 circulations-1, coulombic efficiency maintenance
99% or more, show that the composite material of the present embodiment has height ratio capacity and excellent stable circulation in sodium-ion battery field
Property.From the high rate performance figure that the present embodiment prepares composite material, in 0.2,0.5,1.0,2.0 and 5.0A g-1Under current density
Specific capacity respectively reaches 543,496,416,330 and 257mAh g-1.When current density resets to 0.2A g-1When, battery capacity
Return to 544mAh g-1。
One of Examples 1 to 3 carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure is assembled into sodium
It is as shown in table 1 in maximum discharge capacity of the difference under current density after ion battery:
Table 1
Based on above-mentioned, it is an advantage of the current invention that of the invention, the method combined using Shui Re ﹑ water-bath with calcining prepares carbon packet
Molybdenum sulfide/water hyacinth biomass composite is covered, low in cost, preparation process is simple, it is easy to accomplish large production；It is prepared
Carbon coating molybdenum sulfide/water hyacinth biomass composite, have core-shell structure, carbon coating layer be 2-10nm thickness, be conducive to
It improves the electric conductivity of material and effectively inhibits the shuttle and problems of dissolution of polysulfide in charge and discharge process；With water hyacinth biomass
Carbon is carbon carrier, which easily obtains, is from a wealth of sources, processing is convenient, reduces the cost of electrode material；MoS2Nano-chip arrays
It is grown on water hyacinth biomass carbon skeleton, has both the characteristic of hard carbon and soft carbon, the carbon obtained by dopamine polymer carbonization
Clad improves the electric conductivity of electrode and generates the dissolution of polysulfide during inhibiting cycle charge-discharge to overcome specific volume
The fast disadvantage of amount decaying, realizing has height ratio capacity, long circulation life, excellent times of forthright, anode material of lithium-ion battery.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (9)
1. a kind of carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material preparation method, comprising the following steps:
1) sodium molybdate dissolution is taken in deionized water, under normal temperature conditions, stirring forms colourless solution A；
2) it takes thioacetamide to be dissolved in solution A, forms the solution B of yellow；
3) water intaking cucurbit, peeling are cut into bulk again, after ethanol postincubation, are placed in solution B, are transferred in reaction kettle, 160-
200 DEG C hydro-thermal reaction 12-24 hours, wash, it is dry, obtain MoS2/ water hyacinth biomass carbon composite material；
4) Dopamine hydrochloride is weighed, dissolution forms solution in deionized water, then by the resulting MoS of step 3)2/ water hyacinth is raw
Substance carbon composite impregnates and wherein carries out 80-100 DEG C of water-bath polymerization reaction generation in 12-24 hours polymerization dopamine, then quiet
It sets, washs drying；The MoS2Content is 60-70%；
5) it will be calcined 2-6 hours at composite material obtained by step 4) under an inert atmosphere 500-800 DEG C, obtain carbon coating vulcanization
Molybdenum/water hyacinth biomass carbon composite material of core-shell structure.
2. carbon coating molybdenum sulfide according to claim 1/water hyacinth biomass carbon composite material preparation method, feature
Be: in the step 1), the concentration of sodium molybdate in deionized water is 0.7 mmol ml-1-3.0 mmol ml-1。
3. carbon coating molybdenum sulfide according to claim 1/water hyacinth biomass carbon composite material preparation method, feature
Be: in the step 2, the concentration of thioacetamide in deionized water is 2.0 mmol ml-1-8.0 mmol ml-1。
4. carbon coating molybdenum sulfide according to claim 1/water hyacinth biomass carbon composite material preparation method, feature
Be: in the step 3), for the temperature of hydro-thermal reaction at 160 DEG C -200 DEG C, the reaction time is 12-24 h.
5. carbon coating molybdenum sulfide according to claim 1/water hyacinth biomass carbon composite material preparation method, feature
Be: in the step 4), the concentration of dopamine is 2.5mg mL-1-5mg mL-1。
6. carbon coating molybdenum sulfide according to claim 1/water hyacinth biomass carbon composite material preparation method, feature
It is: is high pure nitrogen or argon gas under the inert atmosphere of high temperature cabonization in the step 5), calcination temperature is 500-800 DEG C,
Calcination temperature is 2-6 hours.
7. the preparation of carbon coating molybdenum sulfide according to any one of claim 1 to 6/water hyacinth biomass carbon composite material
The resulting biomass carbon composite material of method, it is characterised in that: using water hyacinth biomass carbon as substrate, with sodium molybdate, thio second
Amide is raw material, is prepared by polymer monomer of Dopamine hydrochloride.
8. the preparation of carbon coating molybdenum sulfide according to any one of claim 1 to 6/water hyacinth biomass carbon composite material
The resulting biomass carbon composite material of method, it is characterised in that:
The resulting carbon coating molybdenum sulfide of step 5)/water hyacinth biomass carbon composite material of core-shell structure is prepared into cell size,
And the slurry is uniformly applied in the nickel foam cut, it is dry, it is stamped and formed out electrode slice, is with sodium piece in inert atmosphere glove box
To electrode assembling button sodium-ion battery.
9. carbon coating molybdenum sulfide according to claim 8/water hyacinth biomass carbon composite material preparation method is resulting
Biomass carbon composite material, it is characterised in that:
The preparation process of the cell size: by carbon coating molybdenum sulfide/water hyacinth biomass carbon composite material of core-shell structure, conduction
Agent acetylene black, binder Kynoar (PVDF) are more uniform than ground and mixed by 80:10:10 mass, and N- methyl -2- is then added
Pyrrolidones (NMP) solvent, is uniformly mixed.
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