CN109037661A - A kind of core-shell structure cobalt disulfide composite material and preparation method - Google Patents
A kind of core-shell structure cobalt disulfide composite material and preparation method Download PDFInfo
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- CN109037661A CN109037661A CN201811037038.0A CN201811037038A CN109037661A CN 109037661 A CN109037661 A CN 109037661A CN 201811037038 A CN201811037038 A CN 201811037038A CN 109037661 A CN109037661 A CN 109037661A
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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
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- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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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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Abstract
The present invention provides a kind of preparation methods of core-shell structure cobalt disulfide composite material, comprising: S1) organic acid cobalt salt, organic sulphur source, glycolic solvents, cetyl trimethylammonium bromide are mixed with organic carbon source, after hydro-thermal reaction, obtain intermediate product；Organic sulphur source contains amino；S2 the intermediate product is mixed with sulphur powder), and is made annealing treatment in protective atmosphere, core-shell structure cobalt disulfide composite material is obtained.Compared with prior art, core-shell structure cobalt disulfide composite material prepared by the present invention has good three-D space structure, specific surface area and more reactivity sites with increase, volume change of the cobalt disulfide in deintercalation sodium ion can also be accommodated, buffer its internal stress as caused by volume change, it prevents substance powder phenomenon-tion from occurring, ensure that structural stability when it is used for anode material of lithium-ion battery；The carbon-coating on surface enhances the ability of electronics conduction, has ensured the performance of cobalt disulfide excellent electrochemical performance.
Description
Technical field
The invention belongs to sodium-ion battery technical field more particularly to a kind of core-shell structure cobalt disulfide composite material and its
Preparation method.
Background technique
Sodium-ion battery has the characteristics that sodium is resourceful and low in cost, has attracted the extensive pass of domestic and international researcher
Note, it is considered to be the optimal candidate of lithium ion battery may be substituted in scale energy storage field from now on.Sodium-ion battery in recent years
Research achieves impressive progress in succession, and research system is enriched constantly.However, due to sodium ion have biggish ionic radius and compared with
Slow kinetic rate becomes the principal element for restricting storage sodium Materials, and developing high performance embedding sodium negative electrode material is to mention
High sodium ion battery specific energy and the key for promoting its application.
The negative electrode material that can be used for sodium-ion battery being currently known mainly has carbon-based material, alloy material, nonmetallic list
Matter, metal oxide and organic compound etc..Wherein transient metal sulfide is abundant because its material itself has aoxidizes also
Former reaction site and higher theoretical storage sodium capacity, have obtained the attention of height in anode material of lithium-ion battery field and have opened
Hair.
Cobalt disulfide is a kind of substance rather important in transient metal sulfide, and cobalt metal ion is in addition to can be in electrification
It learns and is provided other than more binding sites in reaction, moreover it is possible to play electrocatalysis, reduce the reaction energy levels of electrochemical reaction, promote
Quick combine between ion carries out with disengaging, the quick embedding sodium and removing sodium reaction for being advantageously implemented sodium-ion battery.Then, two
The conductivity of cobalt sulfide itself is low, and huge volume change can occur in deintercalation sodium ion for it, or increases or reduce, therefore
When pure cobalt disulfide is as anode material of lithium-ion battery, there is the two to restrict the critical defect that its capacitance plays: first, two sulphur
The conductivity for changing cobalt is excessively poor, in battery work, has a large amount of electronics and ion occurs to shift and exchange, and cobalt disulfide
The process then cannot be quickly carried out, electronic conduction is slow, and macroscopically cause the internal resistance of battery to increase, serious polarization, capacity attenuation
And its it is serious；Second, cobalt disulfide, when sodium ion is embedded in, volume will increase 300%, while in sodium ion abjection, volume
It can reduce again, volume change violent in this way will lead to mutual extrusion between cobalt disulfide material, cause internal stress to be concentrated, most
The dusting for causing cobalt disulfide material eventually is then showing as battery hair when carrying out long circulating charge-discharge test in the performance of battery
Raw serious capacity attenuation, the reduced service life of battery.Therefore, cobalt disulfide is needed for the negative electrode material of sodium-ion battery
There are special structure building and reasonable superficial layer design, the high storage sodium performance of competence exertion cobalt disulfide itself.
The spherical cobalt disulfide that a kind of graphene coated is disclosed in the Chinese patent of Publication No. CN106558690A is multiple
The synthetic method of condensation material wraps up cobalt disulfide particle using graphene, to improve the electric conductivity of material, and graphene
The internal stress variation of material can also be alleviated to provide certain mechanical protection when cobalt disulfide volume change.But specially from it
It sees in the result of benefit report, when the material is used for the cathode of sodium-ion battery, under the current density of 1000mA/g, can provide
The capacity of about 250mAh/g, the capacity only have 29.4% or so of cobalt disulfide theoretical capacity, it is clear that are not able to satisfy high-energy
The requirement of densitybattery.And cyclical stability can only keep 100 circle charge and discharge, occur in cyclic process behind obvious
Decaying, illustrate that the stability of cobalt disulfide structure of graphene package is not highly desirable.
A kind of cobalt disulfide/carbon nano-fiber composite material is disclosed in the Chinese patent of Publication No. CN105600745A
Preparation method.Carbon nano-fiber is prepared with the method for electrostatic spinning first in inventor, then utilizes hydrothermal method by two
Cobalt sulfide is supported on the surface of carbon nano-fiber, obtains cobalt disulfide/carbon nano-fiber composite material.Carbon nano-fiber has excellent
Different electric conductivity, to overcome the defect of cobalt disulfide low conductivity.But the structure not can solve cobalt disulfide in charge and discharge
The problems in the internal stress collection generated when enormousness changes when electricity circulation, it will cause it for sodium-ion battery cathode
When material the problem of poor circulation.In addition, the preparation method is complicated, process is various, while electrospinning process is unfavorable for carbon
Nanofiber volume production.In addition, the density of the resulting cobalt disulfide composite material of the invention is small, it is unfavorable for realizing sodium-ion battery
High quality specific energy.
Comprehensive existing patent and documents and materials, it can be seen that cobalt disulfide anode material of lithium-ion battery exists at present
The problems such as preparation section is complicated, battery long circulating performance is poor.Therefore present urgent need, which designs and prepares one kind, has special three-dimensional
The cobalt disulfide composite material of structure and excellent electrochemical performance.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of with better quality specific capacity and preferable times
The core-shell structure cobalt disulfide composite material and preparation method of rate performance.
The present invention provides a kind of preparation methods of core-shell structure cobalt disulfide composite material, comprising:
S1) organic acid cobalt salt, organic sulphur source, glycolic solvents, cetyl trimethylammonium bromide and organic carbon source are mixed
It closes, after hydro-thermal reaction, obtains intermediate product；Organic sulphur source contains amino；
S2 the intermediate product is mixed with sulphur powder), and is made annealing treatment in protective atmosphere, core-shell structure curing is obtained
Cobalt composite material.
Preferably, the step S1) specifically:
A organic acid cobalt salt, organic sulphur source are mixed with glycolic solvents), obtain mixed liquor；
B the mixed liquor, cetyl trimethylammonium bromide are mixed with organic carbon source), after hydro-thermal reaction, obtain centre
Product.
Preferably, the step A) in mix temperature be 25 DEG C~70 DEG C；The mixed time is 5~60min；The step
Rapid B) in mix temperature be 25 DEG C~70 DEG C；The mixed time is 5~60min.
Preferably, the organic acid cobalt salt is selected from Cobaltous oxalate,tetrahydrate, two hydration cobaltous formates, Cobaltous propionate, carboxylic acid cobalt, diamino
One of base Cobaltous propionate, cobalt iso-octoate and naphthoic acid cobalt are a variety of；Organic sulphur source be selected from thiocarbamide, ammonium thiocyanate, methionine,
One of ethylene thiourea and thiosemicarbazides are a variety of；The glycolic solvents be selected from methylene glycol, ethylene glycol, propylene glycol, oneself
One of glycol, pentanediol and cyclohexane diol are a variety of；The organic carbon source is selected from glucose, mannose, fructose, gala
One of sugar, xylose, rice crisp sweets, sucrose and trehalose are a variety of.
Preferably, the organic acid cobalt salt and the mass ratio of organic sulphur source are (2~8): 1；The organic acid cobalt salt with have
The gross mass of machine sulphur source and the mass ratio of glycolic solvents are 1:(50~150)；It is the cetyl trimethylammonium bromide, organic
The mass ratio of carbon source and organic acid cobalt salt is (1~5): (0.2~2): 1.
Preferably, the step S1) in after hydro-thermal reaction, carry out centrifugal treating, obtain intermediate product；The centrifugal treating
Revolving speed be 6000~12000r/min；The time of the centrifugal treating is 15~60min.
Preferably, the temperature of the hydro-thermal reaction is 100 DEG C~200 DEG C；The time of hydro-thermal reaction is 8~20h；The step
Rapid S2) in make annealing treatment heating rate be 2~8 DEG C/min；The holding temperature of annealing is 300 DEG C~800 DEG C；At annealing
The soaking time of reason is 4~22h.
Preferably, the intermediate product and the mass ratio of sulphur powder are 1:(1~5).
The present invention also provides a kind of core-shell structure cobalt disulfide composite materials, including stratum nucleare and shell；The stratum nucleare by
The cobalt disulfide nanometer sheet of stacking is formed；The stratum nucleare is the carbon-coating of N doping.
The present invention also provides above-mentioned core-shell structure cobalt disulfide composite material answering as anode material of lithium-ion battery
With.
The present invention provides a kind of preparation methods of core-shell structure cobalt disulfide composite material, comprising: S1) by organic acid cobalt
Salt, organic sulphur source, glycolic solvents, cetyl trimethylammonium bromide are mixed with organic carbon source, after hydro-thermal reaction, obtain centre
Product；Organic sulphur source contains amino；S2 the intermediate product is mixed with sulphur powder), and is made annealing treatment in protective atmosphere,
Obtain core-shell structure cobalt disulfide composite material.Compared with prior art, the present invention selects organic acid cobalt salt and organic sulphur source point
Not Zuo Wei cobalt source and sulphur source guide curing while using cetyl trimethylammonium bromide as structure directing agent and soft template
Cobalt forms polyhedral structure under specific hydrothermal condition, while organic carbon source can form carbon in the quiet absorption in the surface of cobalt disulfide
Most core-shell structure cobalt disulfide composite material can be obtained with vulcanization through carbonization afterwards in layer, and preparation method is simple, favorable repeatability,
Period is short；And polyhedral cobalt disulfide nanoparticle has biggish specific surface area, is conducive to the friendship of sodium ion and electronics
It changes and shifts, be also beneficial to the infiltration of electrolyte, improve the chemical property of composite material；Furthermore core-shell structure cobalt disulfide
Composite material has good three-D space structure, has the specific surface area increased and more reactivity sites, can also hold
It receives volume change of the cobalt disulfide in deintercalation sodium ion, buffers its internal stress as caused by volume change, prevent object
Matter powder phenomenon-tion occurs, and ensure that structural stability when it is used for anode material of lithium-ion battery；Finally, two sulphur of core-shell structure
The carbon-coating for changing cobalt composite material surface enhances the ability of electronics conduction, has ensured the hair of cobalt disulfide excellent electrochemical performance
It waves.
The present invention also provides a kind of core-shell structure cobalt disulfide composite materials, including stratum nucleare and shell；The stratum nucleare by
The cobalt disulfide nanometer sheet of stacking is formed；The stratum nucleare is the carbon-coating of N doping.Compared with prior art, core provided by the invention
Shell structure cobalt disulfide composite material is the polyhedral structure of core-shell structure, has good three-D space structure, compared to it
There is the specific surface area increased and more reactivity sites, and unique nucleocapsid polyhedral structure can hold for his structure
It receives volume change of the cobalt disulfide in deintercalation sodium ion, buffers its internal stress as caused by volume change, prevent object
Matter powder phenomenon-tion occurs, and ensure that structural stability when it is used for anode material of lithium-ion battery；Meanwhile the carbon-coating gram on surface
The defect for having taken cobalt disulfide low conductivity itself enhances the ability of electronics conduction, while carbon-coating is firmly wrapped in curing
Cobalt surface can well protect internal cobalt disulfide, to ensure the performance of its excellent electrochemical performance.
Detailed description of the invention
Fig. 1 is the synthesis schematic diagram of core-shell structure cobalt disulfide composite material provided by the invention；
Fig. 2 (a) is the scanning electron microscope (SEM) photograph of core-shell structure cobalt disulfide composite material obtained in the embodiment of the present invention 1；(b)
For the high resolution scanning electron microscope of core-shell structure cobalt disulfide composite material obtained in the embodiment of the present invention 2；
Fig. 3 is the transmission electron microscope picture of core-shell structure cobalt disulfide composite material obtained in the embodiment of the present invention 1；
Fig. 4 is the high-resolution-ration transmission electric-lens figure of core-shell structure cobalt disulfide composite material obtained in the embodiment of the present invention 2；
Fig. 5 is the XRD diagram of core-shell structure cobalt disulfide composite material obtained in the embodiment of the present invention 2；
Fig. 6 be the embodiment of the present invention 3 obtained in core-shell structure cobalt disulfide composite material as negative electrode material sodium from
The long circulating charge and discharge electrograph of sub- battery.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of core-shell structure cobalt disulfide composite material, comprising: S1) by organic acid cobalt
Salt, organic sulphur source, glycolic solvents, cetyl trimethylammonium bromide are mixed with organic carbon source, after hydro-thermal reaction, obtain centre
Product；Organic sulphur source contains amino；S2 the intermediate product is mixed with sulphur powder), and is made annealing treatment in protective atmosphere,
Obtain core-shell structure cobalt disulfide composite material.
Referring to Fig. 1, Fig. 1 is the synthesis schematic diagram of core-shell structure cobalt disulfide composite material provided by the invention.
Preparation method of the present invention is simple, favorable repeatability, and the period is short.In the method, it is only necessary to which the hot self assembly of a moisturizing is
Cobalt disulfide object phase can be formed, is then made annealing treatment, high performance core-shell structure cobalt disulfide composite material can be obtained.It compares
In traditional cobalt disulfide electrode material preparation process, this method process is simple, and repeatability is high.
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available.
The organic acid cobalt salt is organic acid cobalt salt well known to those skilled in the art, has no special limitation, this
It is preferably one of cobalt oxalate, cobaltous formate, Cobaltous propionate, carboxylic acid cobalt, diaminopropionic acid cobalt, cobalt iso-octoate and naphthoic acid cobalt in invention
Or it is a variety of, more preferably Cobaltous oxalate,tetrahydrate, two are hydrated cobaltous formates, Cobaltous propionate, carboxylic acid cobalt, diaminopropionic acid cobalt, cobalt iso-octoate
With one of naphthoic acid cobalt or a variety of；Organic sulphur source is that the amino-containing organic sulphur source of packet well known to those skilled in the art is
Can, special limitation is had no, is preferably in thiocarbamide, ammonium thiocyanate, methionine, ethylene thiourea and thiosemicarbazides in the present invention
It is one or more；The glycolic solvents are glycolic solvents well known to those skilled in the art, have no special limitation,
It is preferably one of methylene glycol, ethylene glycol, propylene glycol, hexylene glycol, pentanediol and cyclohexane diol or a variety of in the present invention；Institute
Stating organic carbon source is organic carbon source well known to those skilled in the art, has no special limitation, is preferably sugar in the present invention
One of class compound, more preferably glucose, mannose, fructose, galactolipin, xylose, rice crisp sweets, sucrose and trehalose or
It is a variety of.
According to the present invention, organic acid cobalt salt, organic sulphur source are mixed with glycolic solvents preferably, obtain mixed liquor；It is described
Organic acid cobalt salt and the mass ratio of organic sulphur source are preferably (2~8): 1, more preferably (2~6): 1, be further preferably (3~5): 1,
Most preferably (3.8~4): 1；The organic acid cobalt salt is preferably with the gross mass of organic sulphur source and the mass ratio of glycolic solvents
1:(50~150), more preferably 1:(60~120), it is further preferably 1:(70~100) and, most preferably 1:(80~90)；It is described mixed
The method of conjunction preferably stirs, i.e., is stirred continuously in mixed process；The mixed temperature is preferably 25 DEG C~70 DEG C, more excellent
35 DEG C~60 DEG C are selected as, is further preferably 40 DEG C~50 DEG C, most preferably 45 DEG C；The mixed time is preferably 5~60min,
More preferably 10~50min is further preferably 10~40min, is further preferably 10~30min, most preferably 15~20min.
Then the mixed liquor, cetyl trimethylammonium bromide are mixed with organic carbon source, preferably by cetyl three
Methyl bromide ammonium adds in mixed liquor with organic carbon source to be mixed；The cetyl trimethylammonium bromide, organic carbon source with it is organic
The mass ratio of sour cobalt salt is preferably (1~5): (0.2~2): 1, more preferably (1~4): (0.4~1.5): 1, it is further preferably (1
~3): (0.5~1.2): 1, it is further preferably (1.4~2): (0.7~1): 1, most preferably (1.4~1.86): (0.7~1): 1；
The mixed method preferably stirs, i.e., is stirred continuously in mixed process；The mixed temperature is preferably 25 DEG C~70
DEG C, more preferably 35 DEG C~60 DEG C, be further preferably 40 DEG C~50 DEG C, most preferably 45 DEG C；The mixed time is preferably 5~
60min, more preferably 10~50min are further preferably 20~40min, most preferably 30min.
After mixing, hydro-thermal reaction is carried out；The hydro-thermal reaction preferably carries out in a kettle, more preferably in stainless steel reaction
It is carried out in kettle；The temperature of the hydro-thermal reaction is preferably 100 DEG C~200 DEG C, more preferably 150 DEG C~200 DEG C, further preferably for
180 DEG C~200 DEG C；The time of the hydro-thermal reaction is preferably 8~20h, more preferably 10~16h, is further preferably 12~14h.
Centrifugal treating is preferably carried out after hydro-thermal reaction, separation product obtains intermediate product after further preferably dry；It is described
The revolving speed of centrifugal treating is preferably 6000~12000r/min, more preferably 8000~12000r/min, further preferably for 9000~
12000r/min, most preferably 10000r/min；The time of the centrifugal treating is preferably 15~60min, more preferably 15~
50min is further preferably 15~30min, most preferably 20min；The drying is preferably dried in vacuo；The temperature of the drying is excellent
45 DEG C~90 DEG C are selected as, more preferably 45 DEG C~80 DEG C, be further preferably 45 DEG C~60 DEG C, most preferably 50 DEG C；The drying
Time is preferably 3~12h, more preferably 5~12h, is further preferably 8~12h, most preferably 10h.
The intermediate product is mixed with sulphur powder, and is made annealing treatment in protective atmosphere, core-shell structure cobalt disulfide is obtained
Composite material.The intermediate product and the mass ratio of sulphur powder are preferably 1:(1~5), more preferably 1:(1~4), it is further preferably 1:
(1~3), most preferably 1:3；The protective atmosphere is protective atmosphere well known to those skilled in the art, and it is special to have no
It limits, is preferably nitrogen and/or argon gas in the present invention；The heating rate of the annealing is preferably 2~8 DEG C/min, more excellent
It is selected as 3~7 DEG C/min, is further preferably 4~6 DEG C/min, most preferably 5 DEG C/min；The holding temperature of the annealing is preferred
It is 300 DEG C~800 DEG C, more preferably 400 DEG C~700 DEG C, be further preferably 500 DEG C~700 DEG C, most preferably 600 DEG C~700
℃；The soaking time of the annealing is preferably 4~22h, more preferably 4~18h, is further preferably 4~15h, and most preferably 5
~10h.
The present invention selects organic acid cobalt salt and organic sulphur source respectively as cobalt source and sulphur source, while with cetyl trimethyl
Ammonium bromide guides cobalt disulfide to form polyhedral structure under specific hydrothermal condition, together as structure directing agent and soft template
When organic carbon source can the surface of cobalt disulfide it is quiet absorption form carbon-coating, most afterwards through carbonization with vulcanization core-shell structure two can be obtained
Vulcanize cobalt composite material, preparation method is simple, favorable repeatability, and the period is short；And polyhedral cobalt disulfide nanoparticle tool
Have biggish specific surface area, be conducive to sodium ion and electronics exchange and transfer, be also beneficial to the infiltration of electrolyte, improve multiple
The chemical property of condensation material；Furthermore core-shell structure cobalt disulfide composite material has good three-D space structure, has and increase
Big specific surface area and more reactivity sites, can also accommodate volume change of the cobalt disulfide in deintercalation sodium ion, delay
Its internal stress as caused by volume change is rushed, prevents substance powder phenomenon-tion from occurring, ensure that it is used for sodium-ion battery
Structural stability when negative electrode material；Finally, the carbon-coating of core-shell structure cobalt disulfide composite material surface enhances electronics conduction
Ability, ensured the performance of cobalt disulfide excellent electrochemical performance.
The present invention also provides a kind of core-shell structure cobalt disulfide composite materials, including stratum nucleare and shell；The stratum nucleare by
The cobalt disulfide nanometer sheet of stacking is formed；The stratum nucleare is the carbon-coating of N doping.
According to the present invention, the partial size of the core-shell structure cobalt disulfide composite material is preferably 200nm, by stratum nucleare and shell
Layer composition；The stratum nucleare is polyhedron made of cobalt disulfide nanometer sheet stacks；The shell is the carbon-coating of N doping, package
On polyhedral cobalt disulfide stratum nucleare surface, the thickness of the carbon-coating is preferably 0.4~1.5nm.
Core-shell structure cobalt disulfide composite material provided by the invention is the polyhedral structure of core-shell structure, is had good
Three-D space structure, compared to having the specific surface area increased and more reactivity sites for other structures, and it is unique
Nucleocapsid polyhedral structure can accommodate volume change of the cobalt disulfide in deintercalation sodium ion, buffer it by volume change institute
The internal stress of generation prevents substance powder phenomenon-tion from occurring, ensure that structure when it is used for anode material of lithium-ion battery is steady
It is qualitative；Meanwhile the carbon-coating on surface overcomes the defect of cobalt disulfide low conductivity itself, enhances the ability of electronics conduction, together
When carbon-coating be firmly wrapped in cobalt disulfide surface, internal cobalt disulfide can be protected well, to ensure it
The performance of excellent electrochemical performance.
The present invention also provides above-mentioned core-shell structure cobalt disulfide composite material answering as anode material of lithium-ion battery
With.
In order to further illustrate the present invention, with reference to embodiments to a kind of core-shell structure cobalt disulfide provided by the invention
Composite material and preparation method is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
It is added in the beaker for filling 70ml ethylene glycol and carries out after taking the Cobaltous oxalate,tetrahydrate of 0.7g and 0.18g thiocarbamide to mix
Stirring in water bath, bath temperature are 45 DEG C, mixing time 15min；Then weigh 1.3g cetyl trimethylammonium bromide and
0.7g glucose is added in above-mentioned solution, and is continued stirring in water bath and be uniformly mixed, and bath temperature is 45 DEG C, and mixing time is
30min。
Homogeneous solution after mixed dissolution is poured into stainless steel cauldron and sealed.Then stainless steel cauldron is put into
In 180 DEG C of convection oven, constant temperature places 12h.After reacting, the suspension in reaction kettle is taken out.Then suspension is carried out
Centrifuge separation, centrifugal rotational speed are set as 10000r/min, and the time of centrifugation is 20min.Isolated solid sediment is put
Enter in 50 DEG C of vacuum drying oven, is taken out after toasting 10h.
Dry powder 2g is taken, is then mixed with the sulphur powder of 2g, and be put into tube furnace and made annealing treatment.Tubular type
Atmosphere in furnace is argon gas, and the heating rate of annealing is 5 DEG C/min, and holding temperature is 600 DEG C, soaking time 5h, most
Core-shell structure cobalt disulfide composite material is obtained eventually.
Core-shell structure cobalt disulfide composite material obtained in embodiment 1 is analyzed using scanning electron microscope,
Its scanning electron microscope image is obtained, as shown in Figure 2.As can be seen that core-shell structure cobalt disulfide composite material is more from Fig. 2 (a)
Face body structure, diameter are about 200nm, and polyhedron nanoparticle is stacked with, uniform in size；By the high resolution scanning of Fig. 2 (b)
Electron microscope can be clearly seen that the pattern of single polyhedron core-shell structure cobalt disulfide composite material；Polyhedron core-shell structure two
Vulcanizing cobalt composite material has biggish specific surface area, be conducive to sodium ion and electronics exchange and transfer, be also beneficial to simultaneously
The infiltration of electrolyte enhances the chemical property of negative electrode material.
Core-shell structure cobalt disulfide composite material obtained in embodiment 1 is analyzed using transmission electron microscope,
Its images of transmissive electron microscope is obtained, as shown in Figure 3.The cobalt disulfide nanoscale twins of fold can be more clearly visible seen from Fig. 3
The internal structure being stacked with.
Embodiment 2
It is added in the beaker for filling 70ml ethylene glycol and carries out after taking the Cobaltous oxalate,tetrahydrate of 0.7g and 0.18g thiocarbamide to mix
Stirring in water bath, bath temperature are 45 DEG C, mixing time 15min.Then weigh 1.0g cetyl trimethylammonium bromide and
0.5g glucose is added in above-mentioned solution, and is continued stirring in water bath and be uniformly mixed, and bath temperature is 45 DEG C, and mixing time is
30min。
Homogeneous solution after mixed dissolution is poured into stainless steel cauldron and sealed.Then stainless steel cauldron is put into
In 180 DEG C of convection oven, constant temperature places 12h.After reacting, the suspension in reaction kettle is taken out.Then suspension is carried out
Centrifuge separation, centrifugal rotational speed are set as 10000r/min, and the time of centrifugation is 20min.Isolated solid sediment is put
Enter in 50 DEG C of vacuum drying oven, is taken out after toasting 10h.
Dry powder 2g is taken, is then mixed with the sulphur powder of 4g, and be put into tube furnace and made annealing treatment.Tubular type
Atmosphere in furnace is argon gas, and the heating rate of annealing is 5 DEG C/min, and holding temperature is 700 DEG C, soaking time 10h, most
Core-shell structure cobalt disulfide composite material is obtained eventually.
Core-shell structure cobalt disulfide composite material obtained in embodiment 2 is analyzed using transmission electron microscope,
Its high-resolution-ration transmission electric-lens image is obtained, as shown in Figure 4.The crystalline substance of cobalt disulfide can be clearlyed distinguish from high resolution electron microscopy figure
Lattice trend and spacing of lattice.It is about 0.4- that clearly a layer thickness, which can have been wrapped up, in polygon cobalt disulfide outermost layer simultaneously
The carbon-coating of the N doping of 1.5nm.It is nucleocapsid knot that the figure further demonstrates synthesized cobalt disulfide nanocomposite really
Structure, and the carbon layers having thicknesses are more uniform, enhance the conductivity of cobalt disulfide, while when electrochemical reaction occurs for cobalt disulfide
It can provide a protective layer, buffer the volume change of cobalt disulfide, be conducive to its stable structure.
Core-shell structure cobalt disulfide composite material obtained in embodiment 2 is analyzed using X diffraction, obtains its XRD
Figure, as shown in Figure 5.By Fig. 5 it can be found that the XRD diffraction maximum of sample is corresponding with the XRD diffraction maximum perfection that standard card provides, fill
It defends oneself and synthesized substance is illustrated for cobalt disulfide.
The negative electrode material that core-shell structure cobalt disulfide composite material is used for sodium-ion battery obtained in embodiment 2 is gone forward side by side
Row test, NaCF3SO3/ DEGDME is electrolyte (sodium ion 1mol/L), and sodium metal is to obtain its long circulating charge and discharge to electrode
Figure is as shown in Figure 6.The electrode material carries out the loop test up to 600 times under 1A/g high current density as seen from Figure 6
Capacity is slightly decayed afterwards, and capacity retention ratio capacity after 78% or more, 600 charge-discharge test is positively retained at the left side 600mAh/g
The right side has shown the structural stability of the polyhedron core-shell structure cobalt disulfide nanocomposite and has been applied to sodium-ion battery
High electrochemical performance.
Embodiment 3
Take 0.5g two be hydrated cobaltous formates and 0.2g methionine mixing after be added in the beaker for filling 70ml ethylene glycol into
Row stirring in water bath, bath temperature are 45 DEG C, mixing time 15min.Then weigh 1.0g cetyl trimethylammonium bromide and
0.5g glucose is added in above-mentioned solution, and is continued stirring in water bath and be uniformly mixed, and bath temperature is 45 DEG C, and mixing time is
30min。
Homogeneous solution after mixed dissolution is poured into stainless steel cauldron and sealed.Then stainless steel cauldron is put into
In 180 DEG C of convection oven, constant temperature places 12h.After reacting, the suspension in reaction kettle is taken out.Then suspension is carried out
Centrifuge separation, centrifugal rotational speed are set as 10000r/min, and the time of centrifugation is 20min.Isolated solid sediment is put
Enter in 50 DEG C of vacuum drying oven, is taken out after toasting 10h.
Dry powder 2g is taken, is then mixed with the sulphur powder of 4g, and be put into tube furnace and made annealing treatment.Tubular type
Atmosphere in furnace is argon gas, and the heating rate of annealing is 5 DEG C/min, and holding temperature is 700 DEG C, soaking time 10h, most
Core-shell structure cobalt disulfide composite material is obtained eventually.
Embodiment 4
It is added in the beaker for filling 60ml ethylene glycol and carries out after taking the Cobaltous propionate of 0.54g and 0.18g ammonium thiocyanate to mix
Stirring in water bath, bath temperature are 45 DEG C, mixing time 15min.Then weigh 1.0g cetyl trimethylammonium bromide and
0.5g glucose is added in above-mentioned solution, and is continued stirring in water bath and be uniformly mixed, and bath temperature is 45 DEG C, and mixing time is
30min。
Homogeneous solution after mixed dissolution is poured into stainless steel cauldron and sealed.Then stainless steel cauldron is put into
In 180 DEG C of convection oven, constant temperature places 12h.After reacting, the suspension in reaction kettle is taken out.Then suspension is carried out
Centrifuge separation, centrifugal rotational speed are set as 10000r/min, and the time of centrifugation is 20min.Isolated solid sediment is put
Enter in 50 DEG C of vacuum drying oven, is taken out after toasting 10h.
Dry powder 2g is taken, is then mixed with the sulphur powder of 3g, and be put into tube furnace and made annealing treatment.Tubular type
Atmosphere in furnace is argon gas, and the heating rate of annealing is 5 DEG C/min, and holding temperature is 700 DEG C, soaking time 10h, most
Core-shell structure cobalt disulfide composite material is obtained eventually.
Claims (10)
1. a kind of preparation method of core-shell structure cobalt disulfide composite material characterized by comprising
S1) organic acid cobalt salt, organic sulphur source, glycolic solvents, cetyl trimethylammonium bromide are mixed with organic carbon source, water
After thermal response, intermediate product is obtained；Organic sulphur source contains amino；
S2 the intermediate product is mixed with sulphur powder), and is made annealing treatment in protective atmosphere, it is multiple to obtain core-shell structure cobalt disulfide
Condensation material.
2. preparation method according to claim 1, which is characterized in that the step S1) specifically:
A organic acid cobalt salt, organic sulphur source are mixed with glycolic solvents), obtain mixed liquor；
B the mixed liquor, cetyl trimethylammonium bromide are mixed with organic carbon source), after hydro-thermal reaction, obtain intermediate production
Object.
3. preparation method according to claim 2, which is characterized in that the step A) in mix temperature be 25 DEG C~70
℃；The mixed time is 5~60min；The step B) in mix temperature be 25 DEG C~70 DEG C；The mixed time be 5~
60min。
4. preparation method according to claim 1, which is characterized in that the organic acid cobalt salt be selected from Cobaltous oxalate,tetrahydrate,
One of two hydration cobaltous formates, Cobaltous propionate, carboxylic acid cobalt, diaminopropionic acid cobalt, cobalt iso-octoate and naphthoic acid cobalt are a variety of；It is described to have
Machine sulphur source is selected from one of thiocarbamide, ammonium thiocyanate, methionine, ethylene thiourea and thiosemicarbazides or a variety of；The glycols
Solvent is selected from one of methylene glycol, ethylene glycol, propylene glycol, hexylene glycol, pentanediol and cyclohexane diol or a variety of；It is described organic
Carbon source is selected from one of glucose, mannose, fructose, galactolipin, xylose, rice crisp sweets, sucrose and trehalose or a variety of.
5. preparation method according to claim 1, which is characterized in that the mass ratio of the organic acid cobalt salt and organic sulphur source
For (2~8): 1；The mass ratio of the gross mass and glycolic solvents of the organic acid cobalt salt and organic sulphur source is 1:(50~150)；
The mass ratio of the cetyl trimethylammonium bromide, organic carbon source and organic acid cobalt salt is (1~5): (0.2~2): 1.
6. preparation method according to claim 1, which is characterized in that the step S1) in after hydro-thermal reaction, be centrifuged
Processing, obtains intermediate product；The revolving speed of the centrifugal treating is 6000~12000r/min；The time of the centrifugal treating is 15
~60min.
7. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 100 DEG C~200
℃；The time of hydro-thermal reaction is 8~20h；The step S2) in make annealing treatment heating rate be 2~8 DEG C/min；At annealing
The holding temperature of reason is 300 DEG C~800 DEG C；The soaking time of annealing is 4~22h.
8. preparation method according to claim 1, which is characterized in that the intermediate product and the mass ratio of sulphur powder are 1:(1
~5).
9. a kind of core-shell structure cobalt disulfide composite material, which is characterized in that including stratum nucleare and shell；The stratum nucleare is by stacking
Cobalt disulfide nanometer sheet is formed；The stratum nucleare is the carbon-coating of N doping.
10. core-shell structure cobalt disulfide composite material or as claimed in claim 9 prepared by claim 1~8 any one
Application of the core-shell structure cobalt disulfide composite material as anode material of lithium-ion battery.
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