CN110416508A - A kind of three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material and preparation method and application - Google Patents
A kind of three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material and preparation method and application Download PDFInfo
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- CN110416508A CN110416508A CN201910631425.5A CN201910631425A CN110416508A CN 110416508 A CN110416508 A CN 110416508A CN 201910631425 A CN201910631425 A CN 201910631425A CN 110416508 A CN110416508 A CN 110416508A
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- 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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- H—ELECTRICITY
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Abstract
The present invention discloses a kind of three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material and preparation method and application, the composite material is by soluble cobalt aqueous solution and vulcanizing agent aqueous solution, the mixed solution stirred to get is in 150~280 DEG C of progress hydro-thermal reactions, it is filtered again after furnace cooling, obtains solid A after drying；Solid A is added in diallyl dimethyl ammoniumchloride solution and is stirred, washing obtains solid B；Solid B is put into after being stirred in MXene aqueous solution and is stood, is freeze-dried after centrifuge washing later, obtain solid C；Under the protection of nitrogen, solid C is made in 500~700 DEG C of calcinings.For the present invention through electrostatic interaction self assembly on MXene nanometers of sheet matrixes, which can effectively accommodate bulk effect of the cobalt disulfide in charge and discharge process, which has excellent charge-discharge performance, high rate performance and high coulombic efficiency for the first time.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, three-dimensional more particularly, to a kind of electrostatic self-assembled
Flower-shaped cobalt disulfide/MXene composite material and preparation method and application.
Background technique
With social progress and development, the energy problem that the mankind are faced is increasingly prominent.Lithium ion battery, as current
It is the most successfully commercialized energy storage device, it is worried for the part in terms of energy storage to alleviate people, therefore receive all circles
The heat of personage is held in both hands.Particularly, it due to green/environmental protection of lithium ion battery and the advantages such as can be recycled, is led in electric car
Domain is widely developed application.Currently, negative electrode active material employed in lithium ion battery is usually various leads in the market
Electrically it is good/with layer structure graphite type material, theoretical specific capacity 372mAh/g, relatively be suitble to lithium ion insertion with
Deintercalation, and show higher coulombic efficiency for the first time and preferable cyclical stability.But with the development of industry and technology,
More stringent requirements are proposed for performance parameter such as capacity, energy density and cycle life of the people to lithium ion battery, and graphite-like is negative
The lithium ion battery of pole material preparation is in the requirement for being unable to satisfy energy-density lithium ion battery at present.
For cobalt disulfide as lithium ion battery electrode material, theoretical specific capacity is typically up to > 700mAh/g, is commercialization
More than at least twice of graphite negative electrodes material, in addition, element sulphur reserves are very rich, price is very cheap, and cobalt disulfide
The embedding lithium voltage of material is relatively low, is highly suitable as the negative electrode material of the lithium ion battery cell of next-generation high-energy.So
And such material can generate biggish cubical expansivity, lead to cobalt disulfide material in entering lithium ion charge and discharge process
It dusting and falls off, one side will affect the contact between active material and collector, the electronic transmission process of obstruction；Another party
Face also results in solid electrolyte interface film progressive additive in cyclic process, to constantly consume lithium ion and will increase
Internal battery impedance, so that capacity and coulombic efficiency are constantly decayed, cycle life decline.Therefore, it is necessary in its charge and discharge process
The bulk effect for buffering its generation, to improve its cyclical stability as far as possible.
In view of the above-mentioned problems, currently used solution be prepare vulcanization cobalt nano-particle, and by itself and carbon material into
Row is compound, this is a kind of more promising method.But existing vulcanization cobalt composite material, only to cobalt disulfide material
Simple mechanical cladding is carried out, its capacity is played and the improvement of cycle life is all than relatively limited.It is received by hydro-thermal method synthesis
The cobalt disulfide material of popped rice shape, and it is combined together firmly with MXene using electrostatic self-assembled method, it can be fully
The capacity of cobalt disulfide active material is played, while the superior electric conductivity of MXene and nanometer laminated structure is utilized.Especially
Ground, there is presently no patent report mistakes, and three-dimensional flower-shaped cobalt disulfide electrostatic self-assembled is formed 3D structure in MXene nanometer sheet
Composite material, other than the excellent properties showed on lithium ion battery negative material, other field (sodium ion electricity
Pond/catalysis ORE etc.) also by the favor by scientists.
Summary of the invention
In order to solve in above-mentioned carbon negative pole material in the prior art and its similar composite material in high-energy density lithium
Deficiency and disadvantage present in ion battery application, the primary purpose of the present invention is that it is three-dimensional flower-shaped to provide a kind of electrostatic self-assembled
Cobalt disulfide/MXene composite material.The composite material has preferable three-dimensional flexible structure, can fully play two sulphur
Change the capacity of cobalt nanometer particle, and can effectively accommodate its bulk effect in charge and discharge process, there is good electric conductivity
Can, excellent multiplying power and cycle performance.
Another object of the present invention is to provide a kind of above-mentioned three-dimensional flower-shaped cobalt disulfide/MXene of electrostatic self-assembled is compound
The preparation method of material.
A further object of the present invention is to provide a kind of above-mentioned three-dimensional flower-shaped cobalt disulfide/MXene of electrostatic self-assembled is compound
The application of material.
The purpose of the present invention is realized by following technical proposals:
A kind of three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material, the composite material are by soluble cobalt
Saline solution and vulcanizing agent aqueous solution, the mixed solution stirred to get is in 150~280 DEG C of progress hydro-thermal reactions, after furnace cooling
It is filtered again, obtains solid A after drying；Solid A is added in diallyl dimethyl ammoniumchloride solution and is stirred, is washed
Obtain solid B；Solid B is put into after being stirred in MXene aqueous solution and is stood, is freeze-dried after centrifuge washing, obtain solid C；
Under the protection of nitrogen, solid C is made in 500~700 DEG C of calcinings.
Preferably, soluble cobalt is CoCl in the soluble cobalt aqueous solution2、C4H6CoO4、CoSO4、Co(NO3)2
Or more than one in the hydrate of above-mentioned salt.
Preferably, vulcanizing agent is one of vulcanized sodium, thioacetamide, L-cysteine in the vulcanizing agent aqueous solution
More than.
Preferably, the soluble cobalt and the molar ratio of vulcanizing agent are (0.5~1): 1.
Preferably, 0.01~0.04mol/L of concentration of the soluble cobalt aqueous solution, the vulcanizing agent aqueous solution it is dense
Degree is 0.01~0.04mol/L, and the concentration of the MXene aqueous solution is 0.001~0.01mg/L.
Preferably, diallyl dimethyl ammoniumchloride and solid in the diallyl dimethyl ammoniumchloride solution
The mass ratio of A is (0.05~1): 1；The mass ratio of MXene and solid B are (0.1~1) in the MXene aqueous solution: 1.
The three-dimensional flower-shaped cobalt disulfide of the electrostatic self-assembled/MXene composite material preparation method, including it is following specific
Step:
S1. by soluble cobalt aqueous solution and vulcanizing agent aqueous solution, the mixed solution that stirs to get 150~280 DEG C into
Row hydro-thermal reaction, is filtered again after furnace cooling, obtains solid A after drying；
S2. solid A is added in diallyl dimethyl ammoniumchloride solution and is stirred, washing obtains solid B；
S3. solid B is put into after being stirred in MXene aqueous solution and is stood, be freeze-dried after centrifuge washing later, obtain solid
C；
S4. under the protection of nitrogen, solid C is calcined at 500~700 DEG C, three-dimensional flower-shaped two sulphur of electrostatic self-assembled is made
Change cobalt/MXene composite material.
Preferably, the time of hydro-thermal reaction described in step S1 is 12~36h.
Preferably, the time of stirring described in step S2 be 12~for 24 hours；
Preferably, the time of standing described in step S3 is 24~48h；
Preferably, the time of calcining described in step S4 is 2~12h.
The three-dimensional flower-shaped cobalt disulfide of the electrostatic self-assembled/MXene composite material is in cell negative electrode material field
Using.
Soluble cobalt and vulcanizing agent are first dissolved separately in deionized water by the present invention, are then sufficiently mixed both
It uniformly and completely reacts, then by simple hydro-thermal reaction, cobalt disulfide nanometer sheet is made to grow into flower-like structure.Added later
Enter to make to PDDA solution the surface of flower-shaped cobalt disulfide to coat one layer of PDDA, and the lotus that becomes positively charged.Positive charge will be had later
Flower-shaped cobalt disulfide is put into dispersion in GO solution and stirs evenly, and the two is made to be self-assembly of three-dimensional poroid knot by the effect of electrostatic
Its compound is finally put into high temperature under nitrogen cladding atmosphere sintering and GO is reduced to MXene by structure.Within this material, MXene
Nanometer sheet closely, while also forming orderly phase in conjunction with cobalt disulfide is under the action of electrostatic between its piece and piece
The porous sheet structure to connect.In the negative electrode material obtained by above technical scheme, cobalt disulfide monocrystalline is colored logical with MXene
It crosses electrostatic interaction and is self-assembly of three-dimensional floral structure, finally obtained a kind of three-dimensional manometer and spent three-dimensional porous structure.
Cobalt disulfide is three-dimensional flower-shaped in the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled of the invention/MXene composite material,
Be conducive to improve gram volume performance of the material in charge and discharge process, and flower-shaped cobalt disulfide is made of nano crystal piece, structure
Single stable shows good cyclical stability.Meanwhile the flower-shaped cobalt disulfide electrostatic self-assembled is in MXene nanometer sheet,
Contact resistance between the two can be reduced.And the orderly porous channel interconnected formed between MXene nanometer sheet, have
Conducive to the storage of lithium ion and the infiltration of electrolyte, so that flower-shaped cobalt disulfide be made to have one preferably to contact with electrolyte.This
Outside, electrostatic growth cobalt disulfide nano flower play supporting role to MXene layer, be beneficial to prevent layer structure collapse with
MXene layers of stacking again, keeps preferable flexible structure, provides effective channel for the transmission of electronics and lithium ion, makes
Obtaining flower-shaped cobalt disulfide/MXene composite material has preferable high rate performance.And after being located at the carbonization outside flower-shaped cobalt disulfide
PDDA layer completely cut off directly contacting for flower-shaped cobalt disulfide and electrolyte, guarantee solid electrolyte interface film in the table of graphene
Face forms stable solid electrolyte interface film.And the MXene piece of three-dimension flexible can effectively accommodate cobalt disulfide and fill
Bulk effect in discharge process keeps higher specific capacity.Therefore, three-dimensional flower-shaped two sulphur of electrostatic self-assembled prepared by the present invention
Changing cobalt/MXene composite material has excellent charge-discharge performance and high rate performance.
Compared with prior art, the invention has the following advantages:
1. active material cobalt disulfide is the nanometer flower structure of single crystal nanoplate self-generating in the present invention, is conducive to it and is filling
Capacity is given full play to during discharge cycles and keeps excellent cyclical stability.MXene makes composite material have three simultaneously
Porous structure is tieed up, is conducive to the storage of ion and the infiltration of electrolyte, is preferably contacted convenient for active material with electrolyte, for electricity
The transmission of son and lithium ion provides effective channel, so that cobalt disulfide/MXene composite material is with preferable forthright again
Energy.
2. supporting role of the present invention due to cobalt disulfide nano flower to MXene can keep preferable flexible knot
Structure can effectively accommodate bulk effect of the cobalt disulfide in charge and discharge process, and higher specific capacity is kept to conduct electricity very well,
With excellent charge-discharge performance and high rate performance and higher coulombic efficiency for the first time.
Detailed description of the invention
Fig. 1 is the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled made from embodiment 1/MXene composite material scanning electron microscope
Picture.
Fig. 2 is the three-dimensional flower-shaped cobalt disulfide of 1 gained electrostatic self-assembled of embodiment/MXene composite material rate charge-discharge
Performance curve.
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
1. by 5mmol CoSO4·7H2O and 10mmol Na2S is dissolved separately in 40mL deionized water, and it is molten to obtain pink A
Liquid and transparent B solution；
2. being slowly added in B solution after mixing, 30min be sufficiently stirred to the solution A described in step 1, obtain pale red
Color C solution；
3. solution C described in step 2 is poured into stainless steel cauldron, then it is placed in air dry oven and is heated at 150 DEG C
Heat preservation 36h is carried out, is filtered again after furnace cooling, solid D is obtained after drying；
4. the dilution of 100mL deionized water is added in 4ml 20wt.% diallyl dimethyl ammoniumchloride (PDDA) solution
Afterwards, gained 200mg solid D in step 3 is put into wherein stirring a period of time, solid E is obtained by centrifuge washing；
5. the aqueous solution of the MXene containing 50mg is weighed, after the dilution of 100mL deionized water is added, by gained 200mg in step 4
Solid E is put into wherein be sufficiently stirred after stand the time for 24 hours, centrifuge washing is placed in freeze drying box and is dried later, obtains
Solid F；
It is rapidly heated in resistance furnace 6. the solid F of step 5 is put into, under the protection of nitrogen, is warming up to 600 DEG C of heat preservation 4h
Afterwards to get the three-dimensional flower-shaped cobalt disulfide of the electrostatic self-assembled/MXene composite material.
Fig. 1 is the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled made from the present embodiment/MXene composite material scanning electron microscope
Picture.It will be seen from figure 1 that the resulting negative electrode material of the present embodiment has three-dimensional porous structure above-mentioned.Fig. 2 is the present embodiment
The three-dimensional flower-shaped cobalt disulfide of gained electrostatic self-assembled/MXene composite material rate charge-discharge performance curve.It can from Fig. 2
Out, gained composite material capacity is higher, and higher capacity can be still kept under big circulation, illustrates that material circulation is stablized
Performance is also very excellent.
Embodiment 2
1. by 3mmol CoCl2·6H2O and 3mmol TAA (thioacetamide) is dissolved separately in 40mL deionized water,
Obtain pink solution A and transparent B solution；
2. being slowly added in B solution after mixing, 30min be sufficiently stirred to the solution A described in step 1, obtain pale red
Color C solution；
3. solution C described in step 2 is poured into stainless steel cauldron, then it is placed in air dry oven and is heated at 150 DEG C
Heat preservation 36h is carried out, is filtered again after furnace cooling, solid D is obtained after drying；
4. the dilution of 100mL deionized water is added in 4ml 20wt.% diallyl dimethyl ammoniumchloride (PDDA) solution
Afterwards, gained 200mg solid D in step 3 is put into wherein stirring a period of time, solid E is obtained by centrifuge washing；
5. the aqueous solution of the MXene containing 50mg is weighed, after the dilution of 100mL deionized water is added, by gained 200mg in step 4
Solid E is put into wherein be sufficiently stirred after stand the time for 24 hours, centrifuge washing is placed in freeze drying box and is dried later, obtains
Solid F；
It is rapidly heated in resistance furnace 6. solid F described in step 5 is put into, under the protection of nitrogen, is warming up to 600 DEG C of heat preservations
To get the three-dimensional flower-shaped cobalt disulfide of the electrostatic self-assembled/MXene composite material after 4h.
Embodiment 3
1. by 3mmol CoCl2·6H2O and 3mmolL- cysteine is dissolved separately in 40mL deionized water, obtains powder
Red solution A and B solution；
2. being slowly added in B solution after mixing, 30min be sufficiently stirred to the solution A described in step 1, obtain pale red
Color C solution；
3. solution C described in step 2 is poured into stainless steel cauldron, then it is placed in air dry oven and is heated at 280 DEG C
Heat preservation 36h is carried out, is filtered again after furnace cooling, solid D is obtained after drying；
4. the dilution of 100mL deionized water is added in 4ml 25wt.% diallyl dimethyl ammoniumchloride (PDDA) solution
Afterwards, gained 200mg solid D in step 3 is put into wherein stirring a period of time, solid E is obtained by centrifuge washing；
5. the aqueous solution of the MXene containing 5mg is weighed, after the dilution of 100mL deionized water is added, by gained 200mg in step 4
Solid E is put into wherein be sufficiently stirred after stand the 35h time, centrifuge washing is placed in freeze drying box and is dried later, obtains
Solid F；
It is rapidly heated in resistance furnace 6. solid F described in step 5 is put into, under the protection of nitrogen, is warming up to 500 DEG C of heat preservations
To get the three-dimensional flower-shaped cobalt disulfide of the electrostatic self-assembled/MXene composite material after 12h.
Embodiment 4
1. by 3mmolC4H6CoO4And 3mmol TAA (thioacetamide) is dissolved separately in 40mL deionized water, is obtained
Pink solution A and transparent B solution；
2. being slowly added in B solution after mixing, 30min be sufficiently stirred to the solution A described in step 1, obtain pale red
Color C solution；
3. solution C described in step 2 is poured into stainless steel cauldron, then it is placed in air dry oven and is heated at 220 DEG C
Heat preservation 30h is carried out, is filtered again after furnace cooling, solid D is obtained after drying；
4. the dilution of 100mL deionized water is added in 4ml 15wt.% diallyl dimethyl ammoniumchloride (PDDA) solution
Afterwards, gained 200mg solid D in step 3 is put into wherein stirring a period of time, solid E is obtained by centrifuge washing；
5. the aqueous solution of the MXene containing 10mg is weighed, after the dilution of 100mL deionized water is added, by gained 200mg in step 4
Solid E is put into wherein be sufficiently stirred after stand the 48h time, centrifuge washing is placed in freeze drying box and is dried later, obtains
Solid F；
It is rapidly heated in resistance furnace 6. solid F described in step 5 is put into, under the protection of nitrogen, is warming up to 700 DEG C of heat preservations
To get the three-dimensional flower-shaped cobalt disulfide of the electrostatic self-assembled/MXene composite material after 2h.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material, which is characterized in that the composite material is
By soluble cobalt aqueous solution and vulcanizing agent aqueous solution, the mixed solution that stirs to get in 150~280 DEG C of progress hydro-thermal reactions,
It is filtered again after furnace cooling, obtains solid A after drying；Diallyl dimethyl ammoniumchloride solution is added in solid A
Middle stirring, washing obtain solid B；Solid B is put into after being stirred in MXene aqueous solution and is stood, is freeze-dried after centrifuge washing,
Obtain solid C；Under the protection of nitrogen, solid C is made in 500~700 DEG C of calcinings.
2. the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 1, which is characterized in that
Soluble cobalt is CoCl in the soluble cobalt aqueous solution2、C4H6CoO4、CoSO4、Co(NO3)2Or the hydrate of above-mentioned salt
In more than one.
3. the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 1, which is characterized in that
Vulcanizing agent is one or more of vulcanized sodium, thioacetamide, L-cysteine in the vulcanizing agent aqueous solution.
4. the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 1, which is characterized in that
The soluble cobalt and the molar ratio of vulcanizing agent are (0.5~1): 1.
5. the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 1, which is characterized in that
0.01~0.04mol/L of concentration of the soluble cobalt aqueous solution, the concentration of the vulcanizing agent aqueous solution is 0.01~
0.04mol/L, the concentration of the MXene aqueous solution are 0.001~0.01mg/L.
6. the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 1, which is characterized in that
The mass ratio of diallyl dimethyl ammoniumchloride and solid A are in the diallyl dimethyl ammoniumchloride solution
(0.05~1): 1；The mass ratio of MXene and solid B are (0.1~1) in the MXene aqueous solution: 1.
7. the system of the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 1-6
Preparation Method, which is characterized in that comprise the following specific steps that:
S1. by soluble cobalt aqueous solution and vulcanizing agent aqueous solution, the mixed solution stirred to get is in 150~280 DEG C of progress water
Thermal response is filtered again after furnace cooling, obtains solid A after drying；
S2. solid A is added in diallyl dimethyl ammoniumchloride solution and is stirred, washing obtains solid B；
S3. solid B is put into after being stirred in MXene aqueous solution and is stood, be freeze-dried after centrifuge washing, obtain solid C；
S4. under the protection of nitrogen, solid C is calcined at 500~700 DEG C, the obtained three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/
MXene composite material.
8. the preparation method of the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 7,
It is characterized in that, the time of hydro-thermal reaction described in step S1 is 12~36h.
9. the preparation method of the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material according to claim 7,
It is characterized in that, the time of stirring described in step S2 be 12~for 24 hours；The time of standing described in step S3 is 24~48h；Step
The time of calcining described in rapid S4 is 2~12h.
10. the three-dimensional flower-shaped cobalt disulfide of electrostatic self-assembled/MXene composite material described in any one of claims 1-6 is in battery
Application in negative electrode material field.
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| JIAN XIE等: "Self-assembly of CoS2/graphene nanoarchitecture by a facile one-pot route and its improved electrochemical Li-storage properties", 《NANO ENERGY》 * |
| JIANJIAN FU等: "Two-dimensional titanium carbide (MXene)-wrapped sisal-Like NiCo2S4 as positive electrode for High-performance hybrid pouch-type asymmetric supercapacitor", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111342009A (en) * | 2020-03-02 | 2020-06-26 | 肇庆市华师大光电产业研究院 | Novel high-performance lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111342009B (en) * | 2020-03-02 | 2022-06-03 | 肇庆市华师大光电产业研究院 | High-performance lithium-sulfur battery positive electrode material and preparation method thereof |
| CN115259874A (en) * | 2021-04-29 | 2022-11-01 | 中国科学院福建物质结构研究所 | Toughened and conductive MXene-zirconia composite ceramic and preparation method thereof |
| CN115259874B (en) * | 2021-04-29 | 2023-11-17 | 中国科学院福建物质结构研究所 | Toughened and conductive MXene-zirconia composite ceramic and preparation method thereof |
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| CN110416508B (en) | 2022-06-03 |
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