CN106684357A - Porous cobalt sulfide and nitrogen-doped carbon composite material and preparation method and application thereof - Google Patents
Porous cobalt sulfide and nitrogen-doped carbon composite material and preparation method and application thereof Download PDFInfo
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- CN106684357A CN106684357A CN201710028997.5A CN201710028997A CN106684357A CN 106684357 A CN106684357 A CN 106684357A CN 201710028997 A CN201710028997 A CN 201710028997A CN 106684357 A CN106684357 A CN 106684357A
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- nitrogen
- doped carbon
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001868 cobalt Chemical class 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000012467 final product Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 9
- 238000005987 sulfurization reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002262 Schiff base Substances 0.000 claims description 5
- 150000004753 Schiff bases Chemical class 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 235000001508 sulfur Nutrition 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 150000004987 o-phenylenediamines Chemical class 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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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
- H01M4/364—Composites as mixtures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a porous cobalt sulfide and nitrogen-doped carbon composite material and a preparation method and application thereof. The composite material is mainly prepared from the following raw materials of a cobalt salt containing crystal water, o-phenylenedimine, o-vanillin and elemental sulfur. Compared with the prior art, the composite material obtained by the preparation method is used as a positive electrode material or a negative electrode material of a lithium ion battery, and excellent cycle stability and high rate performance are shown; and moreover, the preparation method does not need any solvent and is a green, simple and energy-saving preparation method for an electrode material.
Description
Technical field
The invention discloses a kind of cobalt sulfide of porous and nitrogen-doped carbon composite and its preparation method and application, belong to
Technical field of lithium ion battery electrode.
Background technology
As the development of society, energy crisis are increasingly serious, environment deteriorates increasingly, and development of the people to new forms of energy is proposed
An urgent demand.Lithium ion battery is because with voltage height, big energy density, good cycle, little self discharge, memory-less effect, work
The advantages of making wide ranges enjoys the favor of people, is referred to as the leading power supply of 21 century.
During lithium ion battery develops, people have been developed colourful new electrode materials, cobalt sulfide
It is exactly one of them, because it has, conductive capability is strong, heat stability is good, theoretical specific capacity is high, by it and after material with carbon element is compound,
Chemical property is more preferable.
However, the current cobalt sulfide synthetic method being combined with material with carbon element of finding report, comparatively complicated process of preparation,
And environment is polluted, the performance of the electrode obtained material is unsatisfactory.
The content of the invention
Goal of the invention：For above-mentioned technical problem, the invention provides a kind of cobalt sulfide of porous is combined with nitrogen-doped carbon
Material and its preparation method and application, using the cobalt salt containing water of crystallization and o-phenylenediamine, o-vanillin and elemental sulfur " one is carried out
Pot " reaction, so as to be uniformly inlaid with sulfuration cobalt nano-particle porous nitrogen-doped carbon composite (cobalt sulfide of porous with
Nitrogen-doped carbon composite).
Technical scheme：The invention provides a kind of cobalt sulfide of porous and nitrogen-doped carbon composite, it is mainly by following
Raw material is made：
Cobalt salt containing water of crystallization, o-phenylenediamine, o-vanillin and elemental sulfur.
It is preferred that, the amount ratio of the material of the cobalt salt containing water of crystallization, o-phenylenediamine, o-vanillin and elemental sulfur is 1:1:2:
(1.5~20).
It is preferred that, the amount ratio of the material of the cobalt salt containing water of crystallization, o-phenylenediamine, o-vanillin and elemental sulfur is 1:1:2:
(2~15).
It is preferred that, the cobalt salt containing water of crystallization is cobalt chloride hexahydrate, four hydration cobaltous acetate, Cobalt monosulfate heptahydrate or six
Nitric hydrate cobalt etc..
It is preferred that, the composite is the porous nitrogen-doped carbon composite for being uniformly inlaid with sulfuration cobalt nano-particle.
Present invention also offers the preparation method of the cobalt sulfide of the porous and nitrogen-doped carbon composite, including following step
Suddenly：O-phenylenediamine, o-vanillin, the cobalt salt containing water of crystallization and elemental sulfur are mixed by proportioning, ground and mixed is uniform, Ran Hou
Under inert atmosphere, reaction is first kept under low heating temperature, make o-phenylenediamine, o-vanillin, the cobalt salt containing water of crystallization that solid phase to occur
The schiff bases complex of self-assembling reaction in-situ preparation cobalt；Subsequently, calcine at high temperature, the schiff bases complex for making cobalt occurs original
Position thermal decomposition, carbon thermal reduction and sulfurization, finally obtain final product the composite.
It is preferred that, cobalt sulfide and the preparation method of nitrogen-doped carbon composite of the porous are comprised the following steps：
(1) o-phenylenediamine, o-vanillin, the cobalt salt containing water of crystallization and elemental sulfur are stoichiometrically mixed, in room
The lower grinding of temperature, so that mixture uniformly mixes；
(2) under an inert atmosphere, the mixture for step (1) being obtained is kept for 2~6 hours at 30~70 DEG C；Heat up again
To 500~800 DEG C, and calcine 2~8 hours at this temperature, natural cooling obtains final product the composite.
It is preferred that, the inert atmosphere is nitrogen or inert gas atmosphere (such as argon).
The present invention finally additionally provides the cobalt sulfide of the porous and nitrogen-doped carbon composite as lithium ion battery just
Pole or the application of negative material.
Preparation method provided by the present invention does not need any solvent, and reaction condition is simple, easy to operate, raw materials used equal
Abundance, without the need for later-period purification or further activation process.Therefore, the method for the present invention be a kind of safety it is easy, pollution-free,
The method for meeting energy-saving and emission-reduction requirement.
The method of the present invention employs the control synthesis of " one pot " solid state reaction, i.e., under inert gas shielding, first low
At hot temperature, there is the Schiff's base of solid phase self-assembling reaction in-situ preparation cobalt in o-phenylenediamine, o-vanillin, the cobalt salt containing water of crystallization
Coordination compound；Subsequently, at high temperature, there is thermal decomposition in situ, carbon thermal reduction and sulfurization in the schiff bases complex of cobalt, so as to make
The standby porous nitrogen-doped carbon composite for being uniformly inlaid with sulfuration cobalt nano-particle.Porous in composite is due to cobalt
The gaseous volatilization that produces of schiff bases complex thermal decomposition after provided.
Technique effect：Relative to prior art, the present invention has the advantage that：
(1) present invention adopts " one pot " solid reaction process, and by temperature programming, a step obtains being inlaid with sulfur in tube furnace
Change the porous carbon composite of cobalt nano-particle；The preparation method is simple, environmentally friendly, yield is big, easily realizes extensive
Production；
(2) negative or positive electrode of the composite of cobalt sulfide and the nitrogen-doped carbon synthesized by the present invention as lithium ion battery
Material, has the advantages that good cycling stability, specific capacity height, high rate performance are superior, is a kind of excellent lithium ion cell electrode
Material.
Description of the drawings
Fig. 1 is the X ray diffracting spectrum of the composite of cobalt sulfide and nitrogen-doped carbon in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the composite of cobalt sulfide and nitrogen-doped carbon in embodiment 1.
Fig. 3 is the transmission electron microscope picture of the composite of cobalt sulfide and nitrogen-doped carbon in embodiment 1.
Fig. 4 is the storage lithium circulation volume figure of the composite of cobalt sulfide and nitrogen-doped carbon in embodiment 1.
Fig. 5 is the storage lithium high rate performance figure of the composite of cobalt sulfide and nitrogen-doped carbon in embodiment 1.
Specific embodiment
Below in conjunction with the accompanying drawings and instantiation, the present invention is further elucidated, it should be understood that these examples are merely to illustrate this
Bright rather than restriction the scope of the present invention.
Embodiment 1
2mmol cobalt chloride hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 5mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, in N2Under atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 40 DEG C, and keep 3 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and kept for 4 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the porous nitrogen-doped carbon composite (cobalt sulfide and nitrogen of porous for being uniformly inlaid with sulfuration cobalt nano-particle is obtained final product
Doping carbon composite).
Fig. 1 is the X ray diffracting spectrum of the cobalt sulfide with the composite of nitrogen-doped carbon of the present embodiment synthesis.As a result show
Show, in cobalt sulfide and the composite of nitrogen-doped carbon CoS is contained2(JCPDS No.89-1492) and CoS (JCPDS No.70-
2864)。
Fig. 2 is the scanning electron microscope (SEM) photograph of the cobalt sulfide with the composite of nitrogen-doped carbon of the present embodiment synthesis.Show in figure
Cobalt sulfide is a kind of material of porous with the composite of nitrogen-doped carbon.
Fig. 3 is the transmission electron microscope picture of the cobalt sulfide with the composite of nitrogen-doped carbon of the present embodiment synthesis.The figure illustrates
Sulfuration cobalt nano-particle is evenly distributed in carbon.
The composite that the present embodiment synthesizes is mixed with Super P and binding agent (PVDF) by certain mass ratio, then
Black paste is modulated into dispersant N-Methyl pyrrolidone (NMP), is evenly applied to thereafter on foam copper, it is true at 90 DEG C
Sky is dried 12 hours, just obtains pole piece.Then using it as positive pole, used as negative pole, Celgard 2400 is barrier film to lithium piece,
1.0mol L-1Lithium hexafluoro phosphate (solvent be volume ratio be 1:1 ethylene carbonate (EC) and dimethyl carbonate (DME) it is mixed
Bonding solvent) it is electrolyte, CR2032 type button cells are assembled into, survey its chemical property.
Fig. 4 is the storage lithium circulation volume figure of the cobalt sulfide with the composite of nitrogen-doped carbon of the present embodiment synthesis.From figure
As can be seen that in 100mA g-1Discharge and recharge under the conditions of, the first discharge specific capacity of the composite of cobalt sulfide and nitrogen-doped carbon
For 1190.5mAh g-1, first charge-discharge coulombic efficiency is up to 60%；After charge and discharge cycles 50 are enclosed, specific capacity is stable in 487mAh
g-1, show that cobalt sulfide has good cyclical stability with the composite of nitrogen-doped carbon.
Fig. 5 is the storage lithium high rate performance figure of the cobalt sulfide with the composite of nitrogen-doped carbon of the present embodiment synthesis.From figure
As can be seen that the high rate performance of the composite of cobalt sulfide and nitrogen-doped carbon is all very superior, imply that and made using this material
Electrode material for lithium ion battery goes for high power field.
Embodiment 2
Weigh 2mmol cobalt chloride hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 30mmol elemental sulfurs, room temperature
Under grind respectively in agate mortar it is uniform after, it is then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat,
Boat will be burnt again to push in tube furnace, in N2Under atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 40 DEG C, and protect at such a temperature
Hold 3 hours.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and kept for 4 hours at such a temperature.Drop with stove afterwards
Temperature obtains final product the cobalt sulfide and nitrogen-doped carbon composite of porous to after room temperature.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 3
2mmol cobalt chloride hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 5mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, in N2Under atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 60 DEG C, and keep 3 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and kept for 4 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 4
2mmol cobalt chloride hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 5mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, in N2Under atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 40 DEG C, and keep 5 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and kept for 4 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 5
2mmol cobalt chloride hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 5mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, in N2Under atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 40 DEG C, and keep 3 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 700 DEG C, and kept for 4 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 6
2mmol cobalt chloride hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 5mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, in N2Under atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 40 DEG C, and keep 3 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and kept for 6 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 7
The hydration cobaltous acetate of 2mmol tetra-, 2mmol o-phenylenediamines, 4mmol o-vanillins and 5mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, in N2Under atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 40 DEG C, and keep 3 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and kept for 4 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 8
2mmol cobalt chloride hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 5mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, under an ar atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 40 DEG C, and keep 3 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and kept for 4 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 9
2mmol Cobalt monosulfate heptahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 3mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, under an ar atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 30 DEG C, and keep 6 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 500 DEG C, and kept for 8 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 10
Weigh 2mmol cabaltous nitrate hexahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 40mmol elemental sulfurs, room temperature
Under grind respectively in agate mortar it is uniform after, it is then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat,
Boat will be burnt again to push in tube furnace, under an ar atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 70 DEG C, and protect at such a temperature
Hold 2 hours.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 800 DEG C, and kept for 2 hours at such a temperature.Drop with stove afterwards
Temperature obtains final product the cobalt sulfide and nitrogen-doped carbon composite of porous to after room temperature.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Embodiment 11
2mmol Cobalt monosulfate heptahydrates, 2mmol o-phenylenediamines, 4mmol o-vanillins and 4mmol elemental sulfurs are weighed, under room temperature
It is after grinding uniformly respectively in agate mortar then four mixing, grinding is uniform.The mixture is transferred to into ceramics and burns boat, then
Boat will be burnt to push in tube furnace, under an ar atmosphere, with 2 DEG C of min-1Heating rate be warmed up to 50 DEG C, and keep 4 at such a temperature
Hour.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 650 DEG C, and kept for 5 hours at such a temperature.Lower the temperature with stove afterwards
To after room temperature, the cobalt sulfide and nitrogen-doped carbon composite of porous is obtained final product.
Relevant characterization and test are carried out similar to embodiment 1 to the composite of prepared cobalt sulfide and nitrogen-doped carbon,
Its result is similar to Example 1.
Claims (9)
1. a kind of cobalt sulfide of porous and nitrogen-doped carbon composite, it is characterised in that it is mainly made up of following raw material：
Cobalt salt containing water of crystallization, o-phenylenediamine, o-vanillin and elemental sulfur.
2. the cobalt sulfide of porous according to claim 1 and nitrogen-doped carbon composite, it is characterised in that described containing crystallization
The amount ratio of the material of the cobalt salt of water, o-phenylenediamine, o-vanillin and elemental sulfur is 1:1:2:(1.5~20).
3. the cobalt sulfide of porous according to claim 1 and nitrogen-doped carbon composite, it is characterised in that described containing crystallization
The amount ratio of the material of the cobalt salt of water, o-phenylenediamine, o-vanillin and elemental sulfur is 1:1:2:(2~15).
4. the cobalt sulfide of porous according to claim 1 and nitrogen-doped carbon composite, it is characterised in that described containing crystallization
The cobalt salt of water is cobalt chloride hexahydrate, four hydration cobaltous acetate, Cobalt monosulfate heptahydrate or cabaltous nitrate hexahydrate.
5. the cobalt sulfide of porous according to claim 1 and nitrogen-doped carbon composite, it is characterised in that the composite wood
Expect to be uniformly inlaid with the porous nitrogen-doped carbon composite of sulfuration cobalt nano-particle.
6. the preparation method of the cobalt sulfide of porous described in any one of claim 1-5 and nitrogen-doped carbon composite, its feature exists
In comprising the following steps：O-phenylenediamine, o-vanillin, the cobalt salt containing water of crystallization and elemental sulfur are mixed by proportioning, grinding is mixed
Close uniform, then under an inert atmosphere, reaction is first kept under low heating temperature, make o-phenylenediamine, o-vanillin, containing water of crystallization
There is the schiff bases complex of solid phase self-assembling reaction in-situ preparation cobalt in cobalt salt；Subsequently, calcine at high temperature, make the Schiff's base of cobalt
There is thermal decomposition in situ, carbon thermal reduction and sulfurization in coordination compound, finally obtain final product the composite.
7. the preparation method of the cobalt sulfide of porous and nitrogen-doped carbon composite according to claim 6, it is characterised in that bag
Include following steps：
(1) o-phenylenediamine, o-vanillin, the cobalt salt containing water of crystallization and elemental sulfur are stoichiometrically mixed, at room temperature
Grinding, so that mixture uniformly mixes；
(2) under an inert atmosphere, the mixture for step (1) being obtained is kept for 2~6 hours at 30~70 DEG C；500 are warming up to again
~800 DEG C, and calcine 2~8 hours at this temperature, natural cooling obtains final product the composite.
8. the preparation method of the cobalt sulfide of porous and nitrogen-doped carbon composite according to claim 6, it is characterised in that institute
Inert atmosphere is stated for nitrogen or inert gas atmosphere.
9. the cobalt sulfide of porous described in any one of claim 1-5 and nitrogen-doped carbon composite as lithium ion cell positive or
The application of negative material.
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