CN109950512A - A kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material and its universality preparation method and application - Google Patents
A kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material and its universality preparation method and application Download PDFInfo
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- CN109950512A CN109950512A CN201910317712.9A CN201910317712A CN109950512A CN 109950512 A CN109950512 A CN 109950512A CN 201910317712 A CN201910317712 A CN 201910317712A CN 109950512 A CN109950512 A CN 109950512A
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Abstract
The present invention discloses a kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material and its universality preparation method and application, vulcanizing agent using trithiocyanuric acid as the agent of nitrogen sulfur doping, the agent of three-dimensional grapheme soft mode and transition metal, using hydro-thermal-heat treatment method composite construction in situ simultaneously for constructing doped graphene and coating transient metal sulfide completely, metal sulfide is completely by nitrogen sulphur codope graphene coated；The structure design can significantly solve transition metal sulfide store up lithium or storage sodium during because of volume expansion caused by capacity fade problem；Preparation method process safety of the invention is easy to operate, it can be achieved that volume production, the composite material of preparation can be used as lithium ion battery and sodium-ion battery negative electrode active material.
Description
Technical field
The invention belongs to lithium ion batteries and sodium ion battery electrode material field, are related to a kind of carbon material cladding metal sulphur
The composite material of compound, and in particular to a kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material and its general
Adaptive preparation method and application.
Background technique
Transient metal sulfide (MSs) due to its high theoretical capacity, inexpensive and good electronic conductivity and be considered
It is one of the most potential candidate of anode material as sodium-ion battery (SIB).However, in duplicate embedding sodium and removing sodium
The dissolution of the dusting effect of MSs and the intermediate sulfide of reaction in the electrolytic solution can all be led because of caused by volume expansion in the process
The circulation volume of MSs is caused sharply to decline.Therefore, the research of MSs cyclical stability in lithium ion battery, sodium-ion battery is improved
The problem of always researchers pay close attention to.
It is considered as overcoming above problem most efficient method that MSs is compound with carbon material.On the one hand, the carbon materials of high conductivity
Material can be used as the matrix of MSs, have the function that effectively to disperse MSs nano particle；On the other hand, in the MSs electricity of carbon material cladding
In extremely, carbon material can hinder electrolyte to contact with the direct of MSs as barrier, to inhibit to react being dissolved in for intermediate sulfide
The utilization rate of electrode material is improved in electrolyte, further reaction is on more stable circulation volume.Importantly, different original
The carbon material of sub (such as N, S, B etc.) doping, because local high reaction activity region can be generated and improve conduction by introducing foreign atom
Property, to obtain higher sodium storge quality.Three-dimensional (3D) structure for establishing carbon material is also a selection well, Ke Yigeng
The volume expansion of good adaptation MSs.The three-dimensional carbon material of doping is constructed however, inventing a kind of simple mild method to realize to synchronize
Compound with transient metal sulfide is still a huge challenge.
Summary of the invention
To overcome above-mentioned the deficiencies in the prior art, it is an object of the present invention to provide a kind of nitrogen sulphur codope three-dimensional grapheme and mistakes
Metal sulfide composite material and its universality preparation method and application are crossed, graphene is adapted to and various metals sulfide is multiple
It closes, there is advantage easy to operate, safe and non-toxic, low in cost.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of universality preparation method of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material, including
Following steps:
1) by graphene oxide, melamine, trithiocyanuric acid, transition metal nitrate be successively distributed to ethyl alcohol and go from
The in the mixed solvent of sub- water is stirred to react sufficiently；
The graphene oxide, melamine, trithiocyanuric acid, transition metal nitrate mass ratio be 1:(0.6~
4.8): (0.85~6.8): (3~24)；
2) then stirring product is transferred in water heating kettle and carries out hydro-thermal reaction；
The time of the hydro-thermal reaction is 4-36h, and hydrothermal temperature is 120~200 DEG C；
3) hydro-thermal reaction product is heat-treated；
Multiple filtering and washing is carried out to hydro-thermal reaction product, freeze-drying protects product after freeze-drying in inert gas
It is heat-treated under shield atmosphere, in the calcination process, heating rate is 2~20 DEG C/min, and holding temperature is 600~1000
DEG C, soaking time is 0.5~4h；After calcining under inert gas shielding atmosphere after sample natural cooling take out to get
To nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material.
Further, the time that is stirred to react of the step 1) is 0.2~3h, and whipping temp is 50~120 DEG C.
Further, the transition metal nitrate is in Fe(NO3)39H2O, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate
One kind.
Further, the volume ratio of the ethyl alcohol and deionized water is 1:(1~4)；
Further, the packing ratio of water heating kettle is 20%-80% when the step 2) hydro-thermal reaction.
Further, in the calcination process, inert gas flow velocity 0-300sccm.
A kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material are as lithium battery or sode cell
The application of negative electrode active material.
Advantageous effect of the invention is embodied in:
Invention provides the method for a kind of nitrogen sulphur codope three-dimensional grapheme and the compound universality of transient metal sulfide,
This method is suitable for preparing the composite material of iron sulfide, cobalt sulfide, nickel sulfide and doped graphene simultaneously；The present invention uses trimerization
Vulcanizing agent of the thiocyanic acid as the agent of nitrogen sulfur doping, the agent of three-dimensional grapheme soft mode and transition metal, using hydro-thermal-heat treatment method
Construction doped graphene in situ coats the composite construction of transient metal sulfide completely simultaneously, and metal sulfide is total to by nitrogen sulphur completely
Doped graphene cladding.The particle of the metal sulfide is controllable, and size is uniform, is uniformly wrapped up by graphene.The structure designs energy
Capacity fade problem caused by significantly solution transition metal sulfide is during storing up lithium or storage sodium because of volume expansion.Of the invention
Preparation method process safety is easy to operate, it can be achieved that volume production.Composite material prepared by this method can be used as lithium ion battery and sodium
Ion battery negative electrode active material.
Detailed description of the invention
Fig. 1 is scanning electron microscopy (SEM) photo of nitrogen sulphur codope three-dimensional grapheme prepared by embodiment 3
Specific embodiment
Present invention is further described in detail combined with specific embodiments below, but not as a limitation of the invention.
Embodiment 1
It disperses 0.1g graphene oxide in the mixed solution of 10ml deionized water and 10ml ethyl alcohol, then sequentially adds
0.06g melamine, 0.085g trithiocyanuric acid and 0.3g Fe(NO3)39H2O continue to stir 30min under conditions of 50 DEG C.
Then the solution is transferred in polytetrafluoroethyllining lining and carries out hydro-thermal reaction, 120 DEG C/8h of hydro-thermal reaction.By hydro-thermal reaction knot
The sample of beam carries out multiple filtering and washing, freeze-drying, then with the heating rate of 2 DEG C/min in the tube furnace of argon gas protection
650 DEG C of heat preservation 1h are warming up to, the flow velocity of argon gas is 0sccm in heat treatment process.
Embodiment 2
It disperses 0.1g graphene oxide in the mixed solution of 20ml deionized water and 10ml ethyl alcohol, then sequentially adds
0.12g melamine, 0.68g trithiocyanuric acid and 0.5g cabaltous nitrate hexahydrate continue to stir 100min under conditions of 70 DEG C.
Then the solution is transferred in polytetrafluoroethyllining lining and carries out hydro-thermal reaction, 150 DEG C/4h of hydro-thermal reaction.By hydro-thermal reaction knot
The sample of beam carries out multiple filtering and washing, freeze-drying, then with the heating rate of 5 DEG C/min in the tube furnace of argon gas protection
750 DEG C of heat preservation 1h are warming up to, the flow velocity of argon gas is 50sccm in heat treatment process.
Embodiment 3
It disperses 0.1g graphene oxide in the mixed solution of 30ml deionized water and 10ml ethyl alcohol, then sequentially adds
0.06g melamine, 0.17g trithiocyanuric acid and 0.8g Nickelous nitrate hexahydrate continue to stir 30min under conditions of 120 DEG C.
Then the solution is transferred in polytetrafluoroethyllining lining and carries out hydro-thermal reaction, 180 DEG C/8h of hydro-thermal reaction.By hydro-thermal reaction knot
The sample of beam carries out multiple filtering and washing, freeze-drying, then with the heating speed of 20 DEG C/min in the tube furnace of argon gas protection
Rate is warming up to 850 DEG C of heat preservation 3h, and the flow velocity of argon gas is 100sccm in heat treatment process.
Referring to Fig.1, Fig. 1 is the SEM photograph that the present embodiment prepares sample.Electricity is scanned with the S-4800 type of Japan Electronics Corporation
Sub- microscope (SEM) carries out morphology observation, can significantly see that graphene coats nickel sulfide nanoparticles completely.
Embodiment 4
It disperses 0.1g graphene oxide in the mixed solution of 40ml deionized water and 10ml ethyl alcohol, then sequentially adds
0.12g melamine, 0.32g trithiocyanuric acid and 1g cabaltous nitrate hexahydrate continue to stir 180min under conditions of 120 DEG C.
Then the solution is transferred in polytetrafluoroethyllining lining and carries out hydro-thermal reaction, the packing ratio of water heating kettle is 50%, hydro-thermal reaction
200℃/4h.The sample that hydro-thermal reaction is terminated carries out multiple filtering and washing, freeze-drying, then in the tube furnace of argon gas protection
In 650 DEG C of heat preservation 3h are warming up to the heating rate of 2 DEG C/min, the flow velocity of argon gas is 200sccm in heat treatment process.
Embodiment 5
It disperses 0.1g graphene oxide in the mixed solution of 40ml deionized water and 20ml ethyl alcohol, then sequentially adds
0.48g melamine, 0.64g trithiocyanuric acid and 1.2g Nickelous nitrate hexahydrate continue to stir 90min under conditions of 100 DEG C.
Then the solution is transferred in polytetrafluoroethyllining lining and carries out hydro-thermal reaction, the packing ratio of water heating kettle is 80%, hydro-thermal reaction
200℃/24h.The sample that hydro-thermal reaction is terminated carries out multiple filtering and washing, freeze-drying, then in the tubular type of argon gas protection
650 DEG C of heat preservation 4h are warming up to the heating rate of 15 DEG C/min in furnace, the flow velocity of argon gas is in heat treatment process
250sccm。
Embodiment 6
It disperses 0.1g graphene oxide in the mixed solution of 40ml deionized water and 40ml ethyl alcohol, then sequentially adds
0.36g melamine, 0.64g trithiocyanuric acid and 2.4g Fe(NO3)39H2O continue to stir 150min under conditions of 80 DEG C.
Then the solution is transferred in polytetrafluoroethyllining lining and carries out hydro-thermal reaction, the packing ratio of water heating kettle is 40%, hydro-thermal reaction
180℃/36h.The sample that hydro-thermal reaction is terminated carries out multiple filtering and washing, freeze-drying, then in the tubular type of argon gas protection
600 DEG C of heat preservation 3.5h are warming up to the heating rate of 10 DEG C/min in furnace, the flow velocity of argon gas is in heat treatment process
300sccm。
Embodiment 7
It disperses 0.1g graphene oxide in the mixed solution of 40ml deionized water and 20ml ethyl alcohol, then sequentially adds
0.36g melamine, 0.50g trithiocyanuric acid and 2.4g Fe(NO3)39H2O continue to stir 12min under conditions of 120 DEG C.
Then the solution is transferred in polytetrafluoroethyllining lining and carries out hydro-thermal reaction, the packing ratio of water heating kettle is 20%, hydro-thermal reaction
180℃/36h.The sample that hydro-thermal reaction is terminated carries out multiple filtering and washing, freeze-drying, then in the tubular type of argon gas protection
1000 DEG C of heat preservation 0.5h are warming up to the heating rate of 10 DEG C/min in furnace, the flow velocity of argon gas is in heat treatment process
300sccm is taken out after sample natural cooling under argon atmosphere to get nitrogen sulphur codope three-dimensional stone is arrived after calcining
Black alkene and transient metal sulfide composite material.
Finally it should be noted that: the above examples are only used to illustrate the technical scheme of the present invention rather than its limitations, to the greatest extent
Pipe is described the invention in detail referring to above-described embodiment, it should be understood by those ordinary skilled in the art that: still may be used
With modifications or equivalent substitutions are made to specific embodiments of the invention, and repaired without departing from any of spirit and scope of the invention
Change or equivalent replacement, should all cover in present claims range.
Claims (8)
1. the universality preparation method of a kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material, feature
Be the following steps are included:
1) graphene oxide, melamine, trithiocyanuric acid, transition metal nitrate are successively distributed to ethyl alcohol and deionized water
In the mixed solvent, be stirred to react sufficiently；
The graphene oxide, melamine, trithiocyanuric acid, transition metal nitrate mass ratio be 1:(0.6~4.8):
(0.85~6.8): (3~24)；
2) then stirring product is transferred in water heating kettle and carries out hydro-thermal reaction；
The time of the hydro-thermal reaction is 4-36h, and hydrothermal temperature is 120~200 DEG C；
3) hydro-thermal reaction product is heat-treated；
Multiple filtering and washing, freeze-drying, by product after freeze-drying in inert gas shielding gas are carried out to hydro-thermal reaction product
It is heat-treated under atmosphere, in the calcination process, heating rate is 2~20 DEG C/min, and holding temperature is 600~1000 DEG C, is protected
The warm time is 0.5~4h；It is taken out after sample natural cooling under inert gas shielding atmosphere to get nitrogen sulphur is arrived after calcining
Codope three-dimensional grapheme and transient metal sulfide composite material.
2. the universality of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material according to claim 1
Preparation method, it is characterised in that: the time that is stirred to react of the step 1) is 0.2~3h, and whipping temp is 50~120 DEG C.
3. the universality of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material according to claim 1
Preparation method, it is characterised in that: the transition metal nitrate is Fe(NO3)39H2O, Nickelous nitrate hexahydrate and six nitric hydrates
One of cobalt.
4. the universality of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material according to claim 1
Preparation method, it is characterised in that: the volume ratio of the ethyl alcohol and deionized water is 1:(1~4).
5. the universality of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material according to claim 1
Preparation method, it is characterised in that: the packing ratio of water heating kettle is 20%-80% when the step 2) hydro-thermal reaction.
6. the universality of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material according to claim 1
Preparation method, it is characterised in that: in the calcination process, inert gas flow velocity 0-300sccm.
7. the nitrogen sulphur codope three-dimensional grapheme and transition metal of a kind of method preparation of any one according to claim 1~6 vulcanize
Object composite material.
8. nitrogen sulphur codope three-dimensional grapheme described in a kind of claim 7 and transient metal sulfide composite material are as lithium battery
Or the application of sode cell negative electrode active material.
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| CN114583127A (en) * | 2022-02-28 | 2022-06-03 | 南京工业大学 | Method for preparing CoNi-S @3D-C nano composite material and modified battery diaphragm |
| CN115332525A (en) * | 2022-08-30 | 2022-11-11 | 陕西科技大学 | Nb-shaped alloy 2 O 5 /GO/VS 2 Composite material and method for producing the same |
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| CN115332525A (en) * | 2022-08-30 | 2022-11-11 | 陕西科技大学 | Nb-shaped alloy 2 O 5 /GO/VS 2 Composite material and method for producing the same |
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Application publication date: 20190628 |