CN108417811B - Carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material and synthesis method thereof - Google Patents

Carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material and synthesis method thereof Download PDF

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CN108417811B
CN108417811B CN201810252712.0A CN201810252712A CN108417811B CN 108417811 B CN108417811 B CN 108417811B CN 201810252712 A CN201810252712 A CN 201810252712A CN 108417811 B CN108417811 B CN 108417811B
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graphene
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ternary iron
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王艳
彭振凯
陈泽祥
张继君
闫欣雨
周智雨
吕慧芳
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University of Electronic Science and Technology of China
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Abstract

The invention provides a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material and a synthesis method thereof, and relates to the field of synthesis of micro-nano materials. The prepared composite material can form a complete conductive network under the dual actions of the graphene and the carbon coating layer; meanwhile, the air holes generated by the high-temperature heat treatment of the graphene surface and the potassium hydroxide enable each rod-shaped composite material to reserve enough channels for electrolyte solution immersion and ion transmission during electrochemical reaction.

Description

Carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material and synthesis method thereof
Technical Field
The invention relates to the field of micro-nano material synthesis, in particular to a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material and a synthesis method thereof.
Background
Graphene is the thinnest material discovered to date as a novel carbon material discovered only in 2004. The graphene shows excellent performances such as strong electrical conductivity, super-strong hardness and toughness, super-large specific surface area, specific thermal conductivity, high light transmittance and the like, so that the graphene becomes a very ideal matrix material. In order to further widen the application field of graphene, researchers compound graphene with a plurality of functional materials to prepare graphene-based composite materials with abundant structures, compositions and properties, and the composite materials can be widely applied to the fields of catalysis, sensing, photoelectricity, medicine, energy storage and the like.
Iron ore and manganese ore are abundant in natural reserves, various in compounds, low in price and harmless to the environment, and are always used as important research objects of electrochemical energy storage, and the combination of the iron ore, the manganese ore and graphene is always favored in the industry.
For example, in chinese patent (CN 106981636 a), iron acetylacetonate and acetone are used as solvents, and a solvothermal method is adopted, and after acetone is completely volatilized, FeS/RGO precursor is obtained by freeze drying; then thiourea is used as a sulfur source, FeS is loaded on the surface of graphene by adopting high-temperature vulcanization to synthesize a binary FeS/RGO composite material which is used as a negative electrode material of a sodium ion battery, FeS particles or sheets are anchored on the graphene sheets, and the conductivity of FeS is improved by using the graphene, so that the rate performance is improved, and good electrochemical performance is shown.
For example, in the chinese patent (CN 106159239 a), firstly, a three-dimensional columnar reduced graphene oxide is prepared by a hydrothermal process at 260 ℃ for 18-20 hours, and then manganese chloride, manganese sulfate, manganese nitrate and the like are used as manganese sources, thioacetamide and thiourea are used as sulfur sources, the three-dimensional reduced graphene oxide is used as a template, and a mixture of two of ethylene glycol, ethanol and isopropanol is used as a solvent; the method comprises the steps that groups on three-dimensional reduced graphene oxide adsorb positive and negative ions in a solution, manganese sulfide directly grows on the surface of graphene in situ through solvothermal synthesis to prepare manganese sulfide/graphene composite material nanoparticles, and the defect of poor stability caused by volume change of the manganese sulfide in the electrochemical reaction process is overcome through the prepared three-dimensional columnar reduced graphene oxide.
However, in the two technologies, as the electrochemical reaction of the material proceeds, FeS particles or sheets inevitably fall off from graphene sheets due to the intercalation and deintercalation process of sodium ions, which inevitably causes the volume expansion or pulverization of the material, and finally leads to the reduction of the electrochemical performance; according to a scanning electron microscope image of the composite material prepared by the latter, the size of the composite material is nano-scale particles, and the nano-particle composite material has a serious agglomeration phenomenon, so that the performance of the composite material at the later stage is obviously reduced.
Disclosure of Invention
The invention provides a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material and a synthesis method thereof, and aims to solve the technical problem that the electrochemical performance of the graphene composite material prepared by the existing preparation method is seriously reduced in the later use stage due to the physical properties of the material.
The purpose of the invention can be realized by the following technical scheme:
the utility model provides a carbon cladding bar-shaped structure ternary ferromanganese sulfide graphite alkene combined material, combined material's sandwich layer is bar-shaped structure's ternary ferromanganese sulfide, the outer cladding of ternary ferromanganese sulfide has graphite alkene layer, and connects through graphite alkene layer between the bar-shaped structure's ternary ferromanganese sulfide, and ternary ferromanganese sulfide corresponds the position cladding that is not clad by graphite alkene layer has the carbon coating, and combined material forms complete conducting network under the dual function of graphite alkene layer and carbon coating, the surface distribution on graphite alkene layer has the gas pocket of intercommunication ternary ferromanganese sulfide.
Preferably, the ternary iron-manganese sulfide with the rod-like structure is a nanorod, the length of the nanorod is 100nm-5 μm, and the width of the nanorod is 10nm-1 μm.
A synthetic method of a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material comprises the following steps:
1) mixing and uniformly stirring graphene and potassium hydroxide in a tube furnace, preparing graphene into a graphene solution at the high temperature of 800 ℃ through 350-plus-800 ℃, reacting the graphene with the potassium hydroxide at high temperature to generate potassium carbonate and hydrogen in the high-temperature reaction, further decomposing the potassium carbonate at high temperature to generate carbon dioxide, and generating air holes on the surface of the graphene after the two-step high-temperature reaction;
2) then, measuring ferric nitrate and manganese nitrate solutions, adding the graphene solution, and fully stirring for 10 min;
3) weighing ammonium fluoride solid, adding the ammonium fluoride solid into the mixed solution, and stirring for 10 min;
4) weighing urea, adding into the mixed solution, and stirring for 20 min;
5) transferring the liquid to a reaction kettle or other corresponding vessels for sealing and storing;
6) carrying out hydrothermal or water bath reaction at 90-200 ℃ for 5-24 h;
7) taking the precipitate to carry out filtration washing or centrifugal washing;
8) weighing deionized water and thioacetamide in the product obtained in the step 7), and fully stirring for 20 min;
9) transferring the liquid obtained in the step 8) to a reaction kettle or other corresponding vessels for sealed preservation;
10) carrying out hydrothermal or water bath reaction at 90-200 ℃ for 5-24 h;
11) taking the precipitate, and filtering and washing or centrifugally washing the precipitate to obtain a clean product, thus obtaining the rod-shaped structure ternary iron-manganese-sulfur graphene compound composite material;
12) at 300 ℃ and 800 ℃ N2And (3) sintering the carbon coating for 1-5h at a high temperature under the environment to obtain the carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material.
Preferably, the concentration of the graphene solution in the step 1) is 0.1-3 g/L.
Preferably, in the solution of ferric nitrate and manganese nitrate in the step 2), Fe3+Is Mn2+1-6 times of the total amount of the ferric nitrate, wherein the concentration of the ferric nitrate is 0.1-5 mol/L.
Preferably, in step 3), the ammonium fluoride concentration is maintained at 0.01-3mol/L after the ammonium fluoride solid is added to the mixed solution.
Preferably, in the step 4), the concentration of the urea is maintained at 0.01-5mol/L after the urea is added into the mixed solution.
Preferably, the material of the reaction kettle or other corresponding vessels in the steps 5) and 9) is polytetrafluoroethylene.
Preferably, in step 8), the concentration of thioacetamide is maintained between 0.01 and 1 mol/L.
Preferably, the carbon source for carbon coating in step 12) is one or more of glucose, phenolic resin, ethylene glycol.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the prepared composite material is rod-shaped, the rod-shaped composite material is partially wrapped by graphene, the rod-shaped composite materials are connected in series by the graphene, and the rod-shaped composite material which is not wrapped by the graphene is subjected to secondary high-temperature carbon wrapping on the surface, so that all the rod-shaped iron-manganese-sulfur graphene composite materials can form a complete conductive network under the dual actions of the graphene and the carbon wrapping layer; meanwhile, due to air holes generated by high-temperature heat treatment of the graphene surface and potassium hydroxide, each rod-shaped composite material can reserve enough channels for electrolyte solution immersion and ion transmission during electrochemical reaction;
2. due to the fact that air holes are formed in the surface of the graphene, transition metal iron manganese sulfide and porous graphene are compounded, the porous graphene wraps the rod-shaped iron manganese sulfide, and the rod-shaped materials are connected through the graphene to form a conductive structure, so that the defects of the metal sulfide in the aspects of diffusion and conductivity can be overcome by utilizing the large specific surface and the conductivity of the graphene, and the pseudo-capacitance property of the metal sulfide can be exerted; because the condition that the rodlike iron-manganese sulfide cannot be completely wrapped by the graphene exists, the rodlike iron-manganese sulfide graphene composite material is subjected to carbon coating treatment, the rodlike iron-manganese sulfide composite material which cannot be completely wrapped by the graphene is subjected to secondary coating, the rodlike iron-manganese sulfide composite materials are connected through the graphene, and a carbon layer is coated outside the composite material to connect all the materials, so that a complete conductive network is finally formed, the structure can effectively reduce the internal resistance of the composite material as an electroactive material, further improve the conductivity of the composite material, and accelerate the transfer of electrons in the formation of electrochemical reaction; on the other hand, the carbon coating plays a certain role in protecting the expansion or contraction of the electroactive material in the electrochemical test circulation process of the composite material, so that the structural stability of the composite material is enhanced, and the composite material has good circulation stability;
3. the formed graphene-coated and surface carbon layer-coated dual-protection structure effectively reduces the collapse of the extremely large specific surface area of the rod-shaped iron-manganese sulfide graphene composite material in the multiple reversible reaction processes and the agglomeration of an electroactive material, and is beneficial to improving the electrochemical cycle stability of the composite material;
4. the ternary iron-manganese-sulfur graphene composite material is prepared by a two-step hydrothermal method, and does not need to be dried after hydrothermal products in the first step and the second step are obtained through washing; the hydrothermal product of the first step is not dried, so that graphene shrinkage caused in the drying process of the product is avoided, and the phenomenon that the shrinkage of the graphene wraps the product of the first step to severely prevent the formation of ternary iron-manganese sulfide in the hydrothermal reaction process of the second step is avoided in the hydrothermal reaction process of the second step; and after washing, adding a proper amount of deionized water and a carbon source into the hydrothermal reaction product of the second step, transferring the hydrothermal reaction product into a quartz boat for high-temperature carbon coating, so that the graphene and the carbon coating layer, the graphene and the rod-shaped material, and the carbon coating layer and the rod-shaped material are tightly adhered to form a stable conductive network structure.
Drawings
FIG. 1 is a scanning electron microscope image of the morphology structure of a ternary iron manganese sulfide graphene composite material in embodiment 1;
FIG. 2 is a scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnSb graphene composite material in example 1;
FIG. 3 is a local scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnSb graphene composite material in example 1;
FIG. 4 is a scanning electron microscope image of the morphology structure of the ternary iron manganese sulfide graphene composite material in embodiment 2;
FIG. 5 is a scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnSb graphene composite material in example 2;
FIG. 6 is a local scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnSb graphene composite material in example 2;
FIG. 7 is a scanning electron microscope image of the morphology structure of the ternary iron manganese sulfide graphene composite material in example 3;
FIG. 8 is a scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnSb graphene composite material in example 3;
FIG. 9 is a local scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnS graphene composite in example 3;
FIG. 10 is a scanning electron microscope image of the morphology structure of the ternary iron manganese sulfide graphene composite material of embodiment 4;
FIG. 11 is a scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnSb graphene composite material in example 4;
FIG. 12 is a local scanning electron microscope image of the morphology structure of the carbon-coated ternary FeMnSb graphene composite material of embodiment 4;
FIG. 13 electrochemical cycling test performance curves for example 1 of the present invention;
FIG. 14 electrochemical cycling test performance curves for example 2 of the present invention;
FIG. 15 electrochemical cycling test performance curves for example 3 of the present invention;
FIG. 16 electrochemical cycling test performance curves for example 4 of the present invention.
Detailed Description
The present invention is further described with reference to the accompanying drawings and specific examples, in which the graphene solution is prepared by uniformly mixing with potassium hydroxide and performing a high-temperature treatment to generate pores on the surface of graphene.
The present invention will be described in detail with reference to fig. 1 to 16.
Example 1
A synthetic method of a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material comprises the following steps:
1) measuring 4ml of 0.5mol/L ferric nitrate solution, 1ml of 0.5mol/L manganese nitrate solution and 20ml of 1g/L graphene solution, preparing the graphene solution after carrying out heat treatment on the graphene and KOH at the high temperature of 500 ℃, and fully stirring for 10 min;
2) weighing 50mg of ammonium fluoride solid, adding into the mixed solution, and stirring for 10 min;
3) weighing 150mg of urea, adding the urea into the mixed solution, and stirring for 20 min;
4) transferring the liquid into a polytetrafluoroethylene lining of a 50ml reaction kettle for sealing and storing;
5) carrying out hydrothermal reaction at 180 ℃ for 10 h;
6) taking the precipitate to carry out filtration washing or centrifugal washing for a plurality of times;
7) adding 25ml of deionized water into the precipitate in the step 6), weighing 200mg of thioacetamide solid, adding the thioacetamide solid into the solution, and stirring for 20 min;
8) transferring the liquid in the step 7) to a polytetrafluoroethylene lining of a 50ml reaction kettle for sealed preservation;
9) carrying out hydrothermal reaction at 90 ℃ for 10 h;
10) taking the precipitate, and carrying out filtration washing or centrifugal washing for several times to obtain the rod-shaped structure ternary iron-manganese-sulfur graphene compound composite material, wherein the appearance structure of the composite material is shown in a scanning electron microscope picture of figure 1;
11) adding 20ml of deionized water into the precipitate obtained in the step 10), adding 10mg of ethylene glycol powder, uniformly dispersing by ultrasonic wave, and transferring the mixture into a high-temperature tubular furnace to be placed in an N mode2And sintering the carbon-coated rod-shaped structure for 1 hour under the protection of 450 ℃ to carry out carbon coating, thus obtaining the carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material, wherein the scanning electron microscope images of the morphology structure of the carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material are shown in figures 2 and 3, and the morphology of the carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material is looser compared with that of the rod-shaped structure ternary iron-manganese sulfide graphene compound composite material.
The carbon-coated rod-shaped structure-free ternary iron manganese sulfide graphene composite material prepared in the embodiment is shown in fig. 1, which shows that the length of a nanorod is about 650nm and the width of the nanorod is about 240nm, and fig. 2 and 3 are respectively a morphology diagram of the carbon-coated rod-shaped structure-free ternary iron manganese sulfide graphene composite material, wherein the morphology of the carbon-coated rod-shaped structure-free ternary iron manganese sulfide graphene composite material can be seen as a rod-shaped structure, and the rod-shaped structure-free ternary iron manganese sulfide graphene composite material is smaller in size and is staggered with each other after carbon coating is performed, so that the adhesion of the carbon-coated rod-; as shown in fig. 13, after the electrochemical cycling performance test, the specific capacity retention rate after 2000 cycles is 94.9%, and the specific capacity is only attenuated by 5.1%.
Example 2
A synthetic method of a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material comprises the following steps:
1) measuring 4ml of 1mol/L ferric nitrate solution, 4ml of 0.5mol/L manganese nitrate solution and 20ml of 1g/L graphene solution, preparing the graphene solution after the graphene is subjected to heat treatment with KOH at the high temperature of 500 ℃, and fully stirring for 10 min;
2) weighing 100mg of ammonium fluoride solid, adding the ammonium fluoride solid into the mixed solution, and stirring for 10 min;
3) weighing 150mg of urea, adding the urea into the mixed solution, and stirring for 20 min;
4) transferring the liquid into a polytetrafluoroethylene lining of a 50ml reaction kettle for sealing and storing;
5) carrying out hydrothermal reaction at 180 ℃ for 10 h;
6) taking the precipitate to carry out filtration washing or centrifugal washing for a plurality of times;
7) adding 25ml of deionized water into the precipitate in the step 6), weighing 350mg of thioacetamide solid, adding the thioacetamide solid into the solution, and stirring for 20 min;
8) transferring the liquid in the step 7) to a polytetrafluoroethylene lining of a 50ml reaction kettle for sealed preservation;
9) carrying out hydrothermal reaction at 100 ℃ for 10 h;
10) taking the precipitate, and carrying out filtration washing or centrifugal washing for several times to obtain the rod-shaped structure ternary iron-manganese-sulfur graphene compound composite material, wherein the appearance structure of the composite material is shown in a scanning electron microscope image in figure 4;
11) adding 20ml of deionized water into the precipitate obtained in the step 10), adding 15mg of glucose powder, uniformly dispersing by ultrasonic, and transferring to a high-temperature tubular typeIn furnace in N2And sintering the carbon-coated rod-shaped structure for 3 hours under the protection of 500 ℃ to carry out carbon coating, thus obtaining the carbon-coated rod-shaped structure ternary iron manganese sulfide graphene composite material, wherein the scanning electron microscope images of the morphology structure of the carbon-coated rod-shaped structure ternary iron manganese sulfide graphene composite material are shown in fig. 5 and 6, and the carbon-coated rod-shaped structure ternary iron manganese sulfide graphene composite material is more uniformly distributed compared with the rod-shaped structure ternary iron manganese sulfide graphene compound composite material.
The carbon-free coated rod-shaped structure ternary iron-manganese sulfide graphene composite material prepared in the embodiment is shown in fig. 4, and shows that the length of the nanorod is about 1 μm, and the width of the nanorod is about 200 nm. Fig. 5 and 6 are morphology diagrams of the carbon-coated rod-shaped structure ternary fe-mn-s-graphene composite material, and it can be seen that the morphology of the carbon-coated rod-shaped structure ternary fe-mn-s-graphene composite material is a rod-shaped structure, but after the carbon coating, the rod-shaped structures are smaller in size and are staggered with each other, so that the adhesion with graphene is firmer, and the porosity between the composite materials is increased; as shown in fig. 14, after the electrochemical cycling performance test, the specific capacity retention rate is 91.4% and the specific capacity attenuation rate is 8.6% after 2000 cycles.
Example 3
A synthetic method of a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material comprises the following steps:
1) measuring 4ml of 3mol/L ferric nitrate solution, 4ml of 1mol/L manganese nitrate solution and 15ml of 2g/L graphene solution, preparing the graphene solution after carrying out heat treatment on graphene and KOH at the high temperature of 800 ℃, and fully stirring for 10 min;
2) weighing 100mg of ammonium fluoride solid, adding the ammonium fluoride solid into the mixed solution, and stirring for 10 min;
3) weighing 300mg of urea, adding into the mixed solution, and stirring for 20 min;
4) transferring the liquid into a polytetrafluoroethylene lining of a 50ml reaction kettle for sealing and storing;
5) carrying out hydrothermal reaction at 120 ℃ for 10 h;
6) taking the precipitate to carry out filtration washing or centrifugal washing for a plurality of times;
7) adding 25ml of deionized water into the precipitate in the step 6), weighing 500mg of thioacetamide solid, adding the thioacetamide solid into the solution, and stirring for 20 min;
8) transferring the liquid in the step 7) to a polytetrafluoroethylene lining of a 50ml reaction kettle for sealed preservation;
9) carrying out hydrothermal reaction at 100 ℃ for 10 h;
10) taking the precipitate, and carrying out filtration washing or centrifugal washing for several times to obtain the rod-shaped structure ternary iron-manganese-sulfur graphene compound composite material, wherein the appearance structure of the composite material is shown in a scanning electron microscope image in figure 7;
11) adding 20ml of deionized water into the precipitate obtained in the step 10), adding 20mg of glucose powder, uniformly dispersing by ultrasonic wave, and transferring the mixture into a high-temperature tubular furnace to be placed in an N mode2And sintering at 550 ℃ for 3h under protection for carbon coating to obtain the carbon-coated rod-like structure ternary iron-manganese sulfide graphene composite material, wherein the scanning electron microscope images of the morphology structure of the carbon-coated rod-like structure ternary iron-manganese sulfide graphene composite material are shown in fig. 8 and 9, so that the morphology of the carbon-coated rod-like structure ternary iron-manganese sulfide graphene composite material is more uniform compared with that of the rod-like structure ternary iron-manganese sulfide graphene compound composite material.
The carbon-coated rod-shaped structure-free ternary iron-manganese-sulfide graphene composite material prepared in this embodiment is shown in fig. 7, which shows that the length of a nanorod is about 667nm, and the width of the nanorod is about 133nm, and fig. 8 and 9 are respectively a morphology diagram of a carbon-coated rod-shaped structure-free ternary iron-manganese-sulfide graphene composite material, and it can be seen that the morphology of the carbon-coated rod-shaped structure-free ternary iron-manganese-sulfide graphene composite material is a rod-shaped structure, but after carbon coating, the rod-shaped materials are smaller in size and are staggered with each other, so that adhesion with graphene is firmer, and the porosity; as shown in fig. 15, after the electrochemical cycling performance test, the specific capacity retention rate after 2000 cycles is 92.1%, and the specific capacity is attenuated by 7.9%.
Example 4
A synthetic method of a carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material comprises the following steps:
1) measuring 4ml of 0.5mol/L ferric nitrate solution, 1ml of 0.5mol/L manganese nitrate solution and 20ml of 1g/L graphene solution, preparing the graphene solution after carrying out heat treatment on graphene and KOH at the high temperature of 800 ℃, and fully stirring for 10 min;
2) weighing 2.5mmol of ammonium fluoride solid, adding into the mixed solution, and stirring for 10 min;
3) weighing 2.5mmol of urea, adding into the mixed solution, and stirring for 20 min;
4) transferring the liquid into a polytetrafluoroethylene lining of a 50ml reaction kettle for sealing and storing;
5) carrying out hydrothermal reaction at 120 ℃ for 24 hours;
6) taking the precipitate to carry out filtration washing or centrifugal washing for a plurality of times;
7) adding 25ml of deionized water into the precipitate in the step 6), weighing 2mmol of thioacetamide solid, adding the thioacetamide solid into the solution, and stirring for 20 min;
8) transferring the liquid in the step 7) to a polytetrafluoroethylene lining of a 50ml reaction kettle for sealed preservation;
9) carrying out hydrothermal reaction at 100 ℃ for 10 h;
10) taking the precipitate, and carrying out filtration washing or centrifugal washing for several times to obtain the rod-shaped structure ternary iron-manganese-sulfur graphene compound composite material, wherein the appearance structure of the composite material is shown in a scanning electron microscope image in FIG. 10;
11) adding 20ml of deionized water into the precipitate obtained in the step 10), adding 25mg of ethylene glycol powder, uniformly dispersing by ultrasonic wave, and transferring the mixture into a high-temperature tubular furnace to be placed in an N mode2And sintering at 750 ℃ for 3h under protection for carbon coating to obtain the carbon-coated rod-like structure ternary iron-manganese sulfide graphene composite material, wherein the scanning electron microscope images of the morphology structure of the carbon-coated rod-like structure ternary iron-manganese sulfide graphene composite material are shown in fig. 11 and 12, and the morphology of the carbon-coated rod-like structure ternary iron-manganese sulfide graphene composite material is looser compared with that of the rod-like structure ternary iron-manganese sulfide graphene compound composite material.
The carbon-coated rod-shaped structure-free ternary iron manganese sulfide graphene composite material prepared in this embodiment is shown in fig. 10, which shows that the length of the nanorod is about 760nm and the width of the nanorod is about 120nm, and fig. 11 and 12 are respectively a morphology diagram of the carbon-coated rod-shaped structure-free ternary iron manganese sulfide graphene composite material, and it can be seen that the nanorod is in a rod-shaped structure in morphology, but after the carbon coating, the rod-shaped materials are smaller in size and are staggered with each other, so that the adhesion with graphene is firmer, and the porosity degree between the composite materials is increased; as shown in fig. 16, after the electrochemical cycling performance test, the specific capacity retention rate after 2000 cycles is 91.6%, and only 8.4% of the specific capacity is attenuated.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, the scope of the present invention is defined by the appended claims, and all structural changes that can be made by using the contents of the description and the drawings of the present invention are intended to be embraced therein.

Claims (9)

1. The carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material is characterized in that: the core layer of the composite material is a bar-shaped ternary iron-manganese sulfide, a graphene layer is coated outside the ternary iron-manganese sulfide, the bar-shaped ternary iron-manganese sulfide is connected through the graphene layer, the ternary iron-manganese sulfide is coated with a carbon coating layer at a position which is not coated by the graphene layer, the composite material forms a complete conductive network under the dual actions of the graphene layer and the carbon coating layer, and air holes communicated with the ternary iron-manganese sulfide are distributed on the surface of the graphene layer;
the synthesis method of the carbon-coated rod-shaped structure ternary iron-manganese sulfide graphene composite material comprises the following steps:
1) mixing and stirring graphene and potassium hydroxide uniformly in a tube furnace, and reacting at the high temperature of 350-800 ℃ to prepare graphene solution;
2) then, measuring ferric nitrate and manganese nitrate solutions, adding the graphene solution, and fully stirring for 10 min;
3) weighing ammonium fluoride solid, adding the ammonium fluoride solid into the mixed solution, and stirring for 10 min;
4) weighing urea, adding into the mixed solution, and stirring for 20 min;
5) transferring the mixed solution obtained in the step 4) to a reaction kettle or other corresponding vessels for sealed storage;
6) carrying out hydrothermal or water bath reaction at 90-200 ℃ for 5-24 h;
7) taking the precipitate to carry out filtration washing or centrifugal washing;
8) weighing deionized water and thioacetamide in the product obtained in the step 7), and fully stirring for 20 min;
9) transferring the liquid obtained in the step 8) to a reaction kettle or other corresponding vessels for sealed preservation;
10) carrying out hydrothermal or water bath reaction at 90-200 ℃ for 5-24 h;
11) taking the precipitate, and filtering and washing or centrifugally washing the precipitate to obtain a clean product, thus obtaining the rod-shaped structure ternary iron-manganese-sulfur graphene compound composite material;
12) and sintering the carbon coating at the temperature of 300 plus 800 ℃ and N2 for 1-5h to obtain the carbon-coated rod-like structure ternary iron manganese sulfide graphene composite material.
2. The carbon-coated rod-like structure ternary iron-manganese-sulfide graphene composite material of claim 1, wherein: the ternary iron-manganese sulfide with the rod-shaped structure is a nanorod, the length of the nanorod is 100nm-5 mu m, and the width of the nanorod is 10nm-1 mu m.
3. The method for synthesizing the carbon-coated rod-like structure ternary iron-manganese-sulfide graphene composite material according to claim 1, wherein the method comprises the following steps: the concentration of the graphene solution in the step 1) is 0.1-3 g/L.
4. The method for synthesizing the carbon-coated rod-like structure ternary iron-manganese-sulfide graphene composite material according to claim 1, wherein the method comprises the following steps: in the solution of the ferric nitrate and the manganese nitrate in the step 2), the molar weight of Fe3+ is 1-6 times that of Mn2+, wherein the concentration of the ferric nitrate is 0.1-5 mol/L.
5. The method for synthesizing the carbon-coated rod-like structure ternary iron-manganese-sulfide graphene composite material according to claim 1, wherein the method comprises the following steps: in the step 3), after the ammonium fluoride solid is added into the mixed solution, the concentration of the ammonium fluoride is kept between 0.01 and 3 mol/L.
6. The method for synthesizing the carbon-coated rod-like structure ternary iron-manganese-sulfide graphene composite material according to claim 1, wherein the method comprises the following steps: in the step 4), after the urea is added into the mixed solution, the concentration of the urea is kept between 0.01 and 5 mol/L.
7. The method for synthesizing the carbon-coated rod-like structure ternary iron-manganese-sulfide graphene composite material according to claim 1, wherein the method comprises the following steps: and 5) step 9) the reaction kettle or other corresponding vessels are made of polytetrafluoroethylene.
8. The method for synthesizing the carbon-coated rod-like structure ternary iron-manganese-sulfide graphene composite material according to claim 1, wherein the method comprises the following steps: in the step 8), the concentration of the thioacetamide is kept between 0.01 and 1 mol/L.
9. The method for synthesizing the carbon-coated rod-like structure ternary iron-manganese sulfide graphene composite material according to claim 1, wherein the method comprises the following steps: the carbon source used for carbon coating in the step 12) is one or more of glucose, phenolic resin and ethylene glycol.
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