CN116119728A - Laminated structure composite of graphene with low defect concentration and preparation method and application thereof - Google Patents

Laminated structure composite of graphene with low defect concentration and preparation method and application thereof Download PDF

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CN116119728A
CN116119728A CN202211670606.7A CN202211670606A CN116119728A CN 116119728 A CN116119728 A CN 116119728A CN 202211670606 A CN202211670606 A CN 202211670606A CN 116119728 A CN116119728 A CN 116119728A
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graphene
ldg
defect concentration
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郑灵浪
吴凌
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Jiangsu Carbon Technology Co ltd
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Abstract

The invention discloses a laminated structure compound of graphene with low defect concentration, and a preparation method and application thereof. The laminated structure composite of the graphene with low defect concentration is characterized in that: the defect concentration of the graphene surface is maintained at the level of the original graphite, and the active substance is clamped between graphene sheets with consistent orientation, so that a laminated structure is formed. The preparation method comprises the following steps: iron species are fixed by intercalation of linear fatty amine by taking a graphite interlayer compound of ferric trichloride as a raw material, and then a series of treatments such as oxidation/vulcanization/selenization/phosphating/carbonization are carried out to obtain a laminated structure compound of graphene with low defect concentration and active substances. The compound is used as an alkali metal ion battery cathode material, and the alkali metal ion battery has high initial cycle coulombic efficiency, high specific capacity and excellent multiplying power performance.

Description

Laminated structure composite of graphene with low defect concentration and preparation method and application thereof
Technical Field
The invention relates to a laminated structure compound of graphene with low defect concentration, and a preparation method and application thereof; belonging to the technical field of preparation of electrode materials of alkali metal ion batteries.
Background
Graphene has been reported by Konstantin Novoselov et al since 2004, because of its high conductivity, high specific surface area, high mechanical properties, and the like, which have been widely studied in many fields of contemporary science. At present, the main preparation methods of the graphene comprise two main types from bottom to top and from top to bottom, and the problems of complex process, high energy consumption and pollution, small size of the prepared graphene, uneven layer number and the like exist in any method. Graphene is applied to the field of electrochemistry, and serves as an electrochemical active substance on one hand, and is compounded with various electrochemical active substances (silicon, oxide, sulfide, selenide and the like) on the other hand, so that the conductivity and the cycling stability of the compound are improved.
The active substance is directly compounded with the graphene, but the almost perfect atomic structure of the surface of the graphene makes the chemical bonding between the active substance and the graphene difficult, so that the active substance and the graphene are only physically combined, the binding force is weak, and the active substance and the graphene are difficult to uniformly mix. The weak binding force can separate different components in the composite from each other in the electrochemical process, and the uneven electrode components can cause excessive local current, thereby inducing the generation of dendrites of the counter electrode, so that it is not desirable to directly compound the active material with graphene. Graphene Oxide (GO) is easy to interact with various metal cations or cationic groups because of containing rich oxygen-containing functional groups, and a compound of reduced graphene oxide (rGO) and oxides, sulfides, carbides and the like is obtained after reduction. The compound prepared by the method has strong binding force among various components and good electrochemical cycling stability, but rGO still has higher defect concentration even through high temperature or chemical reduction, and the first week coulomb efficiency of the compound is lower and is generally not more than 70 percent. Therefore, it is important to develop a composite of graphene with low defect concentration and various active substances and a preparation method thereof, and the method can reduce the defect concentration of the composite, improve the coulomb efficiency of the composite and ensure better cycle stability of the composite.
Disclosure of Invention
In view of the shortcomings of the prior art, a first object of the present invention is to provide a graphene and FeX with low defect concentration a (one or more of X= O, S, se, N, C, P, 0.ltoreq.a.ltoreq.3), denoted as LDG/FeX) a Characterized in that the defect concentration of the graphene surface is maintained at the level of original graphite, feX a Sandwiched between graphene layers with highly uniform orientation.
A second object of the present invention is to provide a process for preparing LDG/FeX a The preparation method has mild conditions and strong universality.
A third object of the present invention is to provide the low defect concentration graphene and FeX a Use of a laminate composite in alkali metal ion batteries (lithium ion batteries, sodium ion batteries and potassium ion batteries).
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a laminated composite (FeX) of graphene with low defect concentration and iron-containing active substances a ) Wherein X represents one or more of carbon, nitrogen, oxygen, sulfur, selenium and phosphorus, a is more than or equal to 0 and less than or equal to 3, and when a is more than or equal to 0, the elemental iron particles are positioned between graphene layers.
The invention provides graphene and FeX with low defect concentration a Preparation method of laminated composite comprises mixing graphite interlayer compound (FeCl) of ferric trichloride 3 Adding GICs into amine solution, heating to certain temperature for amine intercalation reaction, separating, cleaning, and drying to obtain amine intercalation compound (FeCl) 3 -An-GICs), then to FeCl 3 Carrying out heat treatment on the-An-GICs to obtain FeX a 。
The preparation method, feCl 3 GICs refer broadly to various pure or mixed phase iron trichloride graphite intercalation compounds, and for simplicity of understanding and description, the present invention selects pure phase first-order FeCl 3 -GICs（Ⅰ-FeCl 3 -GIC) and second order FeCl 3 -GICs（Ⅱ-FeCl 3 -GIC).
The amine substance is a compound conforming to the structural general formula C n H 2n+3 N (3.ltoreq.n.ltoreq.20) is a mono-linear aliphatic amine such as propylamine, butylamine, dodecylamine, octadecylamine, etc.; or conform to the general structural formula C n H 2n+4 N 2 (3.ltoreq.n.ltoreq.20) a dibasic linear aliphatic amine such as 1, 3-propanediamine, 1, 6-hexanediamine, etc.
I-FeCl in the reaction 3 -GIC or ii-FeCl 3 -the mass ratio of GIC to linear fatty amine is 1:5 to 1:100, the reaction temperature is 40-240 ℃, and the heat preservation time is 2-36 hours. The preferred mass ratio is 1: 20-1: 60, preferably the reaction temperature is 60 to 120 ℃, and the heat preservation time is 5 to 12 hours.
In the steps of separation, cleaning and drying, the product is separated by vacuum filtration or centrifugation, then is cleaned with 0.1M diluted hydrochloric acid and absolute ethyl alcohol for three times respectively, and is dried in a blast drying oven at 60 ℃ for 12 hours, thus obtaining the I-FeCl 3 -An-GIC or ii-FeCl 3 -An-GIC。
According to the preparation method, graphene with low defect concentration and FeX are prepared through heat treatment a The heat treatment method of the compound is more than or equal to 0 and less than or equal to 3, and the corresponding heat treatment conditions are different according to the difference of the element X;
in the preparation method, a=0 represents a laminated composite of graphene with low defect concentration and elemental iron particles. I-FeCl 3 -An-GIC is placed in a tube furnace in a reducing atmosphere, H 2 The flow rate of (2) is 5-200 SCCM, and the temperature is 0.1-30 ℃ for min -1 The temperature is raised to 400-700 ℃ and is kept for 1-24 hours, thus obtaining the LDG/Fe. Preferred H 2 The flow rate of the catalyst is 30-80 SCCM, the preferable heating rate is 1-3 ℃ for min -1 The preferable holding temperature is 500-600 ℃, and the preferable holding time is 6-12 hours.
In the preparation method, when X is oxygen element, I-FeCl 3 -An-GIC is placed in a muffle furnace at 0.1-30 ℃ for min -1 Heating to 200-500 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeO a (a is more than or equal to 0 and less than or equal to 3). The preferable heating rate is 1-3 ℃ for min -1 Preferably, the heat is preservedThe temperature is 350-450 ℃, and the preferable heat preservation time is 2-6 hours.
In the preparation method, when X is sulfur element, I-FeCl 3 Mixing An-GIC and sulfur source in certain proportion, and in inert gas protected tubular furnace at 0.1-30 deg.c for min -1 Heating to 400-800 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeS a (a is more than or equal to 0 and less than or equal to 3), and the flow of inert gas in the heat treatment process is 20-300 SCCM. The preferable heating rate is 1-5 ℃ for min -1 The preferable holding temperature is 450-600 ℃, the preferable holding time is 2-6 hours, and the preferable gas flow is 50-150 SCCM.
The sulfur source is selected from sulfur powder, thiourea and H 2 S, one or more of ammonium sulfide and thioacetamide;
the inert gas is selected from any one of nitrogen, helium, neon and argon;
the I-FeCl 3 -An-GIC and sulfur source mass ratio of 1:1 to 1:10, the preferred mass ratio is 1: 2-1: 5.
in the preparation method, when X is selenium element, I-FeCl 3 Mixing An-GIC and selenium source in certain proportion, and heating in a tube furnace at 0.1-30deg.C for 0.1-30 min -1 Heating to 400-800 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeSe a (a is more than or equal to 0 and less than or equal to 3), and the flow of inert gas in the heat treatment process is 20-300 SCCM. The preferable heating rate is 1-5 ℃ for min -1 The preferable holding temperature is 450-600 ℃, the preferable holding time is 2-6 hours, and the preferable gas flow is 50-150 SCCM.
The selenium source is selected from selenium powder, sodium selenite, and H 2 Se、SeS 2 One or more of the following;
the inert gas is selected from any one of nitrogen, helium, neon and argon;
the I-FeCl 3 -An-GIC and selenium source in a mass ratio of 1:5 to 1:50, preferably a mass ratio of 1:10 to 1:30.
in the preparation method, when X is phosphorus element, I-FeCl 3 Mixing An-GIC and phosphorus source in certain proportion, and in inert gas protected tubular furnace at 0.1-30 deg.c for min -1 Heating to 400-800 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeP a (a is more than or equal to 0 and less than or equal to 3), and the flow of inert gas in the heat treatment process is 20-300 SCCM. The preferable heating rate is 1-5 ℃ for min -1 The preferable holding temperature is 350-550 ℃, the preferable holding time is 2-6 hours, and the preferable gas flow is 50-150 SCCM.
The phosphorus source is selected from red phosphorus, sodium hypophosphite and H 3 One or more of P and ammonium phosphate;
the inert gas is selected from any one of nitrogen, helium, neon and argon;
the I-FeCl 3 -An-GIC and sulfur source mass ratio of 1:1 to 1:20, preferably the mass ratio is 1: 2-1: 10.
in the preparation method, when X is nitrogen element, I-FeCl is added 3 -An-GIC insertion of NH 3 In the tube furnace, the flow of ammonia is 5-100 SCCM, and the temperature is 0.1-30 ℃ for min -1 Heating to 400-800 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeN a (a is more than or equal to 0 and less than or equal to 3). The preferable heating rate is 1-5 ℃ for min -1 The preferable heat preservation temperature is 450-600 ℃, the preferable heat preservation time is 2-8 hours, and the preferable ammonia flow is 20-50 SCCM.
In the preparation method, when X is carbon element, I-FeCl 3 In a tube furnace protected by An-GIC inert gas, at 0.1-30 ℃ for min -1 Heating to 700-1100 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeC a (a is more than or equal to 0 and less than or equal to 3), and the flow of inert gas in the heat treatment process is 20-300 SCCM. The preferable heating rate is 5-10 ℃ for min -1 The preferable holding temperature is 800-1000 ℃, the preferable holding time is 4-10 hours, and the preferable gas flow is 50-150 SCCM.
In the preparation method, LDG/FeS a 、LDG/FeSe a 、LDG/FeP a Preparation of LDG/Fe, etc., or preparing LDG/FeO first a The material is then subjected to corresponding heat treatment to obtain the corresponding LDG/FeN a A complex.
The LDG/FeN of the invention x Uses of (1) LDG/FeN x The material is used as an alkali metal ion battery cathode material to be applied to an alkali metal ion battery.
The invention has the beneficial effects that: unlike the preparation process with graphene or graphene oxide as reaction material, the present invention uses FeCl directly 3 GICs are the reactants, I-FeCl 3 The GIC can be seen as having a layer of graphene between every two guest molecule layers, and FeCl 3 And the insertion of the linear fatty amine only changes the charge state of the graphene sheet, no additional defects are introduced, and the low defect concentration and high conductivity states of graphite and graphene are maintained. Due to FeCl 3 GICs are susceptible to decomposition by heat and cannot pass through FeCl 3 The GICs are directly subjected to heat treatment to obtain the corresponding LDG/FeX a A complex. Therefore, the invention utilizes amino and Fe 3+ Strong matching action between them, fe 3+ Anchoring between graphene sheets, and performing reduction/oxidation/vulcanization/selenization/phosphating to obtain a series of corresponding LDG/FeX a (one or more of X= O, S, se, N, C, P, 0.ltoreq.a.ltoreq.3). FeX (Fex) a Particles are clamped between graphene sheets with low defect concentration to form an alternate laminated structure, gaps between the sheets buffer the volume effect of active substances, prevent the active substances from directly contacting with electrolyte, and improve the cycle stability of the composite material; and the substrate with low concentration of defects and high conductivity reduces irreversible capacity introduced by the defects and improves the reversibility of active substances, so that the composite material shows high first-week coulomb efficiency.
In summary, the present invention provides graphene and FeX with low defect concentration a The composite with the laminated structure (a is more than or equal to 0 and less than or equal to 3) has simple preparation process and high repeatability, fully utilizes the high mechanical strength and high conductivity of the graphene material, and avoids the introduction of excessive defects. When the material is applied to alkali metal ion batteries, the material shows high first-week coulomb efficiency and higher first-week coulomb efficiencySpecific capacity and excellent cycle stability, and has a relatively strong application prospect.
Drawings
FIG. 1 is an LDG/Fe prepared in example 1 2 O 3 An XRD pattern of (b);
FIG. 2 is a LDG/FeS prepared in example 1 x An XRD pattern of (b);
FIG. 3 is a LDG/FeS prepared in example 1 x SEM images of (a);
FIG. 4 is a LDG/FeS prepared in example 1 x A TEM image of (a);
FIG. 5 is a LDG/FeS prepared in example 1 x Is a raman spectrum of (a);
FIG. 6 shows the LDG/Fe prepared in example 1 2 O 3 Electrode material at 100 mA g -1 A lithium storage cycle performance diagram under current density;
FIG. 7 is a LDG/FeS prepared in example 1 x Electrode material at 1000 mA g -1 A sodium storage cycle performance diagram under current density;
FIG. 8 is LDG/Fe prepared in example 2 7 S 8 An XRD pattern of (b);
FIG. 9 is a LDG/FeS prepared in example 2 x Electrode material at 1000 mA g -1 A sodium storage cycle performance diagram under current density;
fig. 10 is an XRD pattern of the composite material prepared in example 6.
Detailed Description
The following examples are intended to further illustrate the invention, but not to limit it.
Example 1:
300 mg I-FeCl is taken 3 GIC and 12 g dodecylamine, transferred to a 20 mL reaction flask, heated to 120 ℃ with an oil bath, stirred for 6 hours. After the reaction, separating the product by suction filtration, washing with 0.1. 0.1M dilute hydrochloric acid and absolute ethyl alcohol three times respectively, and drying in a blast drying oven at 60 ℃ for 12 hours to obtain I-FeCl 3 -An-GIC. Taking the dried product, and placing in a muffle furnace at 1 ℃ for min -1 Heating to 400 ℃ at the heating rate, and preserving heat for 2 hours to obtain LDG/Fe 2 O 3 . LDG/Fe 2 O 3 Mixing with sublimed sulfur according to 1: mass ratio of 5Mixing uniformly, and placing in a tubular furnace with argon flow of 100 SCCM at 3deg.C for min -1 Heating to 500 ℃ at a heating rate of (2) and preserving heat for 2 hours to obtain LDG/FeS x 。
XRD analysis was performed using a D8 Advance Davince X ray powder diffractometer from Bruker, germany, LDG/Fe 2 O 3 And LDG/FeS x The XRD patterns of (a) are shown in fig. 1 and fig. 2, respectively. It can be seen that LDG/Fe 2 O 3 Is Fe as the main phase composition 2 O 3 And contains a small amount of graphite; LDG/FeS x Is Fe as the main phase composition 7 S 8 And FeS 2 And contains a small amount of graphite. SEM analysis was performed using Hitachi S4800 cold field emission scanning electron microscope, and the results of the SEM characterization of LDG/are shown in FIG. 3, wherein the composite maintains the graphite flake structure as a whole, feS x The particles are sandwiched between graphene sheets. LDG/FeS was performed using a Tecnai F20 transmission electron microscope from FEI Co., USA x TEM analysis was performed, and the results are shown in FIG. 4, further demonstrating that graphene and FeS x And (3) forming a stacked structure. LDG/FeS x The raman spectrum of (a) shows (fig. 5) that the complex prepared is I D /I G The ratio of (2) is only 0.24, and the defect concentration is kept at a low level, which is equivalent to that of the original graphite for preparing the ferric trichloride graphite intercalation compound.
The prepared LDG/Fe 2 O 3 And LDG/FeS x The material is prepared from the following active substances: super P: cmc=8:1:1, and is uniformly mixed to prepare slurry, uniformly coated on copper foil, vacuum-dried at 80 ℃ for 12 h and then punched, and then the alkali metal ion battery is assembled, and the voltage range of electrochemical performance test is 0.01-3.0V. FIG. 6 shows the use of LDG/Fe 2 O 3 The lithium ion battery assembled by the electrode materials is 100 mAg -1 The initial reversible lithium storage capacity of the cycling performance chart is 587.2 mAh g -1 After 100 weeks of circulation, the reversible lithium storage capacity of the lithium ion battery rises to 827.0 mAh g -1 . FIG. 7 shows the use of LDG/FeS x The cycling performance diagram of the sodium ion battery assembled by the electrode material has the current density of 1000 mA g -1 Initial discharge capacity of 628.4 mAh g -1 Initial specific chargeThe amount is 579.4 mAh g -1 The first week coulomb efficiency is as high as 92.2%. The specific capacity after 300 weeks of circulation is 550.9 mAh g -1 Exhibits excellent cycle stability.
Example 2:
300 mg I-FeCl is taken 3 GIC and 12 g dodecylamine, transferred to a 20 mL reaction flask, heated to 120 ℃ with an oil bath, stirred for 6 hours. After the reaction, separating the product by suction filtration, washing with 0.1. 0.1M dilute hydrochloric acid and absolute ethyl alcohol three times respectively, and drying in a blast drying oven at 60 ℃ for 12 hours to obtain I-FeCl 3 -An-GIC. Mixing the dried product with sublimed sulfur according to a ratio of 1:5, mixing uniformly in a tubular furnace with argon flow of 100 SCCM at 5 ℃ for min -1 Heating to 500 ℃ at a heating rate of (2) and preserving heat for 2 hours to obtain LDG/Fe 7 S 8 . The XRD results of FIG. 8 show that the main phase composition of the prepared material is Fe 7 S 8 While containing a small amount of graphite phase. FIG. 9 is a graph of 1000 mA g for an assembled sodium ion battery -1 The initial discharge capacity was 707.5 mAh g in a cycle test under current density -1 Initial charge specific capacity of 623.2 mAh g -1 The coulomb efficiency at the first week is as high as 88.1%. The specific capacity after 300 weeks of circulation is 590.9 mAh g -1 Exhibits excellent cycle stability.
Example 3:
300 mg II-FeCl is taken 3 GIC and 8 g propylamine were transferred to a 20 mL reaction flask, heated to 90 ℃ using an oil bath, and stirred for 8 hours. After the reaction is finished, separating a product by suction filtration, respectively washing the product three times by 0.1M dilute hydrochloric acid and absolute ethyl alcohol, and then drying the product in a blast drying oven at 60 ℃ for 12 hours to obtain II-FeCl 3 -An-GIC. Mixing the dried product with sublimed sulfur according to a ratio of 1:4, mixing uniformly in a tubular furnace with argon flow of 100 SCCM at 3 ℃ for min -1 Heating to 500 ℃ at a heating rate of (2) and preserving heat for 2 hours to obtain LDG/Fe 7 S 8 。
Example 4:
300 mg I-FeCl is taken 3 -GIC and 14 g octadecylamine, transferring into 20 mL reaction flask, heating to 140deg.C with oil bath, stirringMix for 10 hours. After the reaction, separating the product by suction filtration, washing with 0.1. 0.1M dilute hydrochloric acid and absolute ethyl alcohol three times respectively, and drying in a blast drying oven at 60 ℃ for 12 hours to obtain I-FeCl 3 -An-GIC. Mixing the dried product with selenium powder according to the following weight ratio of 1:200, mixing uniformly in a tubular furnace with argon flow of 150 SCCM at 2 deg.C for min -1 Heating to 550 ℃ at a heating rate of (2) and preserving heat for 4 hours to obtain the LDG/FeSe x 。
Example 5:
300 mg I-FeCl is taken 3 GIC and 10 g hexamethylenediamine are transferred into a 20 mL reaction flask, heated to 95 ℃ using an oil bath, and stirred for 12 hours. After the reaction, separating the product by suction filtration, washing with 0.1. 0.1M dilute hydrochloric acid and absolute ethyl alcohol three times respectively, and drying in a blast drying oven at 60 ℃ for 12 hours to obtain I-FeCl 3 -An-GIC. Mixing the dried product with sodium hypophosphite according to a ratio of 1:20, mixing uniformly in a tubular furnace with argon flow of 50 SCCM at 5 ℃ for min -1 Heating to 450 ℃ at the heating rate, and preserving heat for 2 hours to obtain the LDG/FeP x 。
Example 6:
300 mg I-FeCl is taken 3 GIC and 6 g butylamine, transferred to a 20 mL reaction flask, heated to 90 ℃ using an oil bath, stirred for 12 hours. After the reaction, separating the product by suction filtration, washing with 0.1. 0.1M dilute hydrochloric acid and absolute ethyl alcohol three times respectively, and drying in a blast drying oven at 60 ℃ for 12 hours to obtain I-FeCl 3 -An-GIC. Placing the dried product into a nitrogen-protected tubular furnace, and placing the dried product into the tubular furnace with nitrogen flow of 200 SCCM at 10deg.C for min -1 Heating to 800 ℃ at a heating rate, and preserving heat for 12 hours to obtain the LDG/FeC x . As shown in FIG. 10, the materials produced are graphite, elemental iron and Fe 5 C 2 Is a mixed phase of (a) and (b).
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. A composite with laminated structure of low-defect-concentration graphene is prepared from low-defect-concentration graphene and active substance FeX a A composite of composition wherein one or more of x= O, S, se, N, C, P, 0.ltoreq.a.ltoreq.3, characterized in that the defect concentration of the graphene surface is maintained at the level of the original graphite, and FeX a Sandwiched between graphene layers with highly uniform orientation.
2. A method for preparing a low defect concentration graphene laminated structure composite according to claim 1, which is characterized in that: graphite intercalation compound of ferric trichloride (FeCl) 3 Adding GICs into amine solution, heating to certain temperature for amine intercalation reaction, separating, cleaning, and drying to obtain amine intercalation compound (FeCl) 3 -An-GICs), then to FeCl 3 Carrying out heat treatment on the-An-GICs to obtain FeX a 。
3. The method of stacking structured composites of low defect concentration graphene of claim 2, wherein:
the preparation method, feCl 3 GICs generally refer to various pure or mixed phase graphite intercalation compounds of ferric trichloride;
the amine substance is a compound conforming to the structural general formula C n H 2n+3 N (3.ltoreq.n.ltoreq.20) is a mono-linear aliphatic amine, such as propylamine, butylamine, dodecylamine, octadecylamine; or conform to the general structural formula C n H 2n+4 N 2 (3.ltoreq.n.ltoreq.20) a dibasic linear aliphatic amine such as 1, 3-propanediamine, 1, 6-hexanediamine.
4. The method of stacking structured composites of low defect concentration graphene of claim 2, wherein:
FeCl in the reaction 3 The mass ratio of GICs to linear fatty amines is 1:5 to 1:100, the reaction temperature is 40-240 ℃, and the heat preservation time is 2-to-up36 hours.
5. The method of stacking structured composites of low defect concentration graphene of claim 2, wherein:
fex production by heat treatment a The heat treatment method of the compound is more than or equal to 0 and less than or equal to 3, and the corresponding heat treatment conditions are different according to the difference of the element X;
in the preparation method, a=0 represents a laminated composite of graphene with low defect concentration and elemental iron particles, and the laminated composite is represented by H 2 Under the reducing atmosphere with the flow of 5-200 SCCM, the temperature is 0.1-30 ℃ for min -1 Heating to 400-700 ℃, and preserving heat for 1-24 hours to obtain LDG/Fe;
in the preparation method, when X is oxygen element, the temperature is 0.1-30 ℃ for min under the air atmosphere -1 Heating to 200-500 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeO a (0≤ a ≤3)；
In the preparation method, when X is nitrogen element, under the atmosphere of ammonia gas with the flow of 5-100 SCCM, the temperature is 0.1-30 ℃ for min -1 Heating to 400-800 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeN a (0≤ a ≤3)；
In the preparation method, when X is carbon element, the temperature is 0.1-30 ℃ for min under the atmosphere of inert gas flow of 20-300 SCCM -1 Heating to 700-1100 deg.C, and preserving heat for 1-24 hr to obtain LDG/FeC a (0≤ a ≤3)。
6. The method of stacking structured composites of low defect concentration graphene of claim 2, wherein:
in the preparation method, when X is sulfur, selenium and phosphorus, the dried product is mixed with sulfur source, selenium source or phosphorus source according to a certain proportion, and the mixture is stirred for 0.1-30 ℃ for min under the protection atmosphere of inert gas flow of 20-300 SCCM -1 The temperature is raised to 400-800 ℃ and is kept for 1-24 hours, and the graphene with low defect concentration and corresponding activity can be obtainedA layered composite of a sexual substance;
the inert gas is selected from any one of nitrogen, helium, neon and argon;
the sulfur source is selected from sulfur powder, thiourea and H 2 S, one or more of ammonium sulfide and thioacetamide; the mass ratio of the dried product to the sulfur source is 1:1 to 1:10;
the selenium source is selected from selenium powder, sodium selenite, and H 2 Se、SeS 2 One or more of the following; the mass ratio of the dried product to the selenium source is 1:5 to 1:50;
the phosphorus source is selected from red phosphorus, sodium hypophosphite and H 3 One or more of P and ammonium phosphate; the mass ratio of the dried product to the phosphorus source is 1:1 to 1:20.
7. the method of stacking structured composites of low defect concentration graphene of claim 2, wherein:
in the preparation method, LDG/FeS a 、LDG/FeSe a 、LDG/FeP a Preparing LDG/FeO, preparing LDG/Fe first a The material is then subjected to corresponding heat treatment to obtain the corresponding LDG/FeN a A complex.
8. The laminate structure composite of low-defect-concentration graphene according to claim 1 or 2, which is applied to an alkali metal ion battery as an alkali metal ion battery anode material.
CN202211670606.7A 2022-12-26 2022-12-26 Laminated structure composite of graphene with low defect concentration and preparation method and application thereof Pending CN116119728A (en)

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