CN114899365A - Phosphate ion doped SnS crystal/nitrogen doped rGO composite material and preparation method and application thereof - Google Patents

Phosphate ion doped SnS crystal/nitrogen doped rGO composite material and preparation method and application thereof Download PDF

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CN114899365A
CN114899365A CN202210194106.4A CN202210194106A CN114899365A CN 114899365 A CN114899365 A CN 114899365A CN 202210194106 A CN202210194106 A CN 202210194106A CN 114899365 A CN114899365 A CN 114899365A
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CN114899365B (en
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李犁
王颖
王淑兰
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Northeastern University China
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    • 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
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a phosphate ion doped SnS crystal/nitrogen doped rGO composite material and a preparation method and application thereof, belonging to the field of battery materials. The composite material consists of a nitrogen-doped rGO nano sheet and a phosphate ion-doped SnS nano sheet deposited on the surface of the nitrogen-doped rGO nano sheet, wherein the doped SnS crystal has a SnS crystal structure, namely PO 4 3‑ And Sn and O, O are bonded with P through covalent bonds by being embedded between SnS crystal lattices. The phytic acid is injected into the SnS crystal lattice, so that the intrinsic electronic conductivity of the SnS is obviously improved, and the problem of volume expansion of the SnS crystal caused by the embedding/removing of sodium ions is effectively solved.

Description

Phosphate ion doped SnS crystal/nitrogen doped rGO composite material and preparation method and application thereof
Technical Field
The invention relates to a phosphate ion doped SnS crystal/nitrogen doped rGO composite material and a preparation method and application thereof, belonging to the field of battery materials.
Background
The method has important significance for developing high-efficiency energy storage technology as a powerful support for renewable and sustainable energy. In order to alleviate the pressure caused by energy shortage and environmental deterioration, the utilization of clean renewable energy has become a necessary requirement for the global energy revolution and green development. The utilization of non-petrochemical clean new energy is greatly promoted, the efficiency of an energy storage system is improved, and the clean low-carbon development is realized. Among them, the secondary battery has met with a new development opportunity in a new round of energy revolution and energy structure upgrade as a main energy storage technology that can convert energy in other forms into electric energy and store it in the form of chemical energy. Sodium Ion Batteries (SIBs) have attracted much attention as a new generation of alkali metal ion batteries due to their abundant natural reserves and low cost effectiveness. Numerous studies have shown that the key to the electrochemical performance of batteries is the energy storage density and power density, which are largely dependent on the performance of the positive and negative electrode materials.
Among the different anode material choices, metal sulfides with high theoretical capacity and energy density are considered promising candidates for the development of high capacity and long lifetime SIBs. As a representative of metal sulfides, SnS having a unique layered structure, in combination with its particular physicochemical properties, including significant semiconductor properties, strong ferroelectric/piezoelectric properties in the structural plane, etc., provides an ideal platform for high-performance negative electrode research. Currently, the major problems with using SnS in SIBs remain their severe volume expansion and extremely poor electronic conductivity. During the sodium ion intercalation/deintercalation, the layered structure of SnS is heavily stacked, inducing irreversible phase transition and causing pulverization of the active material, thereby causing continuous occurrence of side reactions and deterioration of cycle properties.
Existing methods can improve electron/ion conductivity by external modification, but they are not effective in improving intrinsic conductivity of SnS. To address this problem, non-metallic heteroatom doping (N, C, O and P) has been shown to be an improvement in metal sulfide intrinsic conductivity and electricityA very efficient method of ion/ion mobility. In addition to non-metallic heteroatom doping, doping or intercalation of macromolecules or non-metallic ionic groups is also an effective way to induce lattice distortion. The doping or embedding of the ionic groups is proved to adjust the energy band structure to improve the conductivity and provide more active sites for the metal sulfide, thereby improving the electrochemical performance. Recently, phosphate ion (PO) 4 3- ) Due to doping thereof
Figure RE-GDA0003691734590000021
Has attracted a great deal of attention due to the large ionic radius and high electronegativity. On one hand, phosphate ions with large ionic radius can be used as doping sites to be introduced into the interlayer, so that the interlayer spacing of sulfide is increased, and Na is promoted + The transfer of (2). On the other hand, phosphate ions having high electronegativity may substitute for the S atom of the sulfide to form an O-metal bond, thereby improving the intrinsic conductivity of the metal sulfide and facilitating electron transfer. Thus, through PO 4 3- It is reasonable that the doping further improves the electrochemical performance of the SnS.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for improving the intrinsic conductivity of SnS, which is applied to a negative electrode material of a sodium ion battery. Meanwhile, compared with an unsafe phosphorus source, the ecological environment-friendly nontoxic biomass phosphorus source has more attraction, and the high-efficiency stable sodium ion battery cathode material is prepared in a safer and faster synthetic process.
In order to solve the problems in the prior art, the invention provides a method for implanting phosphate ions into SnS crystals to realize high-efficiency and stable sodium storage, and PO is prepared by one-step hydrothermal method 4 3- Doped SnS while achieving high pyridine nitrogen doping in the carbon matrix material. PO (PO) 4 3- Directional doping is constructed in the SnS crystal in a Sn-O-P covalent bond form, so that the Sn-O-P covalent bond form has definite doping sites, the lattice spacing of the SnS is effectively increased, and the electronic conductivity of the SnS is obviously improved. With the aid of controlled advantageous heteroatom doping, the intrinsic reaction kinetics of SnS can be greatly enhanced and lead to an increase in capacity and energy/power densityAnd good cycle stability. Introduction of PO by Biomass phosphorus source 4 3- The group can realize the modification of a layered structure and the efficient and stable sodium ion battery cathode material. This concept is not limited to SnS, but may be extended to a wider range of layered structures and transition metal compounds. The phytic acid is used as a phosphorus source, so that the biomass material is effectively utilized, and the research concept is green and environment-friendly. The whole preparation process has the advantages of simple steps, mild conditions, good stability, low energy consumption, small influence on the environment and remarkable advantages.
In order to achieve the purpose, the invention adopts the main technical scheme that:
the composite material consists of a nitrogen-doped rGO (reduced graphene oxide) nanosheet and a phosphate ion-doped SnS nanosheet deposited on the surface of the nanosheet, wherein the doped SnS crystal has a SnS crystal structure, and PO is in a structure of PO 4 3- Embedded between SnS crystal lattice layers, Sn and O, O are covalently bonded with P.
The phosphate ion doped SnS crystal/nitrogen doped rGO composite material is marked as PO in the text 4 -an SnS/NG composite.
In the SnS nanosheet doped with phosphate radical ions, P is represented as PO 4 3- In the form of a composite system comprising Sn-O-P covalent bonds, i.e. PO 4 3- Is bonded with SnS in a covalent bond mode and exists in the crystal lattices.
According to the phosphate ion doped SnS crystal/nitrogen doped rGO composite material, the size of the phosphate ion doped SnS nanosheet is 10-35 nm. Further, the thickness of the SnS nanosheet is 9 nm.
In the SnS crystal doped with phosphate radical ions, the PO is 4 3- The doping amount is 1.0-4.0% by atomic percentage of phosphorus atoms in the composite material, and is preferably 3.32%.
In the nitrogen-doped rGO nanosheet, the doped nitrogen exists in the forms of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, and mainly is pyridine nitrogen, and the pyridine nitrogen is beneficial to improving the adsorption effect of an electrode material on sodium ions.
Preferably, the nitrogen-doped rGO nanoplates have a pyridine, pyrrole and graphite nitrogen content of 67.82%, 26.58% and 5.6%.
The invention also aims to provide a preparation method of the SnS crystal/nitrogen-doped rGO composite material doped with phosphate ions.
A preparation method of a phosphate ion doped SnS crystal/nitrogen doped rGO composite material comprises the steps of carrying out hydrothermal reaction on tin salt, a sulfur source, a graphene oxide aqueous solution, melamine and phytic acid serving as raw materials, collecting precipitates after the reaction is finished, and carrying out freeze drying to obtain a composite material precursor; and (3) roasting the composite material precursor in an inert atmosphere to prepare the SnS crystal/nitrogen-doped rGO composite material doped with phosphate ions.
In the technical scheme, the biomass phytic acid is adopted for selecting the phosphorus source in the reaction system. Phytic acid, also known as phytic acid, is found mainly in the seeds, roots, stems and stalks of plants. The phytic acid contains 6 phosphate groups which are symmetrical to each other, and the symmetrical structure has good conductivity. And the phosphate group and most of metal cations have strong coordination effect, and a phytic acid metal cross-linked structure is easily formed. Melamine was chosen as nitrogen-doped nitrogen source. The hydrogen bond between the phytic acid and the melamine effectively regulates and controls the proportion of different nitrogen species in nitrogen doping. PO with large ionic radius 4 3- Introducing SnS interlamination as doping site to increase sulfide interlamination distance, thereby promoting Na + The transfer of (2).
Preferably, the temperature of the hydrothermal reaction is 160-180 ℃, and the reaction time is 10-12 h.
Preferably, the tin salt, the sulphur source and the tin atoms in the melamine: sulfur atom: the molar ratio of melamine is 2:2: 5; the ratio of the phytic acid to the melamine is 0.5-2 mL:5 mol; the volume ratio of the phytic acid to the graphene oxide aqueous solution is 0.5-2: 65, wherein the concentration of the graphene oxide aqueous solution is 2mg mL -1 。
Preferably, the composite material precursor is placed in a nitrogen or argon atmosphere and roasted at 400-600 ℃ for 2-6 h to obtain the SnS crystal doped with phosphate ions.
Preferably, the tin salt of the invention is SnCl 4 ·5H 2 O、SnCl 2 . The sulfur source is thiourea, thioacetamide and sodium sulfide.
The invention further aims to provide application of the phosphate ion doped SnS crystal/nitrogen doped rGO composite material as a sodium ion battery negative electrode material.
The beneficial effects of the invention are:
(1) aiming at the problems of serious volume expansion and poor electronic conductivity of SnS, the phytic acid is injected into the SnS crystal lattice, so that the intrinsic electronic conductivity of the SnS is obviously improved, and the volume expansion problem of the SnS crystal caused by the insertion/extraction of sodium ions is effectively relieved.
(2) Preparation of PO by one-step hydrothermal process 4 3- Doped SnS while achieving high pyridine nitrogen doping in the carbon matrix material. The existence of phytic acid in a system modifies the inherent crystal structure of SnS and influences the electronic/ionic state, band gap and crystal structure stability for sodium ion storage. PO (PO) 4 3- The implantation of (a) results in charge redistribution of the SnS crystal unit cell, in particular charge distortion on surface atoms and promotes electron transport. In addition, the phytic acid has another effect of regulating and controlling a nitrogen-doped configuration, so that the content of pyridine nitrogen in a carbon matrix is 67.82%, the electronic conductivity and the chemical activity are effectively improved, and the electron/Na is improved + And provide greater capacity.
(3) The invention has no expensive raw materials, and accords with the concept of low cost of the sodium-ion battery. The preparation process takes phytic acid as a phosphorus source, does not use toxic solvents and is environment-friendly. The biomass material is effectively utilized, and the research concept is green and environment-friendly.
(4) The negative electrode material PO of the sodium-ion battery prepared by the method 4 SnS/NG, with excellent specific capacity and ultra-long cycle life (at 2A g) -1 The specific capacity is kept at 186.4mA h g after 10000 cycles of circulation under the current density of (1) -1 The rate of capacity decay per cycle is only0.0028 percent) and meets the performance requirement of the cathode material of the sodium-ion battery.
(5) The invention obtains PO by roasting the precursor after a one-step hydrothermal method 4 The SnS/NG composite material has the advantages of simple process, mild operation conditions, good stability, low energy consumption, small influence on the environment and commercial production.
The invention uses PO 4 3- The directional doping (Sn-O-P covalent bond) is constructed by implanting the SnS crystal, has a definite doping part, effectively increases the lattice spacing of the SnS and obviously improves the electronic conductivity of the SnS. With the aid of controlled, favorable heteroatom doping, the intrinsic reaction kinetics of the SnS can be greatly enhanced and lead to an increase in capacity and energy/power density and good cycling stability. Introduction of PO by Biomass phosphorus source 4 3- The group can realize the modification of a layered structure and the efficient and stable sodium ion battery cathode material. The concept is not limited to SnS, but also can be expanded to a wider layered structure and a transition metal compound, and provides a new research visual angle for the cathode material of the sodium-ion battery.
Drawings
FIGS. 1(a) to (h) show PO products of example 1 4 -a topography profile of the SnS/NG composite under different magnification; FIG. 1(i) is PO of example 1 4 -SnS/NG composite energy dispersive X-ray spectrogram.
FIG. 2 is PO of example 1 4 -XRD pattern of SnS/NG composite.
FIGS. 3(a) to (f) show PO products of example 2 4 XPS plots of SnS/NG composites.
FIGS. 4(a) - (e) are PO of example 3 4 -sodium storage properties of the SnS/NG composite.
FIGS. 5(a) - (e) are PO of example 4 4 And (4) an electrochemical performance curve tested after the sodium ion battery cathode made of the SnS/NG composite material is assembled into a sodium ion full battery.
FIG. 6 is a PO of the present invention 4 -schematic view of the microstructure of the SnS/NG composite.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The basic idea of the invention is to use 0.5-2 mL phytic acid, 2mmol tin salt (calculated by tin atom), 2mmol sulfur source (calculated by sulfur atom), 5mmol melamine and 65mL (2mg mL) -1 ) Graphene Oxide (GO) aqueous solution is used as a raw material, a simple preparation process is adopted to prepare the SnS doped with phosphate radical and rGO doped with high pyridine nitrogen, and the product is used for preparing a sodium ion battery cathode material, so that the sodium ion battery can obtain excellent charge-discharge specific capacity and ideal cycling stability.
The invention provides a preparation method of a SnS crystal/nitrogen-doped rGO composite material doped with phosphate ions, which comprises the following steps:
s1: one-step hydrothermal method for preparing phosphate radical ions (PO) deposited and grown on nitrogen-doped reduced graphene oxide substrate 4 3- ) Implanting an SnS crystal (note: PO (PO) 4 SnS/NG) carrying out hydrothermal reaction on tin salt, sulfur source, graphite oxide, melamine and phytic acid, collecting precipitate after the reaction is finished, freeze-drying to obtain a composite material precursor, and roasting the composite material precursor in an inert atmosphere to obtain PO (phosphorus oxide) 4 -an SnS/NG composite.
Specifically, biomass phytic acid is adopted as the phosphorus source in the reaction system. The ratio of phytic acid to other raw materials in the system is that the system contains 0.5-2 mL of phytic acid, 2mmol of tin salt, 2mmol of sulfur source, 5mmol of melamine and 65mL (2mg mL) -1 ) An aqueous GO solution.
Melamine was chosen as nitrogen-doped nitrogen source. The hydrogen bond between the phytic acid and the melamine effectively regulates and controls the proportion of different nitrogen species in nitrogen doping. PO with high electronegativity 4 3- By means of Sn-O-P covalent bond, the metal sulfide is embedded into SnS crystal lattice, thereby improving the intrinsic conductivity of the metal sulfide and promotingAnd (4) electron transfer.
The temperature of the hydrothermal reaction is 160-180 ℃, and the reaction time is 10-12 h. Placing the composite material precursor in a nitrogen or argon atmosphere, and roasting at 400-600 ℃ for 2-6 h to obtain PO 4 -an SnS/NG composite.
To further illustrate the technical effects of the present invention, the following description will be given with reference to specific examples.
Example 1
One, PO 4 -SnS/NG composite morphology characterization
One-step hydrothermal method for preparing phosphate radical ions (PO) deposited and grown on nitrogen-doped reduced graphene oxide nanosheet substrate 4 3- ) Implanting SnS crystals: the system contains 1mL of phytic acid and 2mmol of SnCl 4 ·5H 2 O, 2mmol of thiourea, 5mmol of melamine and 65mL (2mg mL) -1 ) Carrying out hydrothermal reaction on GO aqueous solution (12 h at 180 ℃), collecting precipitates (washing with deionized water/absolute ethyl alcohol for three times respectively) after the reaction is finished, freeze-drying to obtain a composite material precursor, and placing the composite material precursor in N 2 Calcining in atmosphere (500 ℃ for 4h) to prepare PO 4 -an SnS/NG composite.
Meanwhile, in order to deeply investigate the effect of phytic acid in the reaction system, a control group was prepared in example 1, i.e., the same reaction conditions were used except that phytic acid was not added to the reaction system, and the obtained sample was recorded as SnS/NG.
See FIG. 1, which is product PO of this example 4 SEM and TEM images of SnS/NG composites. At different magnifications, 3D silver ear layered structure is presented. PO (PO) 4 In SnS/NG, SnS nanosheets are deposited on the surface of the high pyridine nitrogen-doped rGO in a large amount, so that the surface of the high pyridine nitrogen-doped rGO becomes more wrinkled and fluffy (FIGS. 1 a-b). The hierarchical micro-nano structure forms a conductive network which is mutually communicated, and contains abundant reaction active sites and ion/electron diffusion channels. The absence of particles in the product indicates that SnS is uniformly deposited on the nitrogen doped rGO flakes, which is also supported by TEM images and elemental mapping. At PO 4 In the SnS/NG TEM images (fig. 1c-d) it can be found that well distributed SnS nanoplates with particle sizes of 10-35nm are present in the nitrogen doped rGO flakes. HRTEM image (picture)1e-h) detected sharp lattice fringes with pitches of 0.348, 0.330, 0.286, 0.282, and 0.298, corresponding to the lattice distances of the (120) (021) (111) (040) and (101) planes of the SnS, respectively. The remarkable reduction of the size of SnS and the increase of the lattice spacing indicate that the phytic acid can be injected into the SnS lattice and effectively inhibit the growth of microcrystals. FIG. 1i is the result of element mapping, revealing the PO 4 -homogeneous distribution of Sn, S, C, N and P elements in the SnS/NG sample, while demonstrating the presence of P species.
Referring to FIG. 2, XRD patterns of samples of the present invention, SnS/NG and PO 4 The SnS/NG samples all showed similar characteristic diffraction peaks, corresponding to the standard orthorhombic phase SnS (JCPDS 39-0354). In addition, PO 4 The shift of the main peak of the SnS/NG composite material to the low diffraction angle direction indicates PO 4 3- Introduction of (2) into PO 4 The layer spacing of the SnS/NG increased, which is consistent with TEM results.
Two, PO 4 -structural characterization of SnS/NG composite
Referring to FIG. 3, PO was studied carefully by XPS 4 -chemical state and composition of SnS/NG and SnS/NG. In PO compared to SnS/NG 4 A signal for P was found in SnS/NG, indicating successful introduction of P species. As shown in fig. 3. In the P2P spectrum, there are peaks at 139eV and 133eV with SnP 2 O 7 Characteristic peak corresponding to P-C bond, PO appeared at 134eV 4 3- The corresponding characteristic peak. Indicating that the P species is PO 4 3- Is present in the form of PO 4 -SnS/NG system. In the O1s spectrum, a characteristic peak corresponding to Sn-O-P appears at 531.5, which fully confirms PO 4 3- Bound as SnS in the form of covalent bonds, present in its lattice spacing. PO (PO) 4 In the high resolution Sn 3d and S2 p spectra of SnS/NG (FIGS. 3c-d), the combination energy is observed to move to higher energy by 0.2 and 0.1eV, which shows that the surrounding environment of the atom in the system is changed to form a bond with the atom with high electronegativity, and the combination energy of the inner layer electron is increased. Thus, PO 4 The higher bond energy in SnS/NG is due to PO 4 3- Because it has a high electronegativity. SnS/NG and PO as shown in FIGS. 3e-f 4 pyridine-N in-SnS/NG,The content of pyrrole-N and graphite-N is 46.91%/67.82%, 36.23%/26.58% and 16.86%/5.6%, respectively. PO (PO) 4 The pyridine-N content in the SnS/NG system is obviously increased and the graphite-N content is obviously reduced. The hydrogen bond and chelation between the phytic acid and the melamine effectively regulate and control the nitrogen species. The single or three N pyridine vacancies generated by pyridine nitrogen doping can enhance the storage performance and rate performance of sodium.
Three, PO 4 -sodium storage capacity of SnS/NG composite material
PO prepared in this example 4 The mass ratio of the SnS/NG composite material serving as an active material of the negative electrode of the sodium-ion battery to acetylene black and a binder PVDF/NMP is 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is 1.2mg cm -2 Left and right. A metal sodium sheet is used as a counter electrode, sodium perchlorate electrolyte (NC-008) and Whatman glass microfiber membrane with the model of GF/D are used, and the CR2032 type button half cell is assembled in a glove box filled with argon. In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-3.0V. The rate capability and coulombic efficiency curves of the cell were tested and the results are shown in figure 4.
To characterize PO 4 Electrochemical properties of the SnS/NG composite material, two comparative samples of SnS/NG and SnS/G composite materials are present in the present example. Namely, under the same reaction conditions, only the phytic acid is not added into the reaction system, the obtained sample is marked as SnS/NG, and the sample which is not added with the phytic acid and the melamine is marked as SnS/G.
FIG. 4a is PO 4 SnS/NG at 0.2A g -1 Constant current charge and discharge curves for cycles 1, 2, 20, 50, 100, 200 at current density. The initial charge-discharge specific capacity is 452.3/1056.4mA h g -1 Initial Coulombic Efficiency (ICE) was about 42.8%, and irreversible capacity loss may be related to the generation of SEI layers and decomposition of electrolytes. PO (PO) 4 The coincidence of the GDC curves from cycle 2 on the SnS/NG electrode is excellent. The coulombic efficiency increased to 93.16% in the second cycle, and the electrode got good activity as the number of cycles increasedHigh coulombic efficiency of the subsequent cycle (>99%) also confirmed PO 4 Good reversibility of SnS/NG during charging and discharging. FIG. 4b shows three electrode materials at 0.2A g -1 Cycling performance curve at current density. After 300 cycles, the SnS/NG and SnS/G electrodes can only provide 144.3mA h G -1 And 111.4mA h g -1 Reversible capacity of (2), and PO 4 The SnS/NG electrode maintains the highest reversible capacity of 445.1mA h g -1 The corresponding capacity retention was 98.4% and the capacity fade per cycle was only 0.0053%. FIG. 4c Studies PO 4 Rate capability of SnS/NG, SnS/NG and SnS/G, where PO 4 The best performance is shown by the SnS/NG electrode. At 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0A g -1 At current density of (2), PO 4 Reversible capacity of the-SnS/NG electrode 476.1, 427.0, 364.5, 324.7, 276.9, 219.9mA h g, respectively -1 . Even at 10A g -1 In case of (2), 182.0mA h g can be maintained -1 High capacity of (2). When the current density was switched to 0.1A g -1 When being in PO 4 The capacity of the SnS/NG electrode can be restored to 452.7mA h g -1 . When the current density is reduced, PO 4 The reversible capacity of the SnS/NG material can be basically restored to the initial value, and excellent rate capability is shown. Further test PO 4 SnS/NG at 1.0 and 5.0A g -1 Long term cycling stability at current density to better evaluate its electrochemical performance. As shown in fig. 4d, at 1.0A g -1 After 1500 cycles, PO 4 The SnS/NG electrode provides 380.5mA h g -1 The capacity retention rate of (2) was 95%, and the capacity fade rate per cycle was 0.0033%. When the current density increased to 5.0A g -1 When being in PO 4 The SnS/NG electrode can still provide 184.2mA hr g in 10000 cycles -1 The reversible capacity of (2) shows excellent high rate cycle performance, and the rate of capacity decay per cycle is only 0.0028%. The results show that PO 4 The SnS/NG has good electrochemical performance and excellent sodium ion intercalation/deintercalation kinetics. Notably, few Sn-based materials exhibit such ultra-long cycle life and cycle stability in sodium ion batteries, as compared to previously reported results.
Four, PO 4 -SnS/NG composite assembled full cell
Referring to fig. 5, PO for evaluation of anode material 4 Feasibility of application of SnS/NG, successful Assembly of PO 4 -SnS/CN//Na 3 V 2 (PO 4 ) 3 And (4) a sodium ion full cell. The current density and specific capacity of the full cell were measured using the mass of the negative electrode material as a standard. The full cell was tested at a voltage range of 0.01-4V. Based on the quality of the cathode, the full cell is at 1Ag -1 The product can show 221.6mAh g after 300 times of circulation -1 The reversible capacity of (2) had a capacity retention rate of 65.2% and a capacity fade rate per cycle of 0.116% (FIG. 5 a). The full cell also exhibited very good rate performance at 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0Ag -1 Providing reversible capacities of 418.2, 355.5, 316.5, 282.9, 254.9, 223.5mA hr g at current density -1 . When the current density returns to 0.1Ag -1 When the reversible capacity is recovered to 356.8mA h g -1 The stability of the anode material was demonstrated (fig. 5 b). The total battery is 0.1-5Ag -1 The charging and discharging curves under current density show excellent similarity in curve trend, and the average output voltage is about 2.5V (figure 5 c).
According to PO 4 Negative SnS/NG and Na 3 V 2 (PO 4 ) 3 The capacity of the full cell was calculated for the total mass of the positive electrode to obtain a Ragone plot (fig. 5 d). The total battery is 0.18kW kg -1 Shows 399.3Wh kg at a power density of -1 High energy density. Even if the power density is increased to 2.75kW kg -1 The energy density is still kept at 247.4Wh kg -1 . The assembled full battery of buttons can power a series of small LED lights (fig. 5 e). These encouraging results again verified PO 4 Advantages of the SnS/NG electrodes in practical applications of SIBs negative electrodes.

Claims (9)

1. A phosphate ion doped SnS crystal/nitrogen doped rGO composite material is characterized in that: the composite material consists of a nitrogen-doped rGO nano sheet and a SnS nano sheet which is deposited on the surface of the nitrogen-doped rGO nano sheet and is doped with phosphate ions, wherein the doped SnS crystal has a structure ofSnS crystal structure, PO 4 3- Embedded between SnS crystal lattice layers, Sn and O, O are covalently bonded with P.
2. The material of claim 1, wherein: the size of the SnS nanosheet doped with the phosphate ions is 10-35 nm.
3. The material of claim 1, wherein: the PO 4 3- The doping amount is 1.0-4.0% in terms of atomic percentage of phosphorus atoms in the composite material.
4. A preparation method of a phosphate ion doped SnS crystal/nitrogen doped rGO composite material is characterized by comprising the following steps: carrying out hydrothermal reaction on tin salt, a sulfur source, a graphene oxide aqueous solution, melamine and phytic acid serving as raw materials, collecting precipitates after the reaction is finished, and carrying out freeze drying to obtain a composite material precursor; and (3) roasting the composite material precursor in an inert atmosphere to prepare the SnS crystal/nitrogen-doped rGO composite material doped with phosphate ions.
5. The method of claim 4, wherein: the temperature of the hydrothermal reaction is 160-180 ℃, and the reaction time is 10-12 h.
6. The method of claim 4, wherein: the tin salt, the sulfur source and the tin atoms in the melamine are as follows: sulfur atom: the molar ratio of melamine is 2:2: 5; the ratio of the phytic acid to the melamine is 0.5-2 mL:5 mol; the volume ratio of the phytic acid to the graphene oxide aqueous solution is 0.5-2: 65, wherein the concentration of the graphene oxide aqueous solution is 2mg mL -1 。
7. The method of claim 4, wherein: and (3) placing the composite material precursor in a nitrogen or argon atmosphere, and roasting at 400-600 ℃ for 2-6 h to obtain the phosphate ion doped SnS crystal/nitrogen doped rGO composite material.
8. The method of claim 4, wherein: the tin salt is SnCl 4 ·5H 2 O or SnCl 2 (ii) a The sulfur source is thiourea, thioacetamide or sodium sulfide.
9. The use of the phosphate ion doped SnS crystal/nitrogen doped rGO composite material of any one of claims 1 to 3 as a sodium ion battery negative electrode material.
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