CN110635120A - Tin dioxide/metal elementary substance/graphene ternary composite material and preparation method and application thereof - Google Patents
Tin dioxide/metal elementary substance/graphene ternary composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a tin dioxide/metal simple substance/graphene ternary composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: tin salt and metal salt are used as raw materials and are uniformly loaded on a graphene oxide sheet in an electrostatic adsorption mode, a reducing agent is added after hydrolysis, and a one-pot method is used for obtaining the tin dioxide/metal simple substance/graphene ternary composite material based on different reduction potentials of tin dioxide and metal ions. The ternary composite material obtained by the invention has excellent cycle performance, and has wide application prospect when being used as a lithium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a tin dioxide/metal simple substance/graphene ternary composite material as well as a preparation method and application thereof.
Background
With the rapid development of science and technology, the requirements on the energy density and the cycle life of the lithium ion battery are higher and higher, and based on the working principle and the structural composition of the lithium ion battery, the effective approach is to design a high-specific-capacity electrode material with a stable structure. The tin-based oxide has the advantages of high specific capacity, high energy density, low lithium intercalation potential, good safety performance and the like, and has gradually replaced the application of commercial graphite cathode materials in the field of lithium ion batteries.
However, tin-based oxygen compounds have a considerable problem during charge and discharge: the lithium deintercalation process generates huge volume expansion, thereby causing the capacity attenuation and poor cycle stability. In addition, tin-based oxides, poor conductivity, also limit the performance of the overall rate performance. Therefore, when the performance of the related metal oxide in the lithium ion battery is improved, the stability of the material structure should be improved to resist the volume effect during the lithium intercalation and deintercalation process, and the conductivity should be further improved.
In order to relieve the huge volume expansion in the lithium deintercalation process, the most commonly adopted technical approaches at present are as follows: control of tin dioxide (SnO) on a nano-or micro-scale2) The method improves the lithium storage performance of the tin-based compound to a certain extent, but the result is still unsatisfactory. On the one hand, large-size tin-based compounds are used as lithium-storing agentsIn the case of a material having a large lithium ion diffusion path, Sn and Li are generated after discharge2O can not be well fixed, which causes the problems of material agglomeration, electric contact loss and the like, so that Sn and Li are mixed2O does not contact well and the first lithium storage reaction does not proceed reversibly. On the other hand, Li2The reversible reaction of O is closely related to the conductivity of the material and the diffusion rate of lithium ions, and Li is also used without good electron and ion transmission channels2One of the reasons why O is irreversible.
Recent studies have found that the nanostructure design of active materials is an effective method for improving their electrochemical performance. The nano structure can shorten the migration path of lithium ions and can also lead the conversion reaction of the lithium intercalation process of the tin-based oxide to tend to be reversible.
The patent No. 201310313571.6, chinese patent invention, discloses a tin dioxide/boron doped graphene nanocomposite and a preparation method thereof, wherein boron is added to the composite material, and the addition of boron plays a certain role in overcoming the volume effect, but the conductivity of the elemental boron is not good, and the conductivity of the prepared composite material is not significantly improved. Meanwhile, in the patent, graphene oxide, boric acid and stannous chloride dihydrate are dispersed in an ethanol aqueous solution, and the material is prepared through a hydrothermal reaction. The hydrothermal reaction needs to be finished at high temperature and high pressure, the reaction process is limited by a reaction kettle, the yield is low, and the preparation cost is high.
The Chinese patent with patent number 201710102926.5 discloses a tin dioxide/carbon/nitrogen doped graphene composite material with a pore structure and a preparation method and application thereof, the method prepares a rod-shaped tin dioxide/carbon composite material by mixing a tin compound and an organic substance on graphene, carbon is a substance used by a common electrode material, the addition of the substance can improve the conductivity and volume effect of the material, and hydrazine hydrate steam reduces graphite oxide to obtain nitrogen doped graphene, and the action patent of the material is not specifically expressed. The preparation method of this patent is complicated and employs two heat treatments, namely a pre-heat treatment and a further heat treatment. Firstly, controlling proper pyrolysis temperature and time, carrying out pre-heat treatment on a tin-based metal organic framework compound to obtain an intermediate which is partially decomposed and completely maintains the shape of a precursor, then coating the intermediate by using graphite oxide, and carrying out further heat treatment to finally obtain a tin dioxide/carbon/nitrogen doped graphene composite material with a pore structure, wherein the tin dioxide/carbon/nitrogen doped graphene composite material consists of a one-dimensional rodlike tin dioxide/carbon composite material at an inner layer and nitrogen doped graphene at an outer layer.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a tin dioxide/metal simple substance/graphene ternary composite material, and considering the electric/ionic conductivity and mechanical strength of an inert additive, the metal simple substance nanoparticles are required to promote SnO at an interface2The charge transfer of (2), relieving the volume stress during the insertion/extraction of lithium ions, and blocking metallic tin and LixAnd (4) agglomeration of Sn alloy. The ideal graphene is a two-dimensional crystal with only one atom thickness, with an ultra-large specific surface area (2630 m)2/g) and has unique carrier characteristics and transport characteristics, thus being a very potential energy storage material. The invention designs a two-dimensional structure, tin dioxide with electrochemical activity and metal nanoparticles without activity are tightly fixed on a flexible conductive graphene sheet in a mutual contact mode, so that the problems of volume expansion of the tin dioxide, particle aggregation in an alloying reaction process and the like can be solved to a certain extent, and the capacity and the cycle performance of a composite material are improved. In addition, the invention also provides a preparation method and application of the tin dioxide/metal simple substance/graphene ternary composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a tin dioxide/metal simple substance/graphene ternary composite material, wherein tin dioxide nanoparticles with electrochemical activity and metal nanoparticles without electrochemical activity are in contact with each other, uniformly distributed and fixed on a flexible conductive graphene sheet, and the metal nanoparticles comprise iron, nickel, copper, silver, palladium and platinum.
The second aspect of the invention provides a preparation method of a tin dioxide/metal simple substance/graphene ternary composite material, which utilizes a one-pot method to selectively reduce and prepare the tin dioxide/metal simple substance/graphene ternary composite material, and comprises the following steps:
step 1, preparing a tin dioxide/metal simple substance/graphene ternary composite material precursor;
and 2, calcining the product obtained in the step 1 for a certain time under the protection of an inert atmosphere, further reducing graphene and improving the crystallinity of the composite nano particles to obtain the tin dioxide/metal simple substance/graphene ternary composite material.
As a preferable technical scheme, the calcination temperature in the step 2 is 500-700 ℃.
As a preferred technical solution, the step 1 is specifically as follows: dissolving certain mass of polyvinylpyrrolidone and citric acid in graphene oxide suspension, adding tin salt and metal salt, performing ultrasonic stirring, uniformly mixing, adding ammonia water to adjust the solution to be alkaline, performing hydrolysis reaction on the tin salt and metal salt cations to obtain tin dioxide and metal hydroxide, then adding hydrazine hydrate or sodium borohydride as a reducing agent under the protection of inert atmosphere, fully stirring and reacting at a certain temperature, selectively reducing the metal hydroxide into a metal simple substance, washing the obtained product with deionized water and an ethanol solution, and drying to obtain the tin dioxide/metal simple substance/graphene composite precursor.
Preferably, the inert atmosphere in step 1 and step 2 is nitrogen or argon.
As a preferable technical scheme, the molar ratio of the tin salt to the metal salt is 80-95: 5 to 20.
As a preferable technical scheme, the tin salt in the step 1 is one of stannous chloride and stannic chloride.
Preferably, in the step 1, the redox potential of the metal salt cation is lower than that of tin dioxide, and the metal salt cation is Fe2+、Ni2+、Cu2+、Ag+、Pd2+、Pt2+Wherein the metal salt anion is Cl-、NO3 -、SO4 2-One kind of (1).
In a third aspect of the invention, the tin dioxide/metal simple substance/graphene ternary composite material is applied, and the tin dioxide/metal simple substance/graphene ternary composite material or the tin dioxide/metal simple substance/graphene ternary composite material prepared by the preparation method is applied as a negative electrode material.
Compared with other tin dioxide/carbon materials and tin dioxide/graphene composite materials, the invention has the following beneficial effects:
(1) the preparation method of the composite material is simple and efficient, and the tin dioxide/metal simple substance composite nano particles are uniformly distributed on the graphene sheet in a ternary composite structure by selectively reducing the metal simple substance by a one-pot method by utilizing different reduction potentials of the tin dioxide and the metal ions.
(2) In conventional SnO2In the/graphene composite cathode, a conversion reaction occurs on the interface of the conductive framework/tin dioxide to form metal tin, and the area becomes a focus of further reaction, so that local aggregation of tin and Sn/Li are causedxSn agglomerates, ultimately leading to active material failure and specific volume decay. In the tin dioxide/metal simple substance/graphene ternary composite material, the metal simple substance nanoparticles have good electronic conductivity, can provide multidimensional electronic channels, and enhance charge transfer dynamics, so that SnO is enabled to be in a state of being oxidized2Has more active reaction sites.
(3) With Li+Ion continuous intercalation SnO2The nano particles and the Li-Sn alloy bear huge volume expansion, and the added metal simple substance components are uniformly distributed in SnO2Around the particles, it can effectively act as a skeleton to buffer the volume stress, so that Sn and LixThe agglomeration of the Sn alloy is separated and suppressed. Therefore, the added elemental metal component cannot catalyze Li2Decomposition of O, but good confinement effects can suppress LixSn and amorphousForm Li2Aggregation and agglomeration of O, thereby promoting Sn and Li2And the reversible conversion reaction of O improves the coulomb efficiency and the cyclic specific capacity of the electrode.
Compared with the solutions disclosed in patent No. 201310313571.6 and patent No. 201710102926.5, the present invention has the following advantages:
(1) according to the invention, tin dioxide is used as an active substance of the cathode material, the metal simple substance has good structural stability and conductivity, graphene has certain reaction activity, the tin dioxide and the metal simple substance are dispersed on the graphene, the reaction specific surface area of the material is increased, the stability of the material structure is increased by introducing the metal simple substance, and the conductivity of the material is greatly improved.
(2) The tin dioxide/metal simple substance/graphene ternary composite material serving as the lithium battery cathode material is prepared by a one-pot method, namely all reactants are mixed together, and the metal simple substance is selectively reduced by utilizing different reduction potentials of the tin dioxide and metal ions to obtain the tin dioxide/metal simple substance composite nanoparticles which are uniformly distributed on a graphene sheet.
In conclusion, the tin dioxide/metal monomer/graphene ternary composite material successfully overcomes the defects of a tin dioxide-based negative electrode material, and is a very promising negative electrode material for a lithium ion battery.
Drawings
Fig. 1 is an X-ray diffraction pattern of the tin dioxide/elemental metal/graphene ternary composite material prepared in example 1.
Fig. 2 is a TEM photograph of the tin dioxide/elemental metal/graphene ternary composite material prepared in example 1.
Fig. 3 is an HRTEM photograph of the tin dioxide/elemental metal/graphene ternary composite material prepared in example 1.
Fig. 4 is a cyclic voltammetry graph of the tin dioxide/elemental metal/graphene ternary composite material prepared in example 1.
Fig. 5 is a comparison graph of the charging and discharging curves of the tin dioxide/elemental metal/graphene ternary composite material prepared in example 1 and the tin dioxide/graphene. ((a) 1 st turn, (b) 100 th turn)
Fig. 6 is a cycle performance diagram of the tin dioxide/elemental metal/graphene ternary composite material prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Preparation of tin dioxide/copper/graphene ternary composite material
The preparation method comprises the following steps:
first, polyvinyl pyrrolidone (PVP, 0.01g) and citric acid (0.02g) were added to a Graphene Oxide (GO) suspension with stirring, PVP acting as a surfactant to maintain its dispersibility and morphology. Then 0.203g SnCl2·2H2O (0.9mmol) and 0.017g of CuCl2·2H2O (0.1mmol) is dispersed and added into the mixed solution, and Sn is ensured by electrostatic attraction under the action of stirring and ultrasound2+And Cu2+Uniformly distributed on the surface of graphene oxide, and ammonia water is used for adjusting the solution to be alkaline, Sn2+Hydrolysis to SnO2. Under the protection of nitrogen atmosphere, 0.1 μ L of 50% N was added dropwise2H4·H2Stirring for 2h at 90 ℃, and simultaneously reducing graphene oxide, and adding Cu2+Is reduced to metallic copper. And then cleaning the black product with water and ethanol, and drying to obtain the tin dioxide/copper/graphene composite precursor.
In a tube furnace, N is introduced2At 5 ℃ for min-1And (3) heating to 500 ℃ at a speed, calcining for 2h, further reducing the graphene and improving the crystallinity of the composite nano particles to obtain the tin dioxide/copper/graphene ternary composite material.
And (3) testing the electrical property of the prepared material:
the prepared product was mixed in a composite material: carbon black with: mixing polyvinylidene fluoride according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone for pulping, and dripping on a copper sheet to obtain the working electrode. The lithium metal sheet is taken as a counter electrode, the polypropylene microporous membrane is taken as a diaphragm, and 1mol/L LiPF is used6The mixed solution of EC ethylene carbonate/DMC dimethyl carbonate/DEC diethyl carbonate (weight ratio 1:1:1) is used as an electrolyte, and a CR2032 button cell is assembled in a glove box filled with argon.
The XRD of the product is shown in figure 1, the tin dioxide/copper/graphene ternary composite material prepared by the method contains tin dioxide and copper, and no obvious impurity peak exists in the product. Fig. 2 and 3 are low-power Transmission Electron Microscope (TEM) and high-resolution TEM photographs of the prepared tin dioxide/copper/graphene ternary composite material, and it can be seen that tin dioxide and copper nanoparticles are uniformly loaded on the graphene sheet, and the contact between the tin dioxide and the copper particles is tight. As can be seen from the cyclic voltammetry of fig. 4, the reduction peak and the oxidation peak of the tin dioxide/copper/graphene ternary composite mainly result from the reversible decomposition of tin dioxide and the tin-lithium alloying/dealloying process; from the second turn, the curve shows a higher degree of overlap, indicating that the material has better reversibility. FIG. 5 is a comparison graph of the charging and discharging curves of the tin dioxide/copper/graphene ternary composite material prepared by the invention and the tin dioxide/graphene, and it can be seen from the graph that the charging and discharging platform of the composite material is obvious; the initial discharge specific capacity of the traditional tin dioxide/graphene composite material is 1453.5mAh/g, and the initial discharge specific capacity is quickly attenuated to 618.0mAh/g after 100 circles; the first discharge specific capacity of the tin dioxide/copper/graphene ternary composite material can reach 1565mAh/g, the discharge specific capacity of the 100 th circle is 816.2mAh/g, and the capacity is still kept high. FIG. 6 is a cycle performance diagram of the tin dioxide/copper/graphene ternary composite material at a current density of 0.1A/g, and after 200 cycles, the specific capacity is still maintained at 890.6mAh/g, which shows that the ternary composite material has excellent cycle stability.
Example 2
Preparation of stannic oxide/nickel/graphene ternary composite material
The preparation method comprises the following steps:
first, polyvinyl pyrrolidone (PVP, 0.01g) and citric acid (0.02g) were added to the GO suspension with stirring, PVP acting as a surfactant to maintain its dispersibility and morphology. Then 0.180g SnCl2·2H2O (0.8mmol) and 0.048g NiCl2·6H2O (0.2mmol) is dispersed and added into the mixed solution, and Sn is ensured by electrostatic attraction under the action of stirring and ultrasound2+And Ni2+Uniformly distributed on the surface of graphene oxide, and ammonia water is used for adjusting the solution to be alkaline, Sn2+Hydrolysis to SnO2. Under nitrogen atmosphere, 0.2. mu.L of 50% N was added dropwise2H4·H2O, stirring for 12h at 80 ℃, and Ni accompanying the reduction of graphene oxide2+Is reduced to metallic nickel. And then cleaning the black product with water and ethanol, and drying to obtain the tin dioxide/nickel/graphene composite precursor.
Introducing argon gas into a tube furnace at 5 ℃ for min-1And (3) heating to 600 ℃ at a speed, calcining for 10h, further reducing the graphene and improving the crystallinity of the composite nano particles to obtain the tin dioxide/nickel/graphene ternary composite material.
Example 3
Preparation of tin dioxide/iron/graphene ternary composite material
The preparation method comprises the following steps:
first, polyvinyl pyrrolidone (PVP, 0.01g) and citric acid (0.02g) were added to the GO suspension with stirring, PVP acting as a surfactant to maintain its dispersibility and morphology. Then 0.334g SnCl5·5H2O (0.95mmol) and 0.01g FeCl2·4H2O (0.05mmol) is dispersed and added into the mixed solution, and Sn is ensured by electrostatic attraction under the action of stirring and ultrasound2+And Fe2+Uniformly distributed on the surface of graphene oxide, and ammonia water is used for adjusting the solution to be alkaline, Sn2+Hydrolysis to SnO2. Under the protection of argon atmosphere, dropwise adding 2 mu L of sodium borohydride, stirring for 8h at 75 ℃, and simultaneously reducing graphene oxide to obtain Fe2+Is reduced into metallic iron simple substance. Then washing the black product with water and ethanol, and dryingAnd drying to obtain the stannic oxide/iron/graphene composite precursor.
In a tube furnace, N is introduced2At 5 ℃ for min-1And (3) heating to 600 ℃ at a speed, calcining for 10h, further reducing the graphene and improving the crystallinity of the composite nano particles to obtain the tin dioxide/iron/graphene ternary composite material.
Example 4
Preparation of tin dioxide/platinum/graphene ternary composite material
The preparation method comprises the following steps:
first, polyvinyl pyrrolidone (PVP, 0.01g) and citric acid (0.02g) were added to the GO suspension with stirring, PVP acting as a surfactant to maintain its dispersibility and morphology. Then 0.28g SnCl4·5H2O (0.8mmol) and 0.064g Pt (NO)3)2(0.2mmol) is dispersedly added into the mixed solution, and Sn is ensured by electrostatic attraction under the action of stirring and ultrasound2+And Pt2+Uniformly distributed on the surface of graphene oxide, and ammonia water is used for adjusting the solution to be alkaline, Sn2+Hydrolysis to SnO2. Under nitrogen atmosphere, 1. mu.L of 50% N was added dropwise2H4·H2Stirring for 48h at 90 ℃ and carrying out reduction on the graphene oxide, wherein Pt is2+Is reduced to platinum simple substance. And then cleaning the black product with water and ethanol, and drying to obtain the tin dioxide/platinum/graphene composite precursor.
In a tube furnace, N is introduced2At 5 ℃ for min-1And (3) heating to 700 ℃ at a speed, calcining for 36h, further reducing the graphene and improving the crystallinity of the composite nano particles to obtain the tin dioxide/platinum/graphene ternary composite material.
Although the present invention has been described in detail with respect to the above embodiments, it will be understood by those skilled in the art that modifications or improvements based on the disclosure of the present invention may be made without departing from the spirit and scope of the invention, and these modifications and improvements are within the spirit and scope of the invention.
Claims (9)
1. The tin dioxide/metal simple substance/graphene ternary composite material is characterized in that tin dioxide nanoparticles with electrochemical activity and metal nanoparticles without electrochemical activity are in contact with each other, are uniformly distributed and are fixed on a flexible conductive graphene sheet, and the metal nanoparticles comprise iron, nickel, copper, silver, palladium and platinum.
2. A preparation method of a tin dioxide/metal simple substance/graphene ternary composite material is characterized in that the tin dioxide/metal simple substance/graphene ternary composite material of claim 1 is prepared by selective reduction with a one-pot method, and comprises the following steps:
step 1, preparing a tin dioxide/metal simple substance/graphene ternary composite material precursor;
and 2, calcining the product obtained in the step 1 for a certain time under the protection of an inert atmosphere, further reducing graphene and improving the crystallinity of the composite nano particles to obtain the tin dioxide/metal simple substance/graphene ternary composite material.
3. The method for preparing the tin dioxide/metal element/graphene ternary composite material as claimed in claim 2, wherein the calcination temperature in the step 2 is 500-700 ℃.
4. The method for preparing the tin dioxide/metal element/graphene ternary composite material according to claim 2, wherein the step 1 is specifically as follows: dissolving certain mass of polyvinylpyrrolidone and citric acid in graphene oxide suspension, adding tin salt and metal salt, performing ultrasonic stirring, uniformly mixing, adding ammonia water to adjust the solution to be alkaline, performing hydrolysis reaction on the tin salt and metal salt cations to obtain tin dioxide and metal hydroxide, then adding hydrazine hydrate or sodium borohydride as a reducing agent under the protection of inert atmosphere, fully stirring and reacting at a certain temperature, selectively reducing the metal hydroxide into a metal simple substance, washing the obtained product with deionized water and an ethanol solution, and drying to obtain the tin dioxide/metal simple substance/graphene composite precursor.
5. The method for preparing the tin dioxide/metal element/graphene ternary composite material according to claim 4, wherein the inert atmosphere in the step 1 and the step 2 is nitrogen or argon.
6. The preparation method of the tin dioxide/metal element/graphene ternary composite material according to claim 6, wherein the molar ratio of the tin salt to the metal salt is 80-95: 5 to 20.
7. The method for preparing the tin dioxide/metal element/graphene ternary composite material according to claim 4, wherein the tin salt in the step 1 is one of stannous chloride and stannic chloride.
8. The method for preparing the tin dioxide/metal element/graphene ternary composite material according to claim 4, wherein in the step 1, the oxidation-reduction potential of the metal salt cation is lower than that of tin dioxide, and the metal salt cation is Fe2+、Ni2+、Cu2+、Ag+、Pd2+、Pt2+Wherein the metal salt anion is Cl-、NO3 -、SO4 2-One kind of (1).
9. The tin dioxide/metal simple substance/graphene ternary composite material is used as the anode material, and is characterized in that the tin dioxide/metal simple substance/graphene ternary composite material is used as the anode material.
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| CN111187496A (en) * | 2020-02-12 | 2020-05-22 | 东华大学 | Preparation method and application of multifunctional bio-based degradable polylactic resin |
| CN112209430A (en) * | 2020-09-24 | 2021-01-12 | 广东工业大学 | Tin dioxide/niobium doped carbon composite material for lithium ion battery and preparation method and application thereof |
| CN113999657A (en) * | 2021-11-23 | 2022-02-01 | 安徽碳华新材料科技有限公司 | Processing technology of alkene-carbon composite material |
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| CN112209430B (en) * | 2020-09-24 | 2023-03-31 | 广东工业大学 | Tin dioxide/niobium doped carbon composite material for lithium ion battery and preparation method and application thereof |
| CN113999657A (en) * | 2021-11-23 | 2022-02-01 | 安徽碳华新材料科技有限公司 | Processing technology of alkene-carbon composite material |
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