CN111825091B - Three-dimensional graphene composite material loaded with single-layer flower-like MXene nanosheets and preparation method and application thereof - Google Patents
Three-dimensional graphene composite material loaded with single-layer flower-like MXene nanosheets and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a three-dimensional graphene composite material loaded with a single-layer flower-shaped MXene nanosheet and a preparation method thereof, and the three-dimensional graphene composite material can be applied as an electrode material of a lithium-sulfur battery. The method comprises the following steps: 1) Putting the precursor MAX into an HF solution, and continuously stirring to enable the reaction to be uniform until the reaction is complete; 2) Centrifugally washing the obtained solution to be neutral, and dispersing the solution into a TMAOH solution; 3) Centrifugally washing the obtained solution, protecting the solution with inert gas, performing ultrasonic treatment on the product by low-temperature freezing, transferring the completely frozen product into a freeze dryer, and performing freeze drying; 4) The MXene-loaded three-dimensional graphene composite material is obtained by mixing, stirring and dispersing uniformly a monolayer flower-like MXene nanosheet and graphene oxide after treatment by a spray drying method, finally adding a reducing agent, heating and reacting to obtain the MXene-loaded three-dimensional graphene composite material, and then freeze-drying the MXene-loaded three-dimensional graphene composite material. When the material is used for modifying the positive electrode of the lithium-sulfur battery, excellent high-load performance and excellent cycling stability can be shown.
Description
Technical Field
The invention relates to design of a lithium-sulfur battery electrode material, in particular to a three-dimensional graphene composite material loaded with a single-layer flower-shaped MXene nanosheet and a preparation method thereof, and the three-dimensional graphene composite material can be applied as the lithium-sulfur battery electrode material.
Background
At present, the energy density of the traditional lithium ion battery is limited by the theoretical capacity of the anode and cathode materials, and the requirement of the increasing electric automobile and the like on a high-energy-density energy storage device cannot be met. Lithium-sulfur batteries are considered to be one of the important development directions for next-generation electrochemical energy storage devices due to their very high theoretical capacity (1675 mAh/g) and energy density (2600 Wh/Kg). However, the development and future commercial application of lithium sulfur batteries are still limited by many factors, such as very low conductivity of sulfur and its discharge product, lithium sulfide, performance degradation due to volume change of sulfur during charge and discharge, and shuttling effect of polysulfide as a charge and discharge intermediate.
In order to overcome the above problems, in the preparation process of the sulfur positive electrode, a small amount of polar compound is generally required to be introduced to adsorb lithium polysulfide and inhibit the shuttle effect, but most of the polar compounds have poor conductivity, so that the introduction of the polar compounds inevitably reduces the overall energy density of the battery, thereby losing the advantage of high energy density of the lithium-sulfur battery. Therefore, it is important to prepare a composite positive electrode material having high conductivity and high adsorptivity to lithium polysulfide. MXene, a novel two-dimensional material, belongs to transition metal carbon/nitride (TMC/TMN) and is synthesized from MAX materials. MAX is a generic term for a series of ternary layered compounds, wherein M represents a transition group metal element, A is a third and fourth main group element, and X is a carbon and nitrogen element. In the MAX phase, X atoms fill the octahedral structure formed by the close packing of M atoms, while A atoms are located between the layers of M and X. The MXene can be obtained by selectively etching the A atomic layer because the bonding force between the A atomic layer and the M/X atomic layer is relatively weak. However, due to the strong interaction of surface groups, MXene etched by strong acid still cannot be uniformly dispersed in the form of a single layer sheet, and is easy to agglomerate, so that the specific surface area is reduced, and the application of the MXene in lithium batteries and the like is greatly hindered.
Disclosure of Invention
The invention provides a lithium-sulfur battery electrode material with high specific surface area and high performance and a large-scale preparation method thereof, and particularly provides a three-dimensional graphene composite material loaded with a single-layer flower-shaped MXene nanosheet and a preparation method thereof, so that the conductivity of the whole material is improved, the transmission rate of electrons and ions in a lithium-sulfur battery is enhanced, the MXene nanosheet loaded on a graphene single sheet can effectively inhibit the shuttle effect in the lithium-sulfur battery, and the electrochemical performance of the battery is improved.
In order to realize the purpose, the technical scheme of the invention is as follows: the preparation method of the three-dimensional graphene composite material loaded with the single-layer flower-shaped MXene nanosheets comprises the following steps:
1) Putting the precursor MAX into an HF solution, and continuously stirring to enable the precursor to react uniformly until the reaction is complete;
2) Centrifugally washing the solution obtained in the step 1) to be neutral, and dispersing the solution into a TMAOH solution;
3) Centrifugally washing the solution obtained in the step 2), protecting ultrasound with inert gas, freezing the product at low temperature, transferring the completely frozen product into a freeze dryer, and freeze-drying at ultralow temperature for over 72 hours;
4) Treating the powder sample obtained in the step 3) by using a spray drying method to obtain a monolayer flower-like MXene nanosheet and graphene oxide, blending, stirring and dispersing uniformly, finally adding a reducing agent, heating for reaction to obtain an MXene-loaded three-dimensional graphene composite material, and freeze-drying to obtain the target product, namely the monolayer flower-like MXene nanosheet-loaded three-dimensional graphene composite material.
According to the scheme, the graphene oxide is a commercial graphene oxide dispersion liquid, and the concentration of the graphene oxide dispersion liquid is greater than 1mg/mL.
According to the scheme, the reducing agent is as follows: sodium ascorbate or ascorbic acid.
According to the scheme, the MXene nanosheets comprise Ti 3 C 2 、Hf 3 C 2 Or Ti 2 C metal carbide.
According to the scheme, the heating reaction temperature is 95 ℃, and the heating time is more than 2 hours.
The single-layer flower-like MXene nanosheet and three-dimensional graphene composite material prepared by the preparation method is provided.
The three-dimensional graphene composite material loaded with the single-layer flower-shaped MXene nanosheets is applied as an electrode material of a lithium-sulfur battery.
The invention discloses a single-layer flower-shaped MXene nanosheet and graphene self-assembled aerogel prepared by the method as a lithium-sulfur battery cathode material, which comprises three-dimensional reduced graphene oxide and MXene compounds uniformly dispersed in the three-dimensional reduced graphene oxide. The three-dimensional reduced graphene oxide is prepared by adding a very strong reducing agent into a graphene oxide dispersion liquid, and under the condition of 95 ℃, the graphene oxide is rapidly subjected to self-assembly by losing a large number of functional groups through the interaction of the reducing agent and graphene, the assembly of the three-dimensional graphene comes from the action of the reducing agent, and the graphene oxide is assembled into a three-dimensional columnar structure by losing a large number of functional groups; the MXene loading and the graphene have a physical effect, so that the chemical composition and the micro-morphology of the MXene are not changed by the graphene assembly and loading.
The invention has the beneficial effects that: a single-layer flower-like MXene nanosheet is synthesized through strong acid etching, inert gas protection ultrasonic and a spray drying method, the agglomeration phenomenon can be effectively inhibited, and meanwhile, the method can be popularized and synthesized for other types of MXene materials. The electrochemical performance of the lithium-sulfur battery can be effectively improved by loading the carbon-carbon composite material into the three-dimensional graphene oxide and modifying the sulfur anode. Firstly, the three-dimensional graphene framework can provide excellent conductivity for the whole electrode material, and meanwhile, the porous characteristic can realize a higher-sulfur-loaded positive electrode material; and secondly, the polar single-layer MXene material can effectively adsorb polysulfide, inhibit the shuttle effect in the lithium-sulfur battery and improve the utilization rate of sulfur. These characteristics lead to the material exhibiting excellent high load performance and cycle stability when used to modify the positive electrode of a lithium sulfur battery.
Drawings
FIG. 1 is a schematic view of the preparation of example 1 for supporting a monolayer of flower-like Ti 3 C 2 A flow chart of a three-dimensional graphene composite material of the nanosheets;
FIG. 2 is the single-layered flower-like Ti supported in example 1 3 C 2 A morphology characterization map of the three-dimensional graphene of the nanosheets;
FIG. 3 is the single-layered flower-like Ti supported in example 1 3 C 2 SEM and EDS element distribution maps of the three-dimensional graphene of the nanosheets;
FIG. 4 shows single-layered flower-like Ti of example 1 3 C 2 An X-ray photoelectron spectroscopy (XPS) of the nanoplatelets;
FIG. 5 is the single-layered flower-like Ti supported in example 1 3 C 2 Electrochemical performance diagram of nanosheet three-dimensional graphene, including Ti in composite aerogel 3 C 2 A nanosheet optimal proportion test chart and a long cycle performance chart under 1C current density;
FIG. 6 is the supported single-layered flower-like Ti of example 1 3 C 2 The high-load performance diagram of the three-dimensional graphene composite material of the nanosheet comprises a comparison diagram of the surface capacity of the nanosheet with that of a traditional lithium ion battery under different surface loading amounts.
FIG. 7 is the single-layered flower-like Ti supported in example 2 2 And (3) a long cycle performance diagram of the three-dimensional graphene composite material of the C nanosheet.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
supported Ti 3 C 2 The three-dimensional graphene lithium-sulfur battery electrode material of the nanosheet comprises the following steps:
1) 2g of Ti is added into the inner container of a 250mL reaction kettle 3 AlC 2 (MAX), adding 20mL of 40% HF solution, and stirring to react for 24 hours;
2) Centrifugally washing the product obtained in the step 1) to be neutral, dispersing the product into 20mL 45% TMAOH solution, stirring for 24 hours, and then carrying out ultrasonic treatment for 2 hours under the protection of high-purity argon;
3) Washing the product obtained in the step 2), centrifuging (2500rpm, 30min), separating, treating the separated product with liquid nitrogen, and directly transferring the treated product into a freeze dryer for freeze-drying for 72 hours at the temperature of-40 ℃;
4) Spray drying the product obtained in the step 3) to obtain single-layer flower-shaped Ti 3 C 2 (MXene) nanoplatelets;
5) Adding 2mL of 1mg mL of graphene oxide dispersion liquid into a 10mL sample bottle, and ultrasonically stirring for 10min;
6) Mixing Ti in the step 4) 3 C 2 Ultrasonically stirring the nanosheets in deionized water for 3min;
7) Ti dispersed in the step 6) 3 C 2 Adding the nanosheets into the solution obtained in the step 5) and ultrasonically stirring for 5min;
8) Adding sodium ascorbate into a sample bottle, and shaking uniformly;
9) Heating the sample bottle in a 95 ℃ oven for 2h to completely assemble the graphene oxide dispersion liquid into negativeTi-carrying 3 C 2 Three-dimensionally reducing graphene oxide of the nanosheets;
10 Will carry Ti 3 C 2 Washing the three-dimensional reduced graphene oxide composite material of the nanosheets in deionized water at 95 ℃ for 2 hours, repeating the washing for three times, and then transferring the nanosheets into a freeze dryer to freeze-dry the nanosheets at-40 ℃ for 48 hours;
11 The self-assembled composite material obtained in step 10) was used as a self-supporting electrode material, and the assembly of a lithium sulfur battery was performed in an argon glove box, and an electrochemical performance test was performed.
Loading Ti with the product of the invention 3 C 2 The three-dimensional reduction graphene oxide composite material of the nanosheet is taken as an example, and FIG. 1 is a schematic diagram of preparation, and finally Ti is obtained 3 C 2 The nano sheet is in a composite structure with uniform dispersion inside the three-dimensional graphene oxide. The corresponding microstructure is shown in figure 2, and according to the scanning electron microscope image and the transmission electron microscope image, the three-dimensional graphene has a large number of holes and single-layer flower-shaped Ti 3 C 2 The nano-sheets are uniformly dispersed in the graphene and have good contact with the graphene sheets, and Ti 3 C 2 The size of the nanosheet is micron level, the thickness of the nanosheet reaches nanometer level, and the nanosheet is uniformly dispersed in the three-dimensional graphene to form a complete three-dimensional composite structure.
FIG. 3 is a view of supporting Ti 3 C 2 The element distribution diagram of the nano-sheet three-dimensional reduced graphene oxide composite material can clearly show that C, ti and O elements are uniformly distributed on the composite material, and proves that Ti 3 C 2 The nanosheets are uniformly dispersed inside the three-dimensional graphene.
FIG. 4 is a single layer flower shape Ti 3 C 2 The X-ray photoelectron spectrum (XPS) of the nanosheet can see the chemical composition of the synthesized material according to the marked chemical bond, thereby proving that the required Ti is successfully synthesized 3 C 2 Material (wherein the O and F elements are derived from Ti) 3 C 2 Surface passivating group).
The Ti support prepared in this example 3 C 2 Application of nanosheet three-dimensional reduced graphene oxide composite material as self-supporting lithium-sulfur battery electrode materialThe following were used: and putting the obtained composite material in an oven at 70 ℃ in advance, drying for 24 hours, and taking out the composite material to be directly used as an electrode plate. Wherein the electrolyte is DME (ethylene glycol dimethyl ether) and DOL (1,3-dioxolane) solution containing 1M LiTFSI (lithium bistrifluoromethanesulfonimide), the volume ratio of the two solvents is 1:1, and 1 mass percent of LiNO is added 3 And as an additive, protecting a lithium cathode in the charging and discharging process, and assembling the button lithium-sulfur battery by taking Celgard2325 as a diaphragm and CR2025 type stainless steel as a battery shell. The remaining steps of the preparation method of the lithium sulfur battery are the same as those of the general preparation method.
FIG. 5 shows the load Ti 3 C 2 The electrochemical performance test chart of the nanosheet three-dimensional reduced graphene oxide composite material shows that Ti in the composite material is shown in the a chart 3 C 2 When the mass content of the nanosheets is 40%, the corresponding cycle performance is optimal. Meanwhile, the prepared composite electrode material is far better than the composite electrode material without Ti in both cycle performance and coulombic efficiency 3 C 2 The pure reduced graphene oxide material of the nanosheet has excellent long-term cycle performance under the condition of 1C charge and discharge, and the initial capacity is 980mAh g -1 The capacity after 200 cycles is 837mAh g -1 The average capacity fade was only 0.071%.
FIG. 6 shows the load Ti 3 C 2 High-load performance diagram of three-dimensional reduced graphene oxide composite material of nanosheet, with in-plane loading of 6.75 and 11.08mg cm -2 The composite material has henhaode cycle performance, and can provide performance far exceeding that required by commercial lithium ion batteries by converting into corresponding surface capacity.
Example 2:
carrying Ti 2 The three-dimensional graphene lithium-sulfur battery electrode material of the C nanosheet comprises the following steps:
1) 2g of Ti is added into the inner container of a 250mL reaction kettle 2 Adding 20mL of 40% HF solution into the AlC (MAX), and stirring to react for 24 hours;
2) Centrifugally washing the product obtained in the step 1) to be neutral, dispersing the product into 20mL 45% TMAOH solution, stirring for 24 hours, and then carrying out ultrasonic treatment for 2 hours under the protection of high-purity argon;
3) Washing the product obtained in the step 2), centrifuging (2500rpm, 30min), separating, treating the separated product with liquid nitrogen, and directly transferring to a freeze dryer for freeze drying at-40 ℃ for 72 hours;
4) Spray drying the product obtained in the step 3) to obtain single-layer flower-shaped Ti 2 C (MXene) nanoplatelets;
5) Adding 2mL of 1mg mL of graphene oxide dispersion liquid into a 10mL sample bottle, and ultrasonically stirring for 10min;
6) Mixing Ti in the step 4) 2 C nano-sheet is ultrasonically stirred for 3min in deionized water;
7) The Ti dispersed in the step 6) is added 2 Adding the C nano sheet into the solution obtained in the step 5) and ultrasonically stirring for 5min;
8) Adding sodium ascorbate into a sample bottle, and shaking uniformly;
9) Heating the sample bottle in a 95 ℃ oven for 2h to completely assemble the graphene oxide dispersion liquid into the Ti-loaded material 2 C, three-dimensionally reducing graphene oxide of a nanosheet;
10 Will carry Ti 2 Washing the three-dimensional reduced graphene oxide composite material of the C nano sheet in deionized water at 95 ℃ for 2h, repeating the washing for three times, and then transferring the washed composite material into a freeze dryer to freeze and dry the composite material at-40 ℃ for 48h;
11 The self-assembled composite obtained in step 10) was used as a self-supporting electrode material, and the assembly of a lithium sulfur battery was performed in an argon glove box and an electrochemical performance test was performed.
FIG. 7 shows the load Ti 2 The long-cycle performance of the three-dimensional reduced graphene oxide composite material of the C nanosheet under the current density of 2C is 612mAh g of initial capacity -1 The capacity after 300 cycles of circulation is 587mAh g -1 The capacity retention rate is ultrahigh, and the average capacity attenuation is only 0.001%.
Example 3:
load Hf 3 C 2 The three-dimensional graphene lithium-sulfur battery electrode material of the nanosheet comprises the following steps:
1) 2g of Hf is added into a 250mL reaction kettle liner 3 AlC 2 (MAX), adding 20mL of 40% HF solution, and stirring to react for 24 hours;
2) Centrifugally washing the product obtained in the step 1) to be neutral, dispersing the product into 20mL of 45% TMAH solution, stirring for 24 hours, and then carrying out ultrasonic treatment for 2 hours under the protection of high-purity argon;
3) Washing the product obtained in the step 2), centrifuging (2500rpm, 30min), separating, treating the separated product with liquid nitrogen, and directly transferring to a freeze dryer for freeze drying at-40 ℃ for 72 hours;
4) Spray drying the product of the step 3) to obtain single-layer flower-shaped Hf 3 C 2 (MXene) nanoplatelets;
5) Adding 2mL of 1mg mL of graphene oxide dispersion liquid into a 10mL sample bottle, and ultrasonically stirring for 10min;
6) Hf in step 4) 3 C 2 Ultrasonically stirring the nanosheets in deionized water for 3min;
7) The Hf dispersed in the step 6) 3 C 2 Adding the nanosheets into the solution obtained in the step 5) and ultrasonically stirring for 5min;
8) Adding sodium ascorbate into a sample bottle, and shaking uniformly;
9) Putting the sample bottle into a 95 ℃ oven to be heated for 2h, so that the graphene oxide dispersion liquid is completely assembled into load Hf 3 C 2 Three-dimensionally reducing graphene oxide of the nanosheets;
10 ) will carry Hf 3 C 2 Washing the three-dimensional reduced graphene oxide composite material of the nanosheets in deionized water at 95 ℃ for 2 hours, repeating the washing for three times, and then transferring the nanosheets into a freeze dryer to freeze and dry the nanosheets at-40 ℃ for 48 hours;
11 The self-assembled composite obtained in step 10) was used as a self-supporting electrode material, and the assembly of a lithium sulfur battery was performed in an argon glove box and an electrochemical performance test was performed.
Claims (7)
1. The preparation method of the three-dimensional graphene composite material loaded with the single-layer flower-shaped MXene nanosheets comprises the following steps:
1) Putting the precursor MAX into an HF solution, and continuously stirring to enable the precursor to react uniformly until the reaction is complete;
2) Centrifugally washing the solution obtained in the step 1) to be neutral, and dispersing the solution into a TMAOH solution;
3) Centrifugally washing the solution obtained in the step 2), protecting ultrasonic waves by using inert gas, then freezing the product at low temperature, transferring the completely frozen product into a freeze dryer, and freeze-drying at ultralow temperature for more than 72h;
4) Treating the powder sample obtained in the step 3) by using a spray drying method, blending the powder sample with graphene oxide, stirring and dispersing the mixture uniformly, finally adding a reducing agent, carrying out heating reaction to obtain the MXene-loaded three-dimensional graphene composite material, and carrying out freeze drying on the MXene-loaded three-dimensional graphene composite material to obtain the target product, namely the single-layer flower-shaped MXene nanosheet-loaded three-dimensional graphene composite material.
2. The method for preparing the monolayer flower-like MXene nanosheet-supported three-dimensional graphene composite material according to claim 1, wherein the graphene oxide is a commercial graphene oxide dispersion having a concentration of greater than 1mg/mL.
3. The preparation method of the monolayer flower-like MXene nanosheet-loaded three-dimensional graphene composite material as claimed in claim 1, wherein the reducing agent is: sodium ascorbate or ascorbic acid.
4. The method for preparing the monolayer flower-like MXene nanosheet-loaded three-dimensional graphene composite material as claimed in claim 1, wherein the MXene nanosheet comprises Ti 3 C 2 、Hf 3 C 2 Or Ti 2 C metal carbide.
5. The preparation method of the monolayer flower-like MXene nanosheet-loaded three-dimensional graphene composite material as claimed in claim 1, wherein the heating reaction temperature is 95 ℃ and the heating time is more than 2 h.
6. The monolayer flower-like MXene nanosheet-supported three-dimensional graphene composite material obtained by the preparation method of any one of claims 1 to 5.
7. The application of the monolayer flower-like MXene nanosheet-supported three-dimensional graphene composite material as an electrode material of a lithium-sulfur battery.
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| CN113629249B (en) * | 2021-06-10 | 2023-03-17 | 中国科学院金属研究所 | Preparation method of MXene-based supported platinum catalyst applied to lithium-sulfur battery anode |
| CN113998693A (en) * | 2021-10-22 | 2022-02-01 | 北京石墨烯技术研究院有限公司 | Preparation method of graphene nano-roll |
| CN113860309B (en) * | 2021-10-28 | 2023-05-12 | 赛轮集团股份有限公司 | Aerogel foam with mute function, preparation method thereof and tire |
| CN114249322B (en) * | 2021-12-27 | 2023-04-25 | 北京理工大学 | Nanometer flower-like VO 2 （B）/V 2 CT x Preparation method of composite material and sodium ion battery |
| CN115504473B (en) * | 2022-09-22 | 2023-08-04 | 南京大学 | MXene-based composite material for improving performance of lithium-sulfur battery diaphragm and preparation method thereof |
| CN115676831A (en) * | 2022-10-21 | 2023-02-03 | 南京航空航天大学 | Porous MXene material and preparation method and application thereof |
| CN116355462A (en) * | 2023-03-30 | 2023-06-30 | 南方科技大学 | Conductive ink without polymer matrix, composite sensor and preparation method thereof |
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| CN107633954B (en) * | 2016-07-19 | 2019-12-17 | 中国科学院上海硅酸盐研究所 | graphene/MXene composite electrode material and application thereof |
| CN107938026A (en) * | 2017-11-17 | 2018-04-20 | 浙江大学 | A kind of MXene fibers and preparation method thereof |
| CN108620003B (en) * | 2018-05-25 | 2021-05-18 | 哈尔滨工业大学 | Preparation method of stretchable MXene/graphene composite aerogel with high electromagnetic shielding effect |
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