CN114944481B - Lithium-rich manganese-based composite positive electrode material optimized by Mxene and preparation method thereof - Google Patents

Lithium-rich manganese-based composite positive electrode material optimized by Mxene and preparation method thereof Download PDF

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CN114944481B
CN114944481B CN202210711997.6A CN202210711997A CN114944481B CN 114944481 B CN114944481 B CN 114944481B CN 202210711997 A CN202210711997 A CN 202210711997A CN 114944481 B CN114944481 B CN 114944481B
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mxene
lithium
rich manganese
positive electrode
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CN114944481A (en
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郑俊超
韦韩信
汤林波
罗玉红
黄英德
李沛垚
贺振江
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Central South University
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Abstract

The invention discloses a lithium-rich manganese-based composite positive electrode material optimized by Mxene, wherein the interlayer spacing of a few Mxene layers is 10-16A. Ethanol is added during ultrasonic treatment of the etched Mxene precursor, the prepared multi-layer Mxene dispersion liquid is subjected to centrifugal treatment to obtain a few-layer Mxene dispersion liquid, and then the few-layer Mxene dispersion liquid is compounded with a lithium-rich manganese-based positive electrode material to prepare the few-layer Mxene modified lithium-rich manganese-based positive electrode material with the layer spacing of 10-16A, and a lithium-intercalation voltage platform can be provided at about 2.2V in the discharging process, so that the first coulomb efficiency can be effectively improved, the platform can be kept for a long time in the long-cycle process, the voltage attenuation and capacity decay of the lithium-rich manganese-based material can be weakened, and the multiplying power performance and the cycle performance can be obviously improved.

Description

Lithium-rich manganese-based composite positive electrode material optimized by Mxene and preparation method thereof
Technical Field
The invention belongs to the field of preparation of battery anode materials, and particularly relates to a lithium-rich manganese-based composite anode material optimized by Mxene and a preparation method thereof.
Background
With the progress of science and technology and the development of society, lithium ion batteries have been widely used in the fields of military industry, traffic, electronic equipment, large-scale energy storage and the like. However, the energy density of the positive electrode material is still difficult to meet the increasing demands of people. The specific capacity of the lithium-rich manganese base is up to 300 mAh g -1 Can provide about 1000 Wh kg -1 Is a high energy density. In addition, the main raw material of the lithium-rich manganese base is Mn, and has wide sources and low price, and compared with the high-nickel material commonly used at present, the lithium-rich manganese base has more cost advantages. However, irreversible O-redox of lithium-rich manganese groups at high voltages results in lower first coulombic efficiency, less conductive Li in the composition 2 MnO 3 The rate performance is deteriorated, and unstable surface structure will lead to cycle performance degradation and voltage degradation. The above-mentioned drawbacks seriously hamper the popularization and application of lithium-rich manganese bases.
CN112164792A discloses a preparation method of an MXene-coated nickel-cobalt-manganese ternary cathode material, wherein MXene dispersion liquid is prepared firstly, MAX phase is used as a raw material for preparing accordion-shaped MXene by an acid etching method, the MXene is prepared into MXene single-piece dispersion liquid by means of ultrasonic stripping, and the prepared MXene dispersion liquid is negatively charged based on oxygen-containing functional groups on the surface of the MXene single-piece dispersion liquid. And (3) treating the nickel-cobalt-manganese ternary positive electrode material by using a cationic surfactant to enable the surface of the ternary positive electrode to be positively charged, and enabling the MXene sheet layer to be coated on the surface of the nickel-cobalt-manganese ternary positive electrode material by using electrostatic adsorption self-assembly. The existence of the MXene coating layer effectively isolates three layersThe direct contact of the positive electrode material and the electrolyte effectively avoids the occurrence of direct contact side reaction. The preparation method disclosed by the invention is simple, short in flow, easy to operate in steps, excellent in material processing performance and electrochemical performance, capable of reducing the impedance of the battery and improving the high-rate performance and the cycling stability of the material. Although it is mentioned that the rate performance can be improved, the effect of improving the rate performance is not ideal from the result, and the electrochemical performance of the prepared composite material is still not good at a large rate (5C), and is only 40 mAh g -1 。
CN112103504a discloses a ternary material supported few-layer/rod-shaped MXene composite material and a preparation method thereof, comprising the following steps: adding multilayer two-dimensional MXene powder with preset mass into an intercalation agent, uniformly stirring through magnetic force, performing centrifugal treatment after complete reaction, and taking out a lower layer of sediment; adding the lower layer precipitate into a three-neck flask, pouring deionized water, performing ultrasonic treatment for a preset time under a gas atmosphere, performing centrifugal treatment, taking an upper layer solution, and freeze-drying to obtain a few-layer/rod-shaped MXene; and mixing the less-layer/rod-shaped MXene with the ternary material to prepare electrode slurry, coating the electrode slurry on an aluminum foil, and carrying out vacuum drying to form the ternary material loaded less-layer/rod-shaped MXene composite material. The added MXene can inhibit M-H2 phase transition at higher voltage and absorb Ni/Co/Mn atoms, so that the generation rate of metal dendrites can be reduced, and the nickel-rich positive electrode structure is enhanced and stabilized, and excellent multiplying power and cycle performance are maintained. However, in the summary of the invention, the few-layer/rod-shaped Mxene is mainly used as an additive in the electrode manufacturing process to be mixed with the ternary material, so that the surface of the ternary material is not tightly combined, the defect of unstable surface structure is difficult to improve, and the electrochemical performance improving effect is not clear.
Disclosure of Invention
The invention aims to solve the technical problems, and provides the lithium-rich manganese-based composite positive electrode material optimized by Mxene and the preparation method thereof, and the positive electrode material has higher initial efficiency, improves the problems of unstable structure and poor conductivity of the lithium-rich manganese-based surface, and improves the multiplying power performance and the cycling stability; the preparation method has simple process and low raw material cost.
Based on the characteristic that Mxene materials can improve the cycle performance and the rate performance of the positive electrode material, the inventors tried to modify the lithium-rich manganese-based positive electrode material by using the material, however, the inventors found that the rate performance of the lithium-rich manganese-based positive electrode material modified by using the conventional Mxene material is improved only a limited extent, and the first coulombic efficiency is low. Aiming at the technical problem, the inventor develops a new technical scheme through a large number of researches, and prepares a few-layer Mxene with the layer spacing of 10-16A and modifies the lithium-rich manganese-based positive electrode material, wherein the few-layer Mxene can provide a lithium-embedded voltage platform at about 2.2V in the discharging process, so that the first coulomb efficiency can be effectively improved, and the platform can be kept for a long time in the long-cycle process, so that the voltage attenuation and capacity decay of the lithium-rich manganese-based material can be weakened, and further the multiplying power performance and the cycle performance can be obviously improved. Through analysis, the reason is that after ethanol is added in the ultrasonic treatment of the etched Mxene precursor, the ethanol not only can play a role in washing, but also can obviously increase the interlayer spacing of the few layers Mxene, so that the few layers Mxene with the interlayer spacing obviously widened by the ethanol is obtained, a storage site of Li can be provided, a stable lithium intercalation voltage platform can be provided at about 2.2V in the discharging process, and further, the first effect, the multiplying power performance and the cycle performance of the material are obviously improved.
The technical scheme of the application is as follows:
the lithium-rich manganese-based composite positive electrode material optimized by using Mxene comprises a lithium-rich manganese-based material and a few-layer Mxene, wherein the few-layer Mxene is of a nano-sheet structure, and the interlayer spacing of the few-layer Mxene is 10-16A. The few layers Mxene are typically 3 to 5 layers.
The lithium-rich manganese-based material is (1-x) Li 2 MnO 3 ·xLi(Ni a Co b Mn c )O 2 Wherein a+b+c=1.
Preferably, the mass ratio of the lithium-rich manganese-based material to the Mxene is 100:1-5, the advantage of the material cannot be fully improved due to the fact that the Mxene content is too low, and the energy density of the composite material can be reduced due to the fact that the Mxene content is too high; the grain diameter of the lithium-rich manganese-based material is 5-15 mu m, and the length of the Mxene is 3-10 mu m. Too small a lithium-rich manganese-based particle size results in severe side reactions, and too large a lithium-rich manganese-based particle size may result in less tight recombination with Mxene. Likewise, too small a length of Mxene results in failure to form an effective complex, and too large a length of Mxene results in a tendency to agglomerate itself.
As a general inventive concept, the present application also provides a method for preparing a lithium-rich manganese-based composite cathode material optimized by Mxene, comprising:
s1, etching an Mxene precursor by using LiF and concentrated hydrochloric acid, cleaning, performing ultrasonic treatment by using absolute ethyl alcohol, and obtaining a multilayer Mxene dispersion after centrifugation and solid-liquid separation;
s2, adding deionized water into the multilayer Mxene dispersion liquid, performing centrifugal treatment, and taking supernatant to obtain a few-layer Mxene dispersion liquid;
s3, dispersing the lithium-rich manganese-based material and the few-layer Mxene dispersion liquid in a solvent, stirring, performing ultrasonic treatment, filtering, and drying to obtain a composite material;
and S4, performing vacuum sintering on the obtained composite material to obtain the required lithium-rich manganese-based composite material.
In the technical proposal, li is as follows in the corrosion process of LiF and HCl + Also acts as an intercalating agent.
Preferably, in step S1, the etching conditions are as follows: the temperature is 40-50 ℃, the stirring time is 24-30 h, the concentration of concentrated hydrochloric acid is 8-10 mol/L, the mass ratio of the Mxene precursor to LiF is 1:1-3, and the molar ratio of LiF to concentrated hydrochloric acid is 1:8-12. By optimizing the etching conditions, it is ensured that the etching can be performed mildly without excessively destroying the structure of Mxene itself.
Preferably, in the step S4, the vacuum sintering temperature is 150-220 ℃, the sintering time is 4-18 h, and the vacuum pressure is 10 -4 ～10 -2 Pa. The bonding degree of the lithium-rich manganese base and the few-layer Mxene can be effectively improved through vacuum sintering, the Mxene is prevented from being oxidized to the greatest extent, and the bonding degree of the composite material can be improved through optimized vacuum sintering conditions, and meanwhile the Mxene structure is prevented from being damaged.
Preferably, in the step S2, the centrifugation time is 60-80 min, and the centrifugation rotating speed is 3200-3500 r/min. The centrifugal speed is not too high, otherwise the nano-sheet content of the supernatant fluid is greatly reduced, and the speed is not too low, otherwise a large number of multi-layer Mxene exists in the supernatant fluid, so that the purity of the product is reduced.
Preferably, in step S2, the concentration of the minor-layer Mxene dispersion is 5-8 mg/ml. Too concentrated concentration is easy to agglomerate and disperse well, and too low concentration is insufficient to be compounded with lithium-rich manganese base.
Preferably, in the step S1, the rotation speed of the centrifugation is 3200-3800 r/min, and the centrifugation time is 8-12 min; the power of the ultrasonic wave is 100-200W, and the frequency of the ultrasonic wave is 35-40 kHz; the solid content of the multilayer Mxene dispersion is 12-15 mg/ml.
Preferably, in step S3, the solvent is at least one of deionized water, absolute ethanol and methanol; the solid content of the lithium-rich manganese-based material and the few-layer Mxene nano-sheet dispersion liquid is controlled to be 0.01-0.02 g/ml when the lithium-rich manganese-based material and the few-layer Mxene nano-sheet dispersion liquid are dispersed in a solvent.
Preferably, in the step S3, the stirring time is 12-18 min, the ultrasonic power is 100-200W, and the frequency is 30-40 kHz.
Preferably, in step S3, the drying temperature is 60-80 ℃ and the drying time is 3-6 h.
In step (3), the solvent is preferably one of absolute ethanol and methanol. The proper solid content concentration is beneficial to the good combination of the few-layer Mxene nano-sheets and the lithium-rich manganese-based particles.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the composite material, the composite material of the few-layer Mxene with the interlayer spacing of 10-16A and the lithium-rich manganese-based positive electrode material is prepared, a stable lithium intercalation voltage platform can be provided at the position of about 2.2V in the discharging process, so that the first coulombic efficiency of the negative lithium-manganese-based positive electrode material can be effectively improved, the voltage attenuation and capacity decay of the lithium-rich manganese-based material can be weakened, the multiplying power performance and the cycle performance are improved, the lithium-rich manganese-based positive electrode material is compounded with the few-layer Mxene nano-sheets, the defect of low conductivity of the lithium-rich manganese-based can be improved by utilizing the extremely good conductivity of the Mxene, the surface structure instability of the material can be improved by the few-layer Mxene nano-sheets covered on the surface of the lithium-rich manganese-based material, and the cycle performance is improved.
(2) According to the invention, concentrated hydrochloric acid and LiF are adopted to carry out mild etching on an Mxene precursor, absolute ethyl alcohol is adopted to carry out ultrasonic treatment, centrifugal separation is carried out to obtain a multi-layer Mxene dispersion liquid, further centrifugal treatment is carried out to obtain a few-layer Mxene dispersion liquid, the few-layer Mxene dispersion liquid is compounded with a lithium-rich manganese-based material, and the obtained composite material is subjected to vacuum sintering, so that the composite material of the few-layer Mxene with the layer spacing of 10-16A and the lithium-rich manganese-based positive electrode material can be obtained, on one hand, the conductivity of the lithium-rich manganese-based material is enhanced, and the unstable surface structure of the lithium-rich manganese-based material is improved, on the other hand, the few-layer nano-sheet Mxene with the structure can provide an extra Li storage site, and a stable lithium-intercalation voltage platform is provided at about 2. 2.2V during discharge, so that the first-time coulombic efficiency is greatly improved, and the multiplying power performance and the cycle performance are obviously improved.
(3) The multilayer Mxene not only can enlarge the interlayer spacing through absolute ethyl alcohol in the ultrasonic washing process, but also can increase the yield of few-layer Mxene nano-sheets, and the process flow is simple; the lithium-rich manganese-based composite positive electrode material prepared by the method has excellent performance, simple preparation flow and wide raw material sources, and is suitable for large-scale popularization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described, it will be apparent to those skilled in the art that the drawings in the description are embodiments of the present invention and that the drawings can be made according to the drawings without inventive effort
Other figures are obtained.
FIG. 1 is an SEM image of an Mxene optimized lithium-rich manganese-based composite positive electrode material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of an Mxene optimized lithium-rich manganese-based composite positive electrode material prepared in example 2 of the present invention;
FIG. 3 is an SEM image of an Mxene optimized lithium-rich manganese-based composite positive electrode material prepared in example 3 of the present invention;
FIG. 4 is a graph showing the rate electrochemical performance of the Mxene-optimized lithium-rich manganese-based composite positive electrode materials prepared in examples 1, 2, and 3 and comparative example 1 of the present invention;
FIG. 5 is a first charge-discharge plot of the Mxene optimized lithium-rich manganese-based composite positive electrode material assembled batteries prepared in comparative example 1 and examples 1, 2, 3 at a voltage range of 2.0-4.8V, multiplying power of 0.1C;
FIG. 6 is a dQ/dV plot of discharge curves at different rates for batteries assembled from the Mxene optimized lithium-rich manganese-based composite positive electrode materials prepared in comparative example 1 and example 2;
FIG. 7 is XRD patterns of Mxene prepared in example 1 and comparative example 2;
FIG. 8 is a 1C discharge plot of cells assembled from the Mxene optimized lithium-rich manganese-based composite positive electrode materials prepared in comparative example 2 and example 3;
fig. 9 is an SEM image of the Mxene optimized lithium-rich manganese-based composite positive electrode material prepared in comparative example 2.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Unless otherwise specified, all raw materials were used as common commercial products.
Example 1
The preparation method of the lithium-rich manganese-based composite positive electrode material optimized by Mxene comprises the following steps:
(1) Preparation of a multilayered Mxene dispersion:
adding 1 g LiF into 9M concentrated hydrochloric acid 40 ml, placing into an oil bath, stirring at 45deg.C for 5 min, and slowly adding 1 g Ti 3 AlC 2 Stirring was continued for 24 h. Adding deionized water into the obtained solution, centrifuging for 10 min, separating solid from liquid, adding anhydrous ethanol again, and placing into an ultrasonic machine for ultrasonic treatment for 10 minmin, ultrasonic power 100W, frequency 40kHz, and then centrifuge again in a centrifuge at 3500r/min for 10 min. After repeating the above steps, the multi-layer Mxene dispersion is prepared, at which time the Mxene material has been enlarged in interlayer spacing by the ethanol molecules.
(2) Preparation of few-layer Mxene nanosheets:
adding deionized water into the obtained multilayer Mxene dispersion, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for use. The concentration of the prepared few-layer Mxene nano-sheet dispersion liquid is 6.8 mg/ml. The XRD pattern of the few-layer Mxene nanoplatelets prepared is shown in FIG. 7.
(3) Preparation of the composite material: 0.5 g Li is taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing in 50 ml absolute ethyl alcohol, taking a few-layer Mxene nano-sheet dispersion liquid containing 0.005 g (1 wt%) and adding the nano-sheet dispersion liquid into the absolute ethyl alcohol solution, stirring for 15 min, carrying out ultrasonic treatment for 15 min, wherein the ultrasonic power is 100W, the frequency is 40kHz, filtering, transferring into an oven, and drying at the temperature of 60 ℃ for 6 h.
(4) Vacuum sintering: placing the dried composite material into a vacuum sintering furnace, and controlling the vacuum degree to be 10 -4 Pa～10 -2 Pa, the sintering temperature is 180 ℃, the sintering time is 4 hours, and the final material can be obtained after cooling along with a furnace.
As shown in the SEM graph of the prepared material in FIG. 1, the lithium-rich manganese-based positive electrode material is spherical particles, has unsmooth folds on the surface, is in a flake shape, is a few-layer Mxene nano-sheet, and is tightly combined with the material.
Assembling a battery: weighing 0.08 g of the Mxene optimized lithium-rich manganese-based composite positive electrode material obtained in the embodiment, adding 0.01 g acetylene black as a conductive agent, 0.01 polyvinylidene fluoride as a binder and N-methylpyrrolidone as a dispersing agent, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a metal lithium plate as a negative electrode in a vacuum glove box, taking a composite film of PE and PP as a diaphragm, and 1 mol/L LiPF 6 DMC: EC (volume ratio 1:1) is electrolyte, assembled into a button cell (complex phase material group) of CR 2032.
Comparative example 1
A button cell of CR2032 (comparative example 1) was assembled using a lithium-rich manganese-based material that was not optimized for Mxene according to the above-described battery assembly procedure.
The two groups of batteries assembled by the composite materials prepared in the example 1 and the comparative example 1 are respectively discharged at the temperature of 2.0-4.8V and 25 ℃ at the multiplying power of 0.2, 1 and 5C, the multiplying power performance chart is shown in figure 4, wherein the discharge capacity of the example 1 is 269.6, 234 and 145.8 mAh g respectively -1 。
The assembled cell was further tested for 88% capacity retention after 200 cycles of 1C at 2.0-4.8V.
Upon further testing, the assembled cell had a first coulombic efficiency of 93.68% for 0.1C charge and discharge at 2.0-4.8V, as shown in fig. 5.
Example 2
The preparation method of the lithium-rich manganese-based composite positive electrode material optimized by Mxene comprises the following steps:
(1) Preparation of a multilayered Mxene dispersion:
adding 1 g LiF into 9M concentrated hydrochloric acid 40 ml, placing into an oil bath, stirring at 45deg.C for 5 min, and slowly adding 1 g Ti 3 AlC 2 Stirring was continued for 24 h. Adding deionized water into the obtained solution, centrifuging for 10 min, adding absolute ethyl alcohol again after solid-liquid separation, placing into an ultrasonic machine for ultrasonic treatment for 10 min, wherein the ultrasonic power is 100W and the frequency is 40kHz, and then placing into a centrifuge again for centrifugation for 10 min at 3500r/min. The above steps were repeated to obtain a multi-layered Mxene dispersion.
(2) Preparation of few-layer Mxene nanosheets:
adding deionized water into the obtained multilayer Mxene dispersion, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for use. The concentration of the prepared few-layer Mxene nano-sheet dispersion liquid is 6.5 mg/ml.
(3) Preparation of the composite material: 0.5 g Li is taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing in 50 ml absolute ethanol, collecting 0.015-g (3 wt%) less-layer Mxene nanosheet dispersion, adding into the above absolute ethanol solution, stirring for 15min, ultrasonic for 15 min, the ultrasonic power is 100W, the frequency is 40kHz, the filter is put into an oven for drying, the drying temperature is 60 ℃, and the drying time is 6 h.
(4) Vacuum sintering: placing the dried composite material into a vacuum sintering furnace, and controlling the vacuum degree to be 10 -4 Pa～10 -2 Pa, the sintering temperature is 180 ℃, the sintering time is 4 hours, the final material can be obtained after cooling along with a furnace, and the SEM image of the prepared material is shown in figure 2, and the composite Mxene on the particles gradually increases along with the increase of the Mxene content.
Assembling a battery: weighing 0.08 g of the lithium-rich manganese-based composite positive electrode material obtained in the embodiment, adding 0.01 g acetylene black as a conductive agent, 0.01 g polyvinylidene fluoride as a binder and N-methylpyrrolidone as a dispersing agent, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a metal lithium plate as a negative electrode, taking a composite film of PE and PP as a diaphragm in a vacuum glove box, and 1 mol/L LiPF 6 DMC: EC (volume ratio 1:1) is electrolyte, and the CR2032 button cell is assembled.
Through detection, 0.2, 1 and 5C multiplying power discharge is respectively carried out at 2.0-4.8V and 25 ℃, wherein the discharge capacity of the embodiment 2 is respectively 260.1, 232.7 and 158.3mAh g -1 。
The assembled cell was tested for a capacity retention of 87.6% after 200 cycles of 1C at 2.0-4.8V.
The assembled cell was tested to have a first coulombic efficiency of 93.62% for 0.1C charge and discharge at 2.0-4.8V, as shown in fig. 5.
The dQ/dV graphs of the discharge curves of the cells assembled from the composites prepared in comparative example 1 and example 2 at different rates are shown in FIG. 6, and it can be seen that the 2.2V platform provided by Mxene contributes very much to the capacity.
Example 3
The preparation method of the lithium-rich manganese-based composite positive electrode material optimized by Mxene comprises the following steps:
(1) Preparation of a multilayered Mxene dispersion:
adding 1 g LiF into 9M concentrated hydrochloric acid 40 ml, placing into an oil bath, stirring at 45deg.C for 5 min, and slowly adding 1 g Ti 3 AlC 2 Stirring was continued for 24 h. Adding deionized water into the obtained solution, centrifuging for 10 min, adding absolute ethyl alcohol again after solid-liquid separation, placing into an ultrasonic machine for ultrasonic treatment for 10 min, wherein the ultrasonic power is 100W and the frequency is 40kHz, and then placing into a centrifuge again for centrifugation for 10 min at 3500r/min. The above steps were repeated to obtain a multi-layered Mxene dispersion.
(2) Preparation of few-layer Mxene nanosheets:
adding deionized water into the obtained multilayer Mxene dispersion, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for use. The concentration of the prepared few-layer Mxene nano-sheet dispersion liquid is 6.7 mg/ml.
(3) Preparation of the composite material: 0.5 g Li is taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing in 50 ml absolute ethyl alcohol, taking a few-layer Mxene nano-sheet dispersion liquid containing 0.025 g (5 wt%) and adding the nano-sheet dispersion liquid into the absolute ethyl alcohol solution, stirring for 15 min, carrying out ultrasonic treatment for 15 min, wherein the ultrasonic power is 100W, the frequency is 40kHz, filtering, transferring into an oven, and drying at the temperature of 60 ℃ for 6 h.
(4) Vacuum sintering: placing the dried composite material into a vacuum sintering furnace, and controlling the vacuum degree to be 10 -4 Pa～10 -2 Pa, the sintering temperature is 180 ℃, the sintering time is 4 hours, the final material can be obtained after cooling along with a furnace, the SEM image of the prepared material is shown in figure 3, as the content of Mxene increases, the particles are increasingly coated by the Mxene, the thickness of the particles is increased, and the Mxene nano-sheets are almost combined around the particles.
Assembling a battery: weighing 0.08 g of the lithium-rich manganese-based composite positive electrode material obtained by the embodiment of the invention, adding 0.01 g acetylene black as a conductive agent, 0.01 g polyvinylidene fluoride as a binder and N-methylpyrrolidone as a dispersing agent, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a metal lithium plate as a negative electrode, taking a composite film of PE and PP as a diaphragm and 1 mol/L LiPF in a vacuum glove box 6 DMC: EC (volume ratio 1:1) is electrolyte, and the CR2032 button cell is assembled.
Through detection, at the temperature of 2.0-4.8V and 25 ℃,discharge rates of 0.2, 1, and 5C, respectively, wherein discharge capacities of example 3 were 256.9, 239.8, and 131.1 mAh g, respectively -1 。
The assembled cell was tested for a capacity retention of 85.30% after 200 cycles of 1C at 2.0-4.8V. The discharge graph at 1C is shown in fig. 8, from which it is apparent that a discharge plateau occurs at around 2.2V.
The assembled cell was tested to have a first coulombic efficiency of 94.01% for 0.1C charge and discharge at 2.0-4.8V, as shown in fig. 5. As can be seen from fig. 5, the higher the capacity provided, the greater the first effect, the more pronounced the 2.2V plateau increases with increasing Mxene coating.
Comparative example 2
The preparation method of the lithium-rich manganese-based composite positive electrode material optimized by Mxene comprises the following steps:
(1) Preparation of a multilayered Mxene dispersion:
adding 1 g LiF into 9M concentrated hydrochloric acid 40 ml, placing into an oil bath, stirring at 45deg.C for 5 min, and slowly adding 1 g Ti 3 AlC 2 Stirring was continued 48 h. Adding deionized water into the obtained solution, centrifuging for 10 min, performing solid-liquid separation, placing in an ultrasonic machine for ultrasonic treatment for 10 min, wherein the ultrasonic power is 100W and the frequency is 40kHz, and then placing in a centrifugal machine again for centrifuging for 10 min at 3500r/min. After repeating the above steps, the multi-layer Mxene dispersion liquid, the Mxene material at this time has an enlarged interlayer spacing due to the etching under mild conditions for a long time.
(2) Preparation of few-layer Mxene nanosheets:
adding deionized water into the obtained multilayer Mxene dispersion, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for use. The XRD pattern of the few-layer Mxene nanoplatelets prepared is shown in FIG. 7.
(3) Preparation of the composite material: 0.5 g Li is taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing in 50 ml absolute ethanol, collecting a few-layer Mxene nanosheet dispersion liquid containing 0.005 g (1 wt%) and adding into the absolute ethanol solution, stirring for 15 min, and ultrasonic treating for 15 min with ultrasonic power of 100W at frequencyThe rate is 40kHz, after filtration, the mixture is transferred into an oven for drying, the drying temperature is 60 ℃, and the drying time is 6 h.
(4) Vacuum sintering: placing the dried composite material into a vacuum sintering furnace, and controlling the vacuum degree to be 10 -4 Pa～10 -2 Pa, the sintering temperature is 180 ℃, the sintering time is 4 hours, and the final material can be obtained after cooling along with a furnace, wherein an SEM image is shown in figure 9, and as can be seen from figure 9, the lithium-rich manganese-based positive electrode material is spherical particles, has unsmooth folds on the surface, is flaky and is a few-layer Mxene nano-sheet.
Assembling a battery: weighing the Mxene optimized lithium-rich manganese-based composite positive electrode material obtained in the comparative example of 0.08 and g, adding 0.01 g acetylene black as a conductive agent, 0.01 polyvinylidene fluoride as a binder and N-methylpyrrolidone as a dispersing agent, uniformly mixing, coating on aluminum foil to prepare a positive electrode plate, taking a metal lithium plate as a negative electrode, taking a composite film of PE and PP as a diaphragm and 1 mol/L LiPF in a vacuum glove box 6 DMC: EC (volume ratio 1:1) is electrolyte, assembled into a button cell (complex phase material group) of CR 2032.
Through detection, no corresponding platform appears in 2.2V, and at 2.0-4.8V and 25 ℃, the magnifications of 0.2, 1 and 5C are respectively discharged to 243.7, 198 and 104 mAh g -1 . The discharge graph at 1C is shown in fig. 8, from which it is apparent that no discharge plateau occurs at around 2.2V.
Further testing shows that the initial coulombic efficiency of 0.1C charge and discharge at 2.0-4.8V is 69.06%.
The XRD patterns of the Mxene sheets prepared in comparative example 2 and example 1 are shown in FIG. 7, and it can be seen that the 002 peak of the XRD pattern of example 1 is significantly shifted to the left with respect to comparative example 2, indicating that the interlayer spacing of the Mxene sheets prepared in example 1 is greater. The layer spacing of the Mxene sheets prepared in example 1 was 15.649 a and the layer spacing of the Mxene sheets prepared in comparative example 2 was 13.039 a, calculated according to the bragg diffraction equation. In combination with electrochemical data, it is considered through analysis that the ethanol is added in the embodiment 1, the interlayer spacing of the few layers of Mxene is widened, so that the product has enough interlayer spacing, and the lithium intercalation platform of 2.2V is activated, so that the performance of the compound is improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The lithium-rich manganese-based composite positive electrode material optimized by using Mxene is characterized by comprising a lithium-rich manganese-based material and a few-layer Mxene, wherein the few-layer Mxene is of a nano-sheet structure, and the interlayer spacing of the few-layer Mxene is 10-16A; the few layers Mxene are 3-5 layers; the mass ratio of the lithium-rich manganese-based material to the Mxene is 100:1-5.
2. The Mxene optimized lithium-rich manganese-based composite positive electrode material according to claim 1, characterized in that the particle size of the lithium-rich manganese-based material is 5-15 μm, the length of Mxene is 3-10 μm.
3. A method for preparing the Mxene optimized lithium-rich manganese-based composite positive electrode material according to claim 1 or 2, comprising:
s1, etching an Mxene precursor by using LiF and concentrated hydrochloric acid, cleaning, performing ultrasonic treatment by using absolute ethyl alcohol, and obtaining a multilayer Mxene dispersion by centrifugation and solid-liquid separation;
s2, adding deionized water into the multilayer Mxene dispersion liquid, performing centrifugal treatment, and taking supernatant to obtain a few-layer Mxene dispersion liquid;
s3, dispersing the lithium-rich manganese-based material and the few-layer Mxene dispersion liquid in a solvent, stirring, performing ultrasonic treatment, filtering, and drying to obtain a composite material;
and S4, performing vacuum sintering on the obtained composite material to obtain the required lithium-rich manganese-based composite material.
4. The method for preparing a lithium-rich manganese-based composite positive electrode material optimized by Mxene according to claim 3, wherein in step S1, the etching conditions are as follows: the temperature is 40-50 ℃, the stirring time is 24-30 h, the concentration of concentrated hydrochloric acid is 8-10 mol/L, the mass ratio of the Mxene precursor to LiF is 1:1-3, and the molar ratio of LiF to concentrated hydrochloric acid is 1:8-12.
5. The method for preparing a lithium-rich manganese-based composite positive electrode material optimized by Mxene according to claim 3, characterized in that in step S4, the vacuum sintering temperature is 150-220 ℃, the sintering time is 4-18 h, and the vacuum pressure is 10 -4 ～10 -2 Pa。
6. The method for preparing the lithium-rich manganese-based composite positive electrode material optimized by Mxene according to claim 3, characterized in that in step S2, the centrifugation time is 60-80 min, and the centrifugation rotation speed is 3200-3500 r/min.
7. The method for preparing a lithium-rich manganese-based composite positive electrode material optimized by Mxene according to claim 3, wherein the concentration of the less layer Mxene dispersion liquid in step S2 is 5-8 mg/ml.
8. The method for preparing the lithium-rich manganese-based composite positive electrode material optimized by Mxene according to claim 3, characterized in that in step S1, the rotational speed of the centrifugation is 3200-3800 r/min, and the centrifugation time is 8-12 min; the power of the ultrasonic wave is 100-200W, and the frequency of the ultrasonic wave is 35-40 kHz; the solid content of the multilayer Mxene dispersion is 12-15 mg/ml.
9. The method for preparing a lithium-rich manganese-based composite cathode material optimized by Mxene according to claim 3, wherein in step S3, the solvent is at least one of deionized water, absolute ethanol and methanol; the solid content of the lithium-rich manganese-based material and the few-layer Mxene nano-sheet dispersion liquid is controlled to be 0.01-0.02 g/ml when the lithium-rich manganese-based material and the few-layer Mxene nano-sheet dispersion liquid are dispersed in a solvent.
10. The method for preparing the lithium-rich manganese-based composite positive electrode material optimized by Mxene according to claim 3, characterized in that in step S3, the stirring time is 12-18 min, the ultrasonic power is 100-200W, and the frequency is 30-40 kHz.
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