CN114944481A - Mxene-optimized lithium-rich manganese-based composite positive electrode material and preparation method thereof - Google Patents

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

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CN114944481A
CN114944481A CN202210711997.6A CN202210711997A CN114944481A CN 114944481 A CN114944481 A CN 114944481A CN 202210711997 A CN202210711997 A CN 202210711997A CN 114944481 A CN114944481 A CN 114944481A
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mxene
lithium
rich manganese
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layer
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CN114944481B (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 anode material optimized by using Mxene, wherein the interlayer spacing of the few-layer Mxene is 10-16A. Ethanol is added during ultrasonic treatment of an etched Mxene precursor, a few-layer Mxene dispersion liquid is obtained through centrifugal treatment of the prepared multiple-layer Mxene dispersion liquid, and then the multi-layer Mxene dispersion liquid is compounded with a lithium-rich manganese-based positive electrode material, so that a few-layer Mxene modified lithium-rich manganese-based positive electrode material with an interlayer spacing of 10-16A is prepared, and a lithium insertion voltage platform can be provided at about 2.2V in a discharging process, so that the first coulombic efficiency can be effectively improved, the platform can be maintained for a long time in a long circulation process, the voltage attenuation and the capacity decline of the lithium-rich manganese-based material can be weakened, and the rate performance and the circulation performance can be obviously improved.

Description

Mxene-optimized lithium-rich manganese-based composite positive electrode material 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 using 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 cathode material still has difficulty in satisfying the increasing demand. The specific capacity of the lithium-rich manganese base reaches 300 mAh g -1 Can provide about 1000 Wh kg -1 The energy density of (1). In addition, the main raw material of the lithium-rich manganese base is Mn, the source is wide, the price is low, and the lithium-rich manganese base has cost advantage compared with the current common high-nickel material. However, the irreversible oxidation-reduction of O at high voltage on the lithium-rich manganese basis leads to a lower first coulombic efficiency, a less conductive Li of the composition 2 MnO 3 Is worsened by a multipleRate capability, unstable surface structure will lead to cycle performance decay and voltage decay. The defects seriously hinder the popularization and the application of the lithium-rich manganese base.
CN112164792A discloses a method for preparing MXene coated nickel-cobalt-manganese ternary cathode material, which comprises the steps of firstly preparing MXene dispersion liquid, preparing organ-shaped MXene by using MAX phase as raw material and acid etching, preparing MXene monolithic dispersion liquid by means of ultrasonic stripping, and enabling the prepared MXene dispersion liquid to be negatively charged on the basis of oxygen-containing functional groups on the surface of the MXene dispersion liquid. The positive charge is carried on the surface of the ternary positive electrode material by treating the nickel-cobalt-manganese ternary positive electrode material with a cationic surfactant, and the MXene lamella is coated on the surface of the nickel-cobalt-manganese ternary positive electrode material by electrostatic adsorption self-assembly. The MXene coating layer effectively isolates the direct contact of the ternary cathode material and the electrolyte, and the occurrence of direct contact side reaction is effectively avoided. The preparation method 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 cycle stability of the material. Although it is mentioned that the rate capability can be improved, the effect of improving the rate capability 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 loaded few-layer/rod-shaped MXene composite material and a preparation method thereof, and the preparation method comprises the following steps: adding multilayer two-dimensional MXene powder with preset mass into an intercalating agent, uniformly stirring by magnetic force, performing centrifugal treatment after complete reaction, and taking a lower-layer precipitate; adding the lower-layer precipitate into a three-neck flask, pouring deionized water, performing ultrasonic treatment in a gas atmosphere for a preset time, performing centrifugal treatment, taking the upper-layer liquid, and performing freeze drying to obtain less-layer/rod-shaped MXene; mixing the less-layer/rod-shaped MXene with the ternary material to prepare electrode slurry, coating the electrode slurry on an aluminum foil, and performing vacuum drying to form the ternary material loaded less-layer/rod-shaped MXene composite material. The invention can inhibit M-H2 phase change under higher voltage and absorb Ni/Co/Mn atoms due to the addition of MXene, and can reduce the generation rate of metal dendrites, thereby enhancing and stabilizing the nickel-rich positive electrode structure and keeping excellent multiplying power and cycle performance. However, in 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, the mixture is not tightly combined with the surface of the ternary material, the defect of unstable surface structure is difficult to improve, and the electrochemical performance improvement effect is unclear.
Disclosure of Invention
The invention aims to solve the technical problems that the defects are overcome, and the Mxene optimized lithium-rich manganese-based composite positive electrode material and the preparation method thereof are provided, the positive electrode material has higher first effect, simultaneously solves the problems of unstable surface structure and poor conductivity of the lithium-rich manganese base, and improves the rate capability and the cycling stability; the preparation method has simple process and low cost of raw materials.
Based on the characteristic that the Mxene material can improve the cycle performance and rate capability of the cathode material, the inventor tries to modify the lithium-rich manganese-based cathode material by using the material, however, the inventor finds that the rate capability improvement of the lithium-rich manganese-based cathode material modified by using the conventional Mxene material is limited, and the defects of low first coulombic efficiency and the like exist. Aiming at the technical problem, the inventor develops a new technical scheme through a large amount of researches, a lithium-embedded voltage platform can be provided at about 2.2V in the discharging process by preparing a few-layer Mxene with the interlayer spacing of 10-16A and modifying the lithium-rich manganese-based positive electrode material, so that the first coulombic efficiency can be effectively improved, and in the long circulation process, the platform can be kept for a long time, the voltage attenuation and the capacity decline of the lithium-rich manganese-based material can be weakened, and the multiplying power performance and the circulation performance can be obviously improved. The reason is that after ethanol is added during ultrasonic treatment of the etched Mxene precursor, the ethanol can play a role in washing, the interlayer spacing of the small-layer Mxene can be obviously increased, the small-layer 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 a position of about 2.2V in the discharging process, and the first efficiency, rate capability and cycle performance of the material are obviously improved.
The technical scheme of the application is as follows:
the lithium-rich manganese-based composite cathode material optimized by adopting Mxene comprises a lithium-rich manganese-based material and an few-layer Mxene, wherein the few-layer Mxene is of a nanosheet structure, and the interlayer spacing of the few-layer Mxene is 10-16A. The few-layer Mxene is usually 3-5 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 cannot be fully exerted due to too low Mxene content, and the energy density of the composite material is reduced due to too high Mxene content; the particle size 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 causes severe side reactions, and too large a lithium-rich manganese-based particle size may not allow close recombination with Mxene. Similarly, an excessively small length of Mxene results in failure to form effective recombination, and an excessively large length of Mxene results in self-agglomeration.
As a general inventive concept, the present application also provides a method for preparing a lithium-rich manganese-based composite positive electrode material optimized by using Mxene, comprising:
s1, etching the Mxene precursor by using LiF and concentrated hydrochloric acid, cleaning, performing ultrasonic treatment by using absolute ethyl alcohol, and performing centrifugation and solid-liquid separation to obtain a multilayer Mxene dispersion liquid;
s2, adding deionized water into the multi-layer Mxene dispersion liquid, carrying out centrifugal treatment, and taking supernate to obtain a small-layer Mxene dispersion liquid;
s3, dispersing the lithium-rich manganese-based material and the small-layer Mxene dispersion liquid in a solvent, stirring, carrying out ultrasonic treatment, filtering and drying to obtain a composite material;
and S4, carrying out vacuum sintering on the obtained composite material to obtain the required lithium-rich manganese-based composite material.
In the technical scheme, Li is used for corroding LiF and HCl + And also acts as an intercalant.
Preferably, in step S1, the etching conditions are: 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. Optimizing the etching conditions ensures that the etching can be carried out gently without unduly destroying the structure of Mxene itself.
Preferably, 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. The combination degree of the lithium-rich manganese base and the small-layer Mxene can be effectively improved through vacuum sintering, the Mxene is prevented from being oxidized to the maximum extent, and the combination degree of the composite material can be improved and the Mxene structure can be prevented from being damaged through the optimized vacuum sintering condition.
Preferably, in step S2, the centrifugation time is 60-80 min, and the centrifugation speed is 3200-3500 r/min. The centrifugal rotating speed is not suitable to be too high, otherwise, the content of the nanosheets in the supernatant is greatly reduced, and meanwhile, the rotating speed is not too low, otherwise, a large number of layers of Mxene exist in the supernatant, and the purity of the product is reduced.
Preferably, in step S2, the concentration of the low-layer Mxene dispersion is 5-8 mg/ml. If the concentration is too high, the particles are easy to agglomerate and are not well dispersed, and if the concentration is too low, the particles are insufficiently compounded with the lithium-rich manganese base.
Preferably, in 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 liquid is 12-15 mg/ml.
Preferably, in step S3, the solvent is at least one of deionized water, absolute ethyl alcohol and methanol; when the lithium-rich manganese-based material and the few-layer Mxene nanosheet dispersion liquid are dispersed in a solvent, the solid content is controlled to be 0.01-0.02 g/ml.
Preferably, in step S3, the stirring time is 12-18 min, the ultrasonic power is 100-200W, and the frequency is 30-40 kHz.
Preferably, in the step S3, the drying temperature is 60-80 ℃, and the drying time is 3-6 h.
In addition, in the step (3), the solvent is preferably one of absolute ethanol and methanol. The appropriate solid content concentration is beneficial to the good combination of the few-layer Mxene nanosheets 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, a stable lithium intercalation voltage platform can be provided at a position of about 2.2V in a discharging process by preparing the composite material of the few-layer Mxene and the lithium-rich manganese-based positive electrode material with the interlayer spacing of 10-16A, so that the first coulombic efficiency of the negative lithium-manganese-based positive electrode material can be effectively improved, the voltage attenuation and the capacity decline 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 nanosheets, the defect that the lithium-rich manganese-based conductivity is low can be overcome by utilizing the excellent conductivity of the Mxene, the instability of the surface structure of the material can be improved by utilizing the few-layer Mxene nanosheets covered on the surface of the lithium-rich manganese-based nanosheets, and the cycle performance is improved.
(2) According to the invention, a Mxene precursor is subjected to mild etching by using concentrated hydrochloric acid and LiF, anhydrous ethanol is used for ultrasonic treatment and centrifugal separation to obtain a multilayer Mxene dispersion liquid, a less-layer Mxene dispersion liquid is further obtained through centrifugal treatment, the less-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 a composite material of the less-layer Mxene and the lithium-rich manganese-based anode material with a layer spacing of 10-16 can be obtained, the composite material can enhance the conductivity of the lithium-rich manganese-based material and improve the unstable surface structure of the lithium-rich manganese-based anode material on one hand, and on the other hand, a less-layer nanosheet Mxene of the structure can provide an additional Li storage site and provide a stable lithium insertion voltage platform at about 2.2V during discharge, so that the first-time coulombic efficiency is greatly improved, and the rate performance and the cycle performance are obviously improved.
(3) The multilayer Mxene can enlarge the interlayer spacing through absolute ethyl alcohol in the washing ultrasonic process, increase the yield of few-layer Mxene nanosheets and has simple process flow; the lithium-rich manganese-based composite cathode material prepared by the method has excellent performance, simple preparation process and wide raw material source, and is suitable for large-scale popularization.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention in the prior art, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to do so without inventive work
Other figures were obtained.
FIG. 1 is an SEM image of an Mxene optimized lithium-rich manganese-based composite cathode material prepared in example 1 of the present invention;
fig. 2 is an SEM image of the 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 cathode material prepared in example 3 of the present invention;
FIG. 4 is a graph of the rate electrochemical performance of Mxene optimized lithium-rich manganese-based composite positive electrode materials prepared in examples 1, 2 and 3 of the present invention and comparative example 1;
FIG. 5 is a first-turn charge-discharge curve diagram of a battery assembled by the Mxene optimized lithium-rich manganese-based composite positive electrode material prepared in comparative example 1 and examples 1, 2 and 3 at a voltage range of 2.0-4.8V and a multiplying power of 0.1C;
FIG. 6 is a dQ/dV plot of discharge curves at different rates for cells assembled from Mxene optimized lithium-rich manganese-based composite positive electrode materials prepared in comparative example 1 and example 2;
FIG. 7 is an XRD pattern of Mxene prepared in example 1 and comparative example 2;
fig. 8 is a graph of the 1C discharge of Mxene optimized lithium rich manganese based composite cathode material assembled cells 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
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
All raw materials used are, unless otherwise specified, those commonly available on the market.
Example 1
A preparation method of a lithium-rich manganese-based composite positive electrode material optimized by Mxene comprises the following steps:
(1) preparation of multilayered Mxene dispersion:
1 g LiF was added to 9M of 40 ml concentrated hydrochloric acid, placed in an oil bath, stirred at 45 ℃ for 5 min, after which 1 g Ti was slowly added 3 AlC 2 Stirring was continued for 24 h. Adding deionized water into the obtained solution, centrifuging for 10 min, separating solid and liquid, adding anhydrous ethanol again, placing in an ultrasonic machine for ultrasonic treatment for 10 min with ultrasonic power of 100W and frequency of 40kHz, and then placing in a centrifuge again for centrifuging at 3500r/min for 10 min. The above procedure was repeated to obtain a multi-layer Mxene dispersion, where the Mxene material had been enlarged in interlayer spacing by the ethanol molecules.
(2) Preparation of few-layer Mxene nanosheets:
and adding deionized water into the obtained multilayer Mxene dispersion liquid, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for later use. The concentration of the prepared few-layer Mxene nanosheet dispersion liquid is 6.8 mg/ml. The XRD pattern of the prepared few-layer Mxene nanosheet is shown in fig. 7.
(3) Preparing a composite material: 0.5 g of Li was taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing in 50 ml of absolute ethyl alcohol, taking a small-layer Mxene nanosheet dispersion liquid containing 0.005 g (1 wt%) of the small-layer Mxene nanosheet, adding into the absolute ethyl alcohol solution, stirring for 15 min, performing ultrasonic treatment for 15 min, wherein the ultrasonic power is 100W, the frequency is 40kHz, filtering, and then transferring into an oven to dry at the drying temperature of 60 ℃ for 6 h.
(4) And (3) vacuum sintering: placing the dried composite material in a vacuum sintering furnace, and controlling the vacuum degree to be 10 -4 Pa～10 -2 Pa, sintering temperature of 180 ℃, sintering time of 4h, and furnace cooling to obtain the final material.
The SEM image of the prepared material is shown in figure 1, the lithium-rich manganese-based positive electrode material is spherical particles, has rough wrinkles on the surface and is flaky, and is a few-layer Mxene nanosheet, and the two materials are tightly combined.
Assembling the battery: 0.08 g of Mxene optimized lithium-rich manganese-based composite positive electrode material obtained in the embodiment is weighed, 0.01 g of acetylene black serving as a conductive agent, 0.01 g of polyvinylidene fluoride serving as a binder and N-methylpyrrolidone serving as a dispersing agent are added, the mixture is uniformly mixed and coated on aluminum foil to prepare a positive electrode plate, a metal lithium plate serves as a negative electrode, a composite film of PE and PP serves as a diaphragm, and 1 mol/L LiPF is added in a vacuum glove box 6 EC (volume ratio 1: 1) is used as electrolyte, and the button cell (complex phase material group) of CR2032 is assembled.
Comparative example 1
A button cell of CR2032 (comparative example 1) was assembled from lithium-rich manganese-based material not optimized using Mxene following the cell assembly procedure described above.
Two groups of batteries assembled by the composite materials prepared in example 1 and comparative example 1 are respectively discharged at rates of 0.2, 1 and 5C at the temperature of 25 ℃ and 2.0-4.8V, and a rate performance graph is shown in FIG. 4, wherein the discharge capacities of example 1 are 269.6, 234 and 145.8 mAh g respectively -1 。
Through further detection, the capacity retention rate of the assembled battery after 1C circulation for 200 circles is 88% under 2.0-4.8V.
Further examination revealed that the first coulombic efficiency of the assembled battery at 2.0-4.8V, when charged and discharged at 0.1C, was 93.68%, as shown in fig. 5.
Example 2
A preparation method of a lithium-rich manganese-based composite positive electrode material optimized by Mxene comprises the following steps:
(1) preparation of multilayered Mxene dispersion:
1 g LiF was added to 9M of 40 ml concentrated hydrochloric acid, placed in an oil bath, stirred at 45 ℃ for 5 min, after which 1 g Ti was slowly added 3 AlC 2 Stirring was continued for 24 h. Adding deionized water into the obtained solution, centrifuging for 10 min, separating solid and liquid, adding anhydrous ethanol, placing in ultrasonic machine for ultrasonic treatment for 10 min with ultrasonic power of 100W and frequency of 40kHz, and placing in centrifuge again to 3500 r/based on the weight of the solutionAnd (5) centrifuging for 10 min. The above procedure was repeated to obtain a multi-layered Mxene dispersion.
(2) Preparation of few-layer Mxene nanosheets:
and adding deionized water into the obtained multilayer Mxene dispersion liquid, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for later use. The concentration of the prepared few-layer Mxene nanosheet dispersion liquid is 6.5 mg/ml.
(3) Preparing a composite material: 0.5 g of Li was taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing the mixture into 50 ml of absolute ethyl alcohol, taking a small-layer Mxene nanosheet dispersion liquid containing 0.015 g (3 wt%), adding the small-layer Mxene nanosheet dispersion liquid into the absolute ethyl alcohol solution, stirring for 15 min, carrying out ultrasound for 15 min, wherein the ultrasound power is 100W, the frequency is 40kHz, filtering, and then, transferring the mixture into an oven to dry, wherein the drying temperature is 60 ℃, and the drying time is 6 h.
(4) Vacuum sintering: placing the dried composite material in 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 4h, the final material can be obtained after furnace cooling, and the SEM image of the prepared material is shown in figure 2, and the Mxene compounded on the particles is gradually increased along with the increase of the Mxene content.
Assembling the battery: weighing 0.08 g of the lithium-rich manganese-based composite positive electrode material obtained in the embodiment, adding 0.01 g of acetylene black serving as a conductive agent, 0.01 g of polyvinylidene fluoride serving as a binder and N-methylpyrrolidone serving as a dispersing agent, uniformly mixing, coating the mixture on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, a composite film of PE and PP as a diaphragm and 1 mol/L LiPF in a vacuum glove box 6 EC (volume ratio 1: 1) is electrolyte, and the button cell of CR2032 is assembled.
Through detection, the discharge is respectively carried out at 0.2, 1 and 5C multiplying powers under 2.0-4.8V and 25 ℃, wherein the discharge capacities of the embodiment 2 are respectively 260.1, 232.7 and 158.3mAh g -1 。
Through detection, the capacity retention rate of the assembled battery after 1C circulation for 200 circles is 87.6% under 2.0-4.8V.
The first coulombic efficiency of the assembled battery at 2.0-4.8V and 0.1C charging and discharging is 93.62%, as shown in fig. 5.
The dQ/dV plots of the discharge curves at different rates for the composite assembled cells prepared in comparative example 1 and example 2 are shown in fig. 6, and it can be seen that the 2.2V plateau provided by Mxene contributes significantly to the capacity.
Example 3
A lithium-rich manganese-based composite positive electrode material optimized by Mxene is prepared by the following steps:
(1) preparation of multilayered Mxene dispersion:
1 g LiF was added to 9M of 40 ml concentrated hydrochloric acid, placed in an oil bath, stirred at 45 ℃ for 5 min, after which 1 g Ti was slowly added 3 AlC 2 Stirring was continued for 24 h. Adding deionized water into the obtained solution, centrifuging for 10 min, separating solid and liquid, adding anhydrous ethanol again, placing in an ultrasonic machine for ultrasonic treatment for 10 min with ultrasonic power of 100W and frequency of 40kHz, and then placing in a centrifuge again for centrifuging at 3500r/min for 10 min. The above procedure was repeated to obtain a plurality of Mxene dispersions.
(2) Preparation of few-layer Mxene nanosheets:
and adding deionized water into the obtained multilayer Mxene dispersion liquid, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for later use. The concentration of the prepared few-layer Mxene nanosheet dispersion liquid is 6.7 mg/ml.
(3) Preparing a composite material: 0.5 g of Li was taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing the mixture into 50 ml of absolute ethyl alcohol, adding a small-layer Mxene nanosheet dispersion liquid containing 0.025 g (5 wt%) into the absolute ethyl alcohol solution, stirring for 15 min, performing ultrasonic treatment for 15 min, wherein the ultrasonic power is 100W, the frequency is 40kHz, filtering, and then transferring into an oven to dry, wherein the drying temperature is 60 ℃ and the drying time is 6 h.
(4) And (3) vacuum sintering: placing the dried composite material in a vacuum sintering furnace, and controlling the vacuum degree to be 10 -4 Pa～10 -2 Pa, sintering temperature of 180 ℃, sintering time of 4h, furnace cooling to obtain the final material, SEM picture of the prepared material is shown in figure 3, and with Mxene contentThe number of the particles is increased, the particles are coated with the Mxene more and more, and Mxene nano sheets are almost combined around the particles.
Assembling the battery: weighing 0.08 g of the lithium-rich manganese-based composite positive electrode material obtained in the embodiment of the invention, adding 0.01 g of acetylene black serving as a conductive agent, 0.01 g of polyvinylidene fluoride serving as a binder and N-methylpyrrolidone serving as a dispersing agent, uniformly mixing, coating the mixture on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, a PE and PP composite membrane as a diaphragm and 1 mol/L LiPF in a vacuum glove box 6 EC (volume ratio 1: 1) is electrolyte, and a CR2032 button cell is assembled.
Through detection, the discharge capacity of the embodiment 3 is 256.9, 239.8 and 131.1 mAh g respectively under the discharge rates of 0.2, 1 and 5C under the temperature of 2.0-4.8V and 25 DEG C -1 。
Through detection, the capacity retention rate of the assembled battery after 1C circulation for 200 circles is 85.30% under 2.0-4.8V. The discharge curve at 1C is shown in fig. 8, from which it is evident that a discharge plateau occurs at around 2.2V.
The first coulombic efficiency of the assembled battery at 2.0-4.8V and 0.1C charging and discharging is 94.01%, as shown in fig. 5. As can be seen from fig. 5, the plateau of 2.2V is more pronounced as the amount of Mxene coating increases, providing higher capacity with greater first effect.
Comparative example 2
A preparation method of a lithium-rich manganese-based composite positive electrode material optimized by Mxene comprises the following steps:
(1) preparation of multilayered Mxene dispersion:
1 g LiF was added to 9M of 40 ml concentrated hydrochloric acid, placed in an oil bath, stirred at 45 ℃ for 5 min, after which 1 g Ti was slowly added 3 AlC 2 Stirring was continued for 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 with ultrasonic power of 100W and frequency of 40kHz, and then placing in a centrifuge again for centrifuging at 3500r/min for 10 min. The steps are repeated to obtain a plurality of Mxene dispersion liquid layers, and the Mxene material at the moment is etched under a long-time mild condition, so that the interlayer spacing is enlarged.
(2) Preparation of few-layer Mxene nanosheets:
and adding deionized water into the obtained multilayer Mxene dispersion liquid, setting a centrifuge at 3500r/min, centrifuging for 60 min, sucking out supernatant, and refrigerating for later use. The XRD pattern of the prepared few-layer Mxene nanosheet is shown in fig. 7.
(3) Preparing a composite material: 0.5 g of Li was taken 1.2 Mn 0.54 Ni 0.13 Mn 0.13 O 2 Placing in 50 ml of absolute ethyl alcohol, taking a small-layer Mxene nanosheet dispersion liquid containing 0.005 g (1 wt%) of the small-layer Mxene nanosheet, adding into the absolute ethyl alcohol solution, stirring for 15 min, performing ultrasonic treatment for 15 min, wherein the ultrasonic power is 100W, the frequency is 40kHz, filtering, and then transferring into an oven to dry at the drying temperature of 60 ℃ for 6 h.
(4) And (3) vacuum sintering: placing the dried composite material in 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 4h, the final material can be obtained after furnace cooling, 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 rough wrinkles on the surface, is flaky and is a few-layer Mxene nanosheet.
Assembling the battery: weighing 0.08 g of Mxene optimized lithium-rich manganese-based composite positive electrode material obtained in the comparative example, adding 0.01 g of acetylene black serving as a conductive agent, 0.01 g of polyvinylidene fluoride serving as a binder and N-methylpyrrolidone serving as a dispersing agent, uniformly mixing, coating the mixture on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, a PE and PP composite membrane as a diaphragm and 1 mol/L LiPF in a vacuum glove box 6 EC (volume ratio 1: 1) is used as electrolyte, and the button cell (complex phase material group) of CR2032 is assembled.
Detection shows that no corresponding platform appears at 2.2V, and 243.7 mAh g, 198 mAh g and 104 mAh g are respectively discharged at 0.2, 1 and 5C multiplying powers at 2.0-4.8V and 25 DEG C -1 . The discharge curve at 1C is shown in fig. 8, and it is obvious that no discharge plateau occurs around 2.2V.
Through further detection, the first coulombic efficiency of 0.1C charging and discharging of the assembled battery is 69.06% under 2.0-4.8V.
The XRD patterns of the Mxene 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 relative to comparative example 2, indicating that the interlayer spacing of the Mxene tablet prepared in example 1 is larger. The interlayer spacing of the Mxene sheets prepared in example 1 was 15.649 a and that 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, analysis shows that example 1 widens the interlayer distance of a few layers of Mxene due to the addition of ethanol, so that the product has a sufficiently large interlayer distance, and a 2.2V lithium intercalation platform is activated, so that the performance of the composite is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The lithium-rich manganese-based composite cathode 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 nanosheet structure, and the interlayer spacing of the few-layer Mxene is 10-16A.
2. The Mxene-optimized lithium-rich manganese-based composite positive electrode material as claimed in claim 1, wherein the mass ratio of the lithium-rich manganese-based material to the Mxene is 100: 1-5; the particle size of the lithium-rich manganese-based material is 5-15 mu m, and the length of the Mxene is 3-10 mu m.
3. A preparation method of a lithium-rich manganese-based composite positive electrode material optimized by Mxene is characterized by comprising the following steps:
s1, etching the Mxene precursor by using LiF and concentrated hydrochloric acid, cleaning, performing ultrasonic treatment by using absolute ethyl alcohol, and performing centrifugation and solid-liquid separation to obtain a multilayer Mxene dispersion liquid;
s2, adding deionized water into the multi-layer Mxene dispersion liquid, carrying out centrifugal treatment, and taking supernate to obtain a small-layer Mxene dispersion liquid;
s3, dispersing the lithium-rich manganese-based material and the small-layer Mxene dispersion liquid in a solvent, stirring, carrying out ultrasonic treatment, filtering and drying to obtain a composite material;
and S4, carrying out 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 using an Mxene according to claim 3, wherein in step S1, said etching conditions are: the temperature is 40-50 ℃, the stirring time is 24-30 hours, the concentration of concentrated hydrochloric acid is 8-10 mol/L, the mass ratio of 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 Mxene optimized lithium-rich manganese-based composite cathode material as claimed in claim 3, wherein in step S4, the temperature of the vacuum sintering 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 Mxene optimized lithium-rich manganese-based composite cathode material as claimed in claim 3, wherein in step S2, the time of centrifugation is 60-80 min, and the rotation speed of centrifugation is 3200-3500 r/min.
7. The method for preparing a Mxene optimized lithium-rich manganese-based composite positive electrode material as claimed in claim 3, wherein, in step S2, the concentration of the few-layer Mxene dispersion liquid is 5-8 mg/ml.
8. The method for preparing the Mxene optimized lithium-rich manganese-based composite cathode material as claimed in claim 3, wherein in 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 liquid is 12-15 mg/ml.
9. The method for preparing a Mxene-optimized lithium-rich manganese-based composite positive electrode material as claimed in claim 3, wherein in step S3, the solvent is at least one of deionized water, absolute ethyl alcohol and methanol; when the lithium-rich manganese-based material and the few-layer Mxene nanosheet dispersion liquid are dispersed in a solvent, the solid content is controlled to be 0.01-0.02 g/ml.
10. The method for preparing a Mxene optimized lithium-rich manganese-based composite cathode material as claimed in claim 3, wherein 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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