CN115440964A - Ion battery negative electrode active material, negative electrode, and ion battery - Google Patents

Ion battery negative electrode active material, negative electrode, and ion battery Download PDF

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CN115440964A
CN115440964A CN202211233492.XA CN202211233492A CN115440964A CN 115440964 A CN115440964 A CN 115440964A CN 202211233492 A CN202211233492 A CN 202211233492A CN 115440964 A CN115440964 A CN 115440964A
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mxene
ion battery
ldh
negative electrode
active material
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CN115440964B (en
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汪俊岭
周浩波
王志荣
喻水
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Nanjing Tech University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an ion battery negative electrode active material, which comprises MXene nanosheets and metal selenide Co loaded on the surfaces of the MXene nanosheets x Ni 1‑x Se 2 And said metal selenide Co x Ni 1‑x Se 2 A nitrogen-doped carbon layer coated on the surface; compared with a graphite cathode, the cathode made of the ion battery cathode active material provided by the invention has higher specific capacity, excellent rate performance and cycling stability; this is achieved byIn addition, the peak temperature of the lithium ion battery using the ion battery cathode active material provided by the invention as the cathode material is lower than that of the battery using the graphite cathode when thermal runaway occurs, so that the thermal runaway hazard of the lithium ion battery can be effectively reduced, and the safety is improved.

Description

Ion battery negative electrode active material, negative electrode, and ion battery
Technical Field
The invention relates to the field of electrode materials of ion batteries, in particular to a negative electrode active material of an ion battery, a negative electrode and an ion battery.
Background
Lithium Ion Batteries (LIBs) have been widely used due to their excellent performance, and as the market scale of batteries grows larger, the lithium ore resources are gradually in short supply. The characteristics of Sodium Ion Batteries (SIBs) are similar to those of lithium ion batteries, and sodium resources are abundant, so that the battery has low cost and good development prospect.
The graphite is used as the anode material of the current commercial lithium ion battery, and the highest theoretical specific capacity is 372mAh.g -1 Due to the limitation of various factors, the specific capacity of the material in practical use can not reach 350mAh.g -1 . The volume change of the cathode material caused by the insertion/extraction process of sodium ions is larger due to larger ion radius, and the capacity of the graphite cathode in the sodium ion battery is even lower than 35mAh.g -1 . Therefore, it is difficult for the graphite negative electrode to satisfy the demand for high energy density lithium ion batteries and the development of future sodium ion batteries.
In the development of a new high-specific-capacity negative electrode material, a metal chalcogenide has 2-3 times of theoretical specific capacity of graphite, but has the defects of low conductivity, high volume change rate, fragile structure and the like, so that the serious capacity decline is caused.
Patent literature with publication number CN112079338B, namely three-dimensional foam-shaped composite material, preparation method and application of three-dimensional foam-shaped composite material in sodium-ion batteries provides Ti 3 C 2 MXene and cobalt nickel selenide are compounded into three-dimensional foam Co x Ni 1- x Se @ MXene material, 253.6mAh.g. was obtained in sodium ion batteries -1 Although the reversible specific capacity of the graphite material shows electrical performance superior to that of the graphite material to a certain extent, a larger promotion space still exists in the specific capacity and the cycling stability;
in addition, the safety of the lithium ion battery is always a human problem, and once the battery generates a thermal runaway fire, the battery can cause great damage to life and property. The case report that the fire disaster of the electric automobile causes the car to be destroyed and the people to be killed is frequently repeated. Therefore, it is necessary to improve the safety of the lithium battery by improving the electrode material itself and reduce the damage caused by thermal runaway of the lithium battery.
Disclosure of Invention
Aiming at the defects of the current commercial technology, the invention provides an active material MXene/Co of the negative electrode of the ion battery x Ni 1-x Se 2 /C(0<x<1) Composite nano material, preparation method thereof and application thereof in ion batteries. Compared with a graphite cathode, the cathode manufactured by the negative electrode active material of the ion battery has higher specific capacity, excellent rate capability and cycling stability; in addition, MXene/Co was used x Ni 1-x Se 2 The peak temperature of the lithium ion battery taking the/C as the cathode material is lower than that of a battery using a graphite cathode when thermal runaway occurs, so that the thermal runaway hazard of the lithium ion battery can be effectively reduced, and the safety is improved.
The invention adopts the following technical scheme:
in a first aspect, the invention provides an ion battery negative electrode active material, which comprises MXene nanosheets and metal selenide Co loaded on the surfaces of the MXene nanosheets x Ni 1-x Se 2 And said metal selenide Co x Ni 1-x Se 2 A nitrogen-doped carbon layer coated on the surface;
the MXene nanosheet is obtained by etching MXene precursor, namely MAX-phase raw material, by using a mixed solution of lithium fluoride and hydrochloric acid; in the MAX phase, M represents a transition metal element, A represents a main group element, and X represents carbon or nitrogen, and the variety thereof includes but is not limited to Ti 3 AlC 2 、Mo 3 AlC 2 、Ti 3 AlCN、V 2 AlC、V 4 AlC 3 、Nb 2 AlC、Nb 4 AlC 3 、Ta 2 One or more of AlC; preferably, the MAX phase is Ti 3 AlC 2 The MXene prepared correspondingly is Ti 3 C 2 T x ；
The metal selenide Co loaded on MXene nano-sheets x Ni 1-x Se 2 The carbon layer coated on the surface of the carbon layer is prepared by the following steps: on MXene chipGrowing LDH in a position to obtain an intermediate product MXene/LDH; then, adding dopamine hydrochloride into the intermediate product MXene/LDH to coat Polydopamine (PDA) on the surface of the intermediate product MXene/LDH/PDA to obtain the intermediate product MXene/LDH/PDA; finally, mixing the intermediate product MXene/LDH/PDA with selenium powder and calcining in an inert gas atmosphere to finally obtain the metal selenide Co loaded on the MXene nano-sheet and coated with the carbon layer x Ni 1-x Se 2 (ii) a The LDH is a layered double hydroxide comprising two metals, cobalt and nickel;
the MXene nano-sheet has large specific surface area, high conductivity and rich surface active point sites, is very suitable to be used as a carrier of an electrode active material, and is prepared by mixing flaky Co x Ni 1-x Se 2 Loading on MXene nano-sheet to form porous nano-structure; MXene/Co x Ni 1-x Se 2 Abundant holes are beneficial to the wetting of electrolyte and the quick transmission of electrons and ions, and provide enough ion diffusion space, so that the stress and volume expansion in the insertion/de-intercalation process are relieved, the electrode is prevented from being broken, and the stable structure of the electrode is ensured; using metal selenides Co x Ni 1-x Se 2 As an active material, the material has higher theoretical specific capacity than graphite; however, co x Ni 1- x Se 2 The conductivity is low, so that the negative electrode active material of the ion battery is formed by MXene/Co x Ni 1-x Se 2 The surface is coated with a nitrogen-doped carbon layer, and the conductive carbon layer improves Co x Ni 1-x Se 2 The defect of low conductivity optimizes the overall conductivity, can promote charge transfer, accelerate ion transfer, and can be used as a protective layer to further strengthen the structural stability; MXene/CoNiSe is obtained through the optimized design of three aspects of surface appearance, space structure and material composition 2 the/C composite nanometer negative electrode material.
Preferably, the mass ratio of MXene nanosheets to LDH in the MXene/LDH is 1:5-1; further preferably, the mass ratio of MXene nanosheets to LDH in the MXene/LDH is 1; the molar ratio of nickel and cobalt elements in the LDH is 1.5-1:5; more preferably, the molar ratio of nickel and cobalt elements in the LDH is 1:2;
preferably, the mass ratio of MXene/LDH to dopamine hydrochloride is 1.5-1:2; further preferably, the mass ratio of MXene/LDH to dopamine hydrochloride is 1:1;
preferably, the mass ratio of MXene/LDH/PDA to selenium powder is 1:1-1:4; further preferably, the mass ratio of MXene/LDH/PDA to selenium powder is 1:2;
the invention also provides a preparation method of the negative electrode active material of the ion battery, which comprises the following steps:
step S1, dissolving lithium fluoride powder in hydrochloric acid to obtain a first mixed solution, adding MXene precursor, namely MAX-phase raw material powder, heating in a water bath, keeping stirring, centrifuging a product, and washing the product with deionized water; finally, dispersing the product in water for ultrasonic treatment, and then placing the product in a centrifuge for centrifugal separation to prepare MXene dispersion liquid;
step S2, mixing and stirring a cobalt salt solution, a nickel salt solution and MXene dispersion liquid to obtain a second mixed solution, adding ammonia water into the second mixed solution, heating and stirring the mixture in a water bath in an inert gas atmosphere, then carrying out hydrothermal reaction, carrying out centrifugal treatment on a product, washing the product with deionized water, and carrying out freeze drying to obtain MXene/LDH;
step S3, dispersing MXene/LDH in deionized water, carrying out ultrasonic stirring, adding dopamine hydrochloride and 1mol/L Tris-Cl buffer solution, fully stirring, centrifuging the product, washing with deionized water, and carrying out freeze drying to obtain MXene/LDH/PDA;
step S4, MXene/Co preparation x Ni 1-x Se 2 C: mixing and grinding MXene/LDH/PDA and selenium powder, putting into a tube furnace, and calcining in an inert gas atmosphere to selenize and carbonize; the selenizing calcination temperature range is 300-400 ℃, and the time is 4-6 hours; the carbonization and calcination temperature range is 500-600 ℃, and the time is 1-2 hours.
Step S5, stirring the calcined product in carbon disulfide, washing off redundant elemental selenium, centrifugally separating, and drying in vacuum to obtain MXene/Co x Ni 1-x Se 2 /C。
Preferably, in step S2, the cobalt salt is one of cobalt acetate, cobalt nitrate, cobalt chloride and cobalt oxalate; the nickel salt is one of nickel acetate, nickel nitrate, nickel chloride and nickel oxalate.
Preferably, in step S2 and step S4, the inert gas is nitrogen or argon.
In a second aspect, the invention provides an ion battery anode made of MXene/Co material x Ni 1-x Se 2 the/C is used as a negative active material;
preferably, the manufacturing process of the negative electrode of the ion battery comprises the following steps: mixing MXene/Co x Ni 1-x Se 2 Putting the/C powder, conductive carbon black and binder into a mortar for grinding for 15-30 min to obtain slurry, coating the slurry on a copper foil by a scraper, punching a pole piece into a wafer after drying, and obtaining MXene/Co x Ni 1-x Se 2 a/C pole piece; more preferably, the binder is 5% PVDF/NMP;
in a third aspect, the invention provides an ion battery, wherein the negative electrode of the ion battery is used as a negative electrode, and the ion battery is a lithium ion battery or a sodium ion battery.
Compared with the prior art, the method has the advantages and beneficial effects that:
MXene/CoNiSe 2 the/C has a unique spatial hierarchical structure, small volume change rate and high cycle stability in the electrochemical process; the large number of nanopores and the optimized surface conductivity can support the rapid movement of ions, combined with Co x Ni 1-x Se 2 So that the material shows excellent rate capability and specific capacity. In addition to excellent electrochemical performance, MXene/CoNiSe 2 Compared with commercial graphite, the thermal stability of the material is better, the material can play a role similar to a flame retardant in a lithium battery thermal runaway fire, and metal elements in the material have a catalytic carbonization effect, so that the generation of combustible cracking products is reduced; the flaky structure can reinforce and stabilize the carbon layer, and block oxygen and heat, thereby inhibiting combustion, reducing heat release and improving the safety of the battery.
Drawings
FIG. 1 is Ti of step 1 in example 1 3 AlC 2 Raw material and Ti 3 C 2 T x XRD test spectrogram of the nanosheet;
FIG. 2 is an XRD test spectrum of MXene/LDH product of step 2 in example 1;
FIG. 3 shows MXene/Co product from step 4 of example 1 x Ni 1-x Se 2 XRD test spectrogram of/C;
FIG. 4 is an SEM image of the products of step 1, step 2 and step 4 of example 1 and an elemental distribution map of an EDS analysis of a local position of step 4; wherein the diagram (a) is the product Ti of step 1 in example 1 3 C 2 T x SEM images of the nanoplatelets; (b) The figure is an SEM image of MXene/LDH product of step 2 in example 1; (c) The figure is the product MXene/Co of step 4 in example 1 x Ni 1- x Se 2 SEM image of/C; FIG. d is a partially enlarged image of FIG. c; (e) The plot is (c) an elemental distribution plot of an EDS analysis of the plot location;
FIG. 5 shows MXene/Co, a product of example 1 x Ni 1-x Se 2 BET test results of/C;
FIG. 6 shows the results of the cycle performance test of the assembled lithium ion battery of example 3;
FIG. 7 is the results of a rate capability test of the assembled lithium ion battery of example 3;
fig. 8 is the cycle test results of the assembled lithium ion battery of example 3; wherein the diagram (a) shows MXene/Co after the cycle test of the lithium ion battery assembled in the example 3 x Ni 1-x Se 2 SEM image of/C cathode material; FIG. b is a partially enlarged image of FIG. a; (c) The figure is (a) elemental distribution plots of EDS analysis of the plot locations;
FIG. 9 shows the results of the cycle performance test of the assembled sodium-ion battery of example 4;
figure 10 is the rate performance test results for the assembled sodium ion battery of example 4.
Fig. 11 is a comparison of the peak temperatures of ARC tests for graphite-lithium ion assembled in comparative example 1 and lithium ion assembled in example 3.
Detailed Description
The present invention is described in detail below with reference to preferred embodiments in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may be made in light of the above teachings. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercially available products; the process steps or extraction methods not mentioned in detail are all process steps or extraction methods known to the person skilled in the art.
Example 1
The method for preparing the negative active material MXene/Co of the ion battery comprises the following steps x Ni 1-x Se 2 /C：
Step S1, dissolving 1g of lithium fluoride in 20mL of hydrochloric acid to prepare a solution containing hydrofluoric acid, wherein the concentration of the hydrochloric acid is 9-12 mol/L, and adding 1g of Ti to the solution 3 AlC 2 Keeping stirring the powder in a water bath at 35 ℃, and carrying out etching reaction for 24-48h; after the etching reaction was completed, first centrifugation was performed at 3500rpm, and the lower layer was precipitated to obtain Ti 3 C 2 T x Washing with deionized water to pH 6-7, and adding Ti 3 C 2 T x Dispersing in deionized water, ultrasonically treating for stripping, finally performing second centrifugal treatment at 3500rpm, and taking the upper suspension to obtain MXene dispersion liquid containing MXene nanosheets.
And step S2, dissolving 7.48g of nickel acetate tetrahydrate and 10.62g of cobalt acetate in 600mL of deionized water, uniformly stirring, adding 150mL of MXene dispersion liquid with the concentration of 3mg/mL and 25mL of ammonia water, stirring the mixed system in a water bath at the temperature of 80 ℃ for 10 hours, introducing argon for protection, then transferring into a hydrothermal kettle, and carrying out hydrothermal reaction at the temperature of 150 ℃ for 6 hours. Centrifuging at 10000rpm for 3min, collecting the product, washing with deionized water for 5 times, and freeze-drying to obtain MXene/LDH.
Step S3, 500mg of prepared MXene/LDH was added to 200mL of deionized water and treated with ultrasonic agitation for 10min. Additional 500mg of dopamine hydrochloride was added and stirred vigorously for 1 hour. Then 50mL of 50mM Tris-Cl solution was added and mixed, and the mixture was stirred for 24 hours. The product was collected by centrifugation (10000rpm, 3min), washed 5 times with deionized water, and freeze-dried to obtain MXene/LDH/PDA.
And S4, mixing and grinding MXene/LDH/PDA and selenium powder according to the mass ratio of 1:2, putting the mixture into a tube furnace, introducing argon for calcination, calcining at 350 ℃ for 6h for selenization, and calcining at 600 ℃ for 2h for carbonization.
Step S5, putting the calcined product into carbon disulfide according to the ratio of 1 x Ni 1-x Se 2 /C。
Raw material Ti 3 AlC 2 And Ti 3 C 2 T x The XRD spectrum of (A) is shown in FIG. 1, after etching and stripping, the diffraction peak of Al element disappears, and Ti element 3 C 2 T x The diffraction peak of (a) is shifted to a small angle, which is an indication of increased lamella spacing, indicating that the resulting product is Ti 3 C 2 T x A nanosheet of (a).
The XRD spectrogram of MXene/LDH is shown in figure 2, the diffraction peak of the XRD spectrogram is consistent with the standard card of CoNi-LDH, and the LDH is proved to be successfully coated with Ti 3 C 2 T x The surface of the nanoplatelets.
MXene/Co x Ni 1-x Se 2 The XRD spectrum of/C is shown in figure 3, the diffraction peak is consistent with the standard card of metal selenide, which indicates that the final product of the embodiment is MXene/Co x Ni 1-x Se 2 /C。
The scanning electron microscope image of the product of each step in the present example is shown in fig. 4, in which (a) in fig. 4 is MXene nanosheet; FIG. 4 (b) is MXene/LDH, and it can be seen that the flake LDH is coated on the MXene surface; FIG. 4 (c) shows MXene/Co x Ni 1-x Se 2 FIG. 4 (d) is an enlarged view of part of the structure, and it is clear that Co is in the form of flakes x Ni 1-x Se 2 And a carbon layer having irregularities thereon. FIG. 4 (e) is the element distribution result of the EDS analysis at the position of FIG. 4 (C), and the elements Ti, C, co, ni and Se are observed.
FIG. 5 is MXene/Co x Ni 1-x Se 2 Adsorption/desorption isotherm curve of/C, specific surface area 175.3cm 2 g -1 And an average pore size of about 5.47 nm. The obtained material has a porous structure, provides rich active point positions and space for the storage of lithium/sodium particles, and can shorten the movement path of ions, thereby improving the specific capacity and rate capability of the battery.
The above results show that the preparation method of the embodiment can successfully synthesize MXene/Co with special composition and structure x Ni 1-x Se 2 And C, material.
Example 2
The MXene/Co as the negative electrode of the ion battery is prepared by the following steps x Ni 1-x Se 2 C pole piece:
0.07g of MXene/Co prepared in example 1 was weighed x Ni 1-x Se 2 Grinding the powder C, conductive carbon black Super P0.02 g and PVDF/NMP 0.2g (5% concentration) in a mortar for 30min to obtain slurry, coating the slurry on a copper foil by a scraper with the diameter of 100 mu m, drying, punching the pole piece into a circular sheet with the diameter of 12mm, and obtaining MXene/Co x Ni 1-x Se 2 And putting the/C pole piece into a glove box for later use.
Example 3
The lithium ion battery is assembled according to the following steps:
assembling the lithium ion battery in a glove box, and sequentially placing a lithium sheet, a Celgard2325 diaphragm and 80 mu L of lithium battery secondary electrolyte (1.0M LiPF) into a 2032 type battery negative electrode shell 6 DEC = 1%/EC), MXene/Co made in example 2 x Ni 1-x Se 2 And (3) placing the/C pole piece (the coating surface faces the diaphragm), the gasket and the elastic sheet on the positive shell, and pressing and sealing the positive shell.
The lithium ion battery assembled in the embodiment 3 is subjected to performance test by using a Xinwei battery test system, the multiplying power of the first 5 circles is 0.1C under the cycle test working condition, and then the lithium ion battery is cycled by using the multiplying power of 1C, and the voltage is 0.1-3V; the cycle test working condition is 0.1C/0.5C/1C/2C/4C/0.1C, each multiplying power is 5 circles, and the voltage is 0.1-3V.
The cycle test results of the lithium ion battery are shown in FIG. 6, at 0.1A g -1 At a current density ofThe reversible specific capacity of the ring is 764 mAh.g -1 With 1 A.g -1 After the current density is circulated for 500 circles, the capacity can still retain 365mAh g -1 The coulomb efficiency remains around 100%. The results of the rate test are shown in FIG. 7, at 4A g -1 Can maintain 366mAh g at high current density -1 Specific capacity and current density of (2) are returned to 0.1 A.g -1 Then, the specific capacity is recovered to 678 mAh.g -1 Indicating MXene/Co x Ni 1-x Se 2 the/C cathode material can still keep stable structure under the impact of large current density and is not damaged.
MXene/Co x Ni 1-x Se 2 As shown in fig. 8, after the long-cycle scanning microscope image of/C is operated in a lithium ion battery, a large number of mesh holes are formed on an MXene sheet, and an active material and a carbon material are uniformly distributed therein, so that the morphology structure is very beneficial to the rapid insertion/extraction movement of lithium ions, and the volume expansion is accommodated, and the structure stability is maintained.
The above results show MXene/Co x Ni 1-x Se 2 the/C works as a negative electrode in the lithium ion battery and shows excellent specific capacity, cycling stability and rate capability.
Example 4
The sodium ion battery is assembled according to the following steps:
the batteries were assembled in a glove box, and sodium sheets, glass fiber membranes, and 80 μ L sodium battery secondary electrolyte (1.0M NaCF) were sequentially placed in a 2032 type battery negative electrode case 3 SO 3 /DIGLYME), MXene/Co from example 2 x Ni 1-x Se 2 And (3) placing the/C pole piece (the coating surface faces the diaphragm), the gasket and the elastic sheet on the positive shell, and pressing and sealing the positive shell.
Using a Xinwei battery test system to carry out performance test, wherein the multiplying power of the first 5 circles is 0.1C under the cyclic test working condition, and then using the multiplying power of 1C to circulate, wherein the voltage is 0.1-3V; the cycle test working condition is 0.1C/0.5C/1C/2C/4C/0.1C, each multiplying power is 5 circles, and the voltage is 0.1-3V.
The cycle performance of the sodium ion battery is shown in FIG. 9, using MXene/Co x Ni 1-x Se 2 Sodium ion of/C pole pieceBattery, 0.1A · g -1 The reversible specific capacity of the first loop under the current density reaches 551 mAh.g -1 ，1A·g -1 The current density circulates for 130 circles, the capacity is basically not attenuated, and the capacity is kept at 433.5 mAh.g -1 Coulombic efficiency remained essentially at 100%. The results of the magnification test are shown in FIG. 10, at 4A g -1 Has a high current density of 360mAh g -1 The specific capacity of (A). MXene/Co x Ni 1-x Se 2 The performance of the/C material in the sodium-ion battery is far superior to that of a graphite material, and the material has the potential of serving as a negative electrode of the sodium-ion battery.
Comparative example 1
Assembling the graphite-lithium ion battery according to the following steps:
the assembled graphite-lithium ion battery was compared to the procedure of the assembled lithium ion battery of example 3, except that this example used a graphite pole piece instead of MXene/Co x Ni 1-x Se 2 The graphite pole piece is consistent with MXene/Co manufactured in example 2 in other operations x Ni 1-x Se 2 The difference of the/C pole piece is only that the graphite pole piece uses commercial graphite in place of MXene/Co x Ni 1-x Se 2 powder/C, consistent with the rest.
An adiabatic acceleration calorimeter (ARC) is a thermal analysis based on an adiabatic principle, can enable a sample to be in an adiabatic environment, automatically tracks the reaction exothermic process of the sample after the sample reaches a certain temperature by using a heating-waiting-detecting test mode, and quickly and accurately provides thermodynamic information of the exothermic reaction. The lithium batteries assembled in example 3 and comparative example 1 were tested using ARC, respectively, and the exothermic characteristics of the thermal runaway processes of the two batteries were compared, and the peak temperature of thermal runaway of both batteries is shown in fig. 11, and the peak temperature of the lithium ion battery using commercial graphite as the negative electrode is 505 ℃, and MXene/Co is used x Ni 1-x Se 2 The peak temperature of the battery of the/C pole piece is 452 ℃, and is reduced by 53 ℃ compared with that of a graphite cathode battery. Indicating the use of Co x Ni 1-x Se 2 The lithium ion battery cathode can obviously inhibit the thermal runaway heat release and reduce the thermal runaway accident hazard of the lithium ion battery.

Claims (10)

1. An ion battery negative electrode active material comprises MXene nanosheets and metal selenide Co loaded on the surfaces of the MXene nanosheets x Ni 1-x Se 2 And said metal selenide Co x Ni 1-x Se 2 A nitrogen-doped carbon layer coated on the surface;
the MXene nanosheet is obtained by etching MXene precursor, namely MAX phase raw material, by using a mixed solution of lithium fluoride and hydrochloric acid;
the metal selenide Co loaded on MXene nano-sheets x Ni 1-x Se 2 The carbon layer coated on the surface of the carbon layer is prepared by the following steps: growing LDH on MXene sheet in situ to obtain intermediate product MXene/LDH; then, adding dopamine hydrochloride into the intermediate product MXene/LDH to coat Polydopamine (PDA) on the surface of the intermediate product MXene/LDH/PDA to obtain the intermediate product MXene/LDH/PDA; finally, mixing the intermediate product MXene/LDH/PDA with selenium powder and calcining in an inert gas atmosphere to finally obtain the metal selenide Co loaded on the MXene nano-sheet and coated with the carbon layer x Ni 1-x Se 2 (ii) a The LDH is a layered double hydroxide comprising two metals, cobalt and nickel.
2. The negative electrode active material of an ion battery of claim 1, wherein the MAX phase is Ti 3 AlC 2 The MXene prepared correspondingly is Ti 3 C 2 T x 。
3. The negative electrode active material of the ion battery as claimed in claim 1, wherein the mass ratio of MXene nanosheets to LDH in the MXene/LDH is 1:5-1; the molar ratio of nickel and cobalt elements in the LDH is 1.5-1:5.
4. The negative electrode active material of claim 3, wherein the molar ratio of nickel to cobalt in the LDH is 1:2.
5. The negative electrode active material of the ion battery as claimed in claim 1, wherein the mass ratio of MXene/LDH to dopamine hydrochloride is 1.
6. The negative electrode active material of claim 5, wherein the mass ratio of MXene/LDH to dopamine hydrochloride is 1:1.
7. The negative electrode active material for the ion battery as claimed in claim 1, wherein the mass ratio of MXene/LDH/PDA to selenium powder is 1:1-1:4.
8. The method for preparing the negative active material for ion batteries according to any one of claims 1 to 7, comprising the steps of:
step S1, dissolving lithium fluoride powder in hydrochloric acid to obtain a first mixed solution, adding MXene precursor, namely MAX-phase raw material powder, heating in a water bath, keeping stirring, centrifuging a product, and washing the product with deionized water; finally, dispersing the product in water for ultrasonic treatment, and then placing the product in a centrifuge for centrifugal separation to prepare MXene dispersion liquid;
step S2, mixing and stirring a cobalt salt solution, a nickel salt solution and MXene dispersion liquid to obtain a second mixed solution, adding ammonia water into the second mixed solution, heating and stirring in a water bath in an inert gas atmosphere, then carrying out hydrothermal reaction, carrying out centrifugal treatment on a product, washing with deionized water, and carrying out freeze drying to obtain MXene/LDH;
step S3, dispersing MXene/LDH in deionized water, carrying out ultrasonic stirring, adding dopamine hydrochloride and 1mol/L Tris-Cl buffer solution, fully stirring, centrifuging the product, washing with deionized water, and carrying out freeze drying to obtain MXene/LDH/PDA;
step S4, MXene/Co preparation x Ni 1-x Se 2 C: mixing and grinding MXene/LDH/PDA and selenium powder, putting into a tube furnace, and calcining in an inert gas atmosphere to selenize and carbonize; the selenizing calcination temperature range is 300-400 ℃, and the time is 4-6 hours; the carbonization and calcination temperature range is 500-600 ℃, and the time is 1-2 hoursWhen the current is over;
step S5, stirring the calcined product in carbon disulfide, washing off redundant elemental selenium, centrifugally separating, and drying in vacuum to obtain MXene/Co x Ni 1-x Se 2 /C。
9. An ion battery anode characterized in that the ion battery anode is made of the MXene/Co as the ion battery anode active material of any one of claims 1 to 7 x Ni 1-x Se 2 and/C is used as a negative active material.
10. An ion battery, wherein the negative electrode of the ion battery according to claim 9 is used as a negative electrode, and the ion battery is a lithium ion battery or a sodium ion battery.
CN202211233492.XA 2022-10-10 2022-10-10 Ion battery negative electrode active material, negative electrode, and ion battery Active CN115440964B (en)

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CN112079338A (en) * 2020-09-17 2020-12-15 齐鲁工业大学 Three-dimensional foam-like composite material, preparation method and application thereof in sodium-ion battery
CN114783786A (en) * 2022-04-22 2022-07-22 江苏科技大学 Bimetal selenide-porous carbon composite material for super capacitor and preparation method and application thereof
CN114959780A (en) * 2022-04-22 2022-08-30 中国石油大学(华东) Core-shell structure cobalt-doped nickel diselenide electrocatalytic material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112018361A (en) * 2020-08-31 2020-12-01 华中科技大学 Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof
CN112079338A (en) * 2020-09-17 2020-12-15 齐鲁工业大学 Three-dimensional foam-like composite material, preparation method and application thereof in sodium-ion battery
CN114783786A (en) * 2022-04-22 2022-07-22 江苏科技大学 Bimetal selenide-porous carbon composite material for super capacitor and preparation method and application thereof
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