CN112670501A - Negative electrode material, preparation method of negative electrode material and lithium battery - Google Patents
Negative electrode material, preparation method of negative electrode material and lithium battery Download PDFInfo
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- 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 relates to a negative electrode material which is silane cross-linked modified d-Mxene, wherein M represents transition metal elements, and X represents carbon or nitrogen. The invention also relates to a method for preparing the anode material, which comprises the following steps: selectively etching an A atomic layer of the ternary layered compound MAX to obtain a multilayer MXene agglomerated phase, and performing ultrasonic dispersion to obtain a single-layer or few-layer d-MXene flaky two-dimensional material; and (3) uniformly mixing the two-dimensional flaky compound d-MXene and polysiloxane, and then carrying out annealing treatment. The invention also relates to a lithium battery, and a negative electrode of the lithium battery comprises the negative electrode material.
Description
Technical Field
The invention relates to the field of chemical batteries, in particular to a negative electrode material, a preparation method of the negative electrode material and a lithium battery.
Background
The lithium battery is a new generation of green high-energy battery, has the advantages of high working voltage, light weight, high volumetric specific energy, no environmental pollution and the like, is an ideal chemical power supply for modern communication, IT and portable electronic products, is also a preferred power supply for future electric vehicles, and has wide application prospect and great economic benefit.
The lithium battery mainly comprises a positive electrode material, a negative electrode material and a diaphragm, wherein the positive electrode material mainly adopts lithium cobaltate, lithium nickelate, lithium manganate, ternary materials and the like, the negative electrode material mostly adopts a graphitized carbon material which is low in price, good in thermal stability and environment-friendly, and due to the fact that the lithium intercalation potential of graphite is low, decomposition of electrolyte and separation of dendritic lithium are easily caused, and a series of safety problems are caused. Therefore, a new negative electrode material having a higher lithium intercalation potential than that of a carbon material, which is inexpensive, readily available, safe and reliable is desired.
Mxene, a two-dimensional transition metal carbide or carbonitride, has a structure similar to graphene. Currently, Mxene is mainly obtained by extracting weakly bound a-site elements (e.g., Al atoms) from the MAX phase with HF acid or a mixed solution of hydrochloric acid and fluoride. The nano-composite material has the characteristics of high specific surface area and high conductivity, has the advantages of flexible and adjustable components, controllable minimum nano-layer thickness and the like, has good conductivity and low ion diffusion resistance, and has great potential in the fields of energy storage, adsorption, sensors, conductive fillers and the like. The technical problem of preventing the application of the Mxene material to the lithium battery is as follows: the layered MXene nanosheets with the two-dimensional morphology are easy to collapse and pile again, and the migration rate of lithium ions on the cross section is seriously reduced, so that the electrochemical performance is influenced.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a negative electrode material prepared based on an MXene material, a preparation method of the negative electrode material and a lithium battery using the negative electrode material.
In one aspect, the invention provides a negative electrode material which is silane crosslinking modified d-Mxene, wherein M represents transition group metal elements (Ti, Cr, Ni and the like), and X represents carbon or nitrogen.
In one embodiment, the d-MXene and the siloxane form cross-linking through Si-O-Ti bonds, and the physical and chemical parameters of the negative electrode material are as follows: monoclinic system, space group of C2/m, unit cell volume of
In one embodiment, X is a carbonaceous material capable of absorbing and desorbing lithium, the carbonaceous material being at least one selected from the group consisting of non-graphitized carbon, and graphite.
In another aspect, the present invention provides a method for preparing the above negative electrode material, comprising the steps of: selectively etching an A atomic layer of the ternary layered compound MAX to obtain a multilayer MXene agglomerated phase, and performing ultrasonic dispersion to obtain a single-layer or few-layer d-MXene flaky two-dimensional material; and (3) uniformly mixing the two-dimensional flaky compound d-MXene and polysiloxane, and then carrying out annealing treatment.
Wherein M in the ternary layered compound MAX represents a transition group metal element (Ti, Cr, Ni, etc.), A represents a main group element (Na, Al, Mg, etc.), and X represents carbon or nitrogen. In the MAX phase, X atoms fill the octahedral structure formed by the close packing of M atoms, while A atoms are located between the MX layers. The two-dimensional material MXene is a layered transition metal carbonitride of the general formula Mn+ 1XnTxWherein M represents an early transition metal, X represents carbon or nitrogen, and T represents a functional group (such as-Oh, -F, -O, etc.) on the surface of MXene. The ultrasonic treatment can prepare multilayer MXene nanosheets. The layered MXene nanosheet has good conductivity, large specific surface area and adjustable chemical groups.
Wherein, in the annealing treatment process after the two-dimensional flaky compound d-MXene and the polysiloxane are uniformly mixed, the polysiloxane forms a Si-O-M covalent bond on a metal interface so that the combination between the siloxane and the metal is very firm; on the other hand, the polysiloxane forms a silane film having a three-dimensional network structure of Si-O-Si on the surface of the two-dimensional sheet compound d-MXene by a polycondensation reaction between SiOH groups. And forming a covalent cross-linked d-MXene three-dimensional framework after annealing treatment.
In one embodiment, the ternary layered compound MAX may be Ti3AlC2、Ti2AlC、Ta4AlC3、TiNbAlC、(V0.5Cr0.5)3AlC2、V2AlC、Nb2AlC、Nb4AlC3、Ti3AlCN、Ti3SiC2、Ti2SiC、Ta4SiC3、TiNbSiC、(V0.5Cr0.5)3SiC2、V2SiC、Nb2SiC、Nb4SiC3、Ti3One or more SiCN.
In one embodiment, the ternary layered compound MAX is formed by HF or HNO3Selectively etching the A atomic layer to obtain a multilayer MXene agglomerated phase, and performing ultrasonic dispersion to obtain a single-layer or few-layer d-MXene flaky two-dimensional material.
In one embodiment, the two-dimensional flaky d-MXene and polysiloxane are uniformly mixed and annealed at the temperature of not lower than 100 ℃ for not less than 4 hours, so that the formation of crosslinking between the d-MXene and the polysiloxane through Si-O-Ti bonds is promoted, wherein the mass ratio of the d-MXene to the polysiloxane is 1: 2.
in the annealing treatment process of the uniform mixture of the two-dimensional flaky compound d-MXene and the polysiloxane, the two-dimensional flaky compound d-MXene and the polysiloxane are covalently crosslinked, and the combination of the polysiloxane and the d-MXene can obviously improve the stability of a d-Mxene framework. The silane cross-linked modified d-Mxene material is used as a negative electrode material to be applied to a lithium battery, so that the conductivity can be improved, and the nucleation overpotential of lithium can be reduced.
In another aspect, the invention provides a lithium battery, wherein the negative electrode of the lithium battery adopts the negative electrode material.
Compared with the prior art, the technical scheme of the invention has at least the following beneficial effects:
1. aiming at the technical problems of the Mxene material, the mechanical strength and toughness of the Mxene material are improved by a polymer covalent crosslinking method, so that a metallic lithium carrier with excellent conductivity, lithium affinity and mechanical stability is prepared, and the metallic lithium carrier can be used as a negative electrode material of a lithium battery;
2. according to the invention, the covalent cross-linked d-MXene three-dimensional skeleton is formed by the silanization reaction of the d-MXene and polysiloxane, and the covalently cross-linked d-MXene skeleton shows excellent mechanical strength and toughness, so that the huge internal stress change impact generated in the rapid and deep lithium deposition/stripping process is relieved, and the structural integrity of the three-dimensional skeleton carrier in long-term charge and discharge cycles is ensured.
The following description will be given with reference to specific examples.
Drawings
The figures further illustrate the invention, but the examples in the figures do not constitute any limitation of the invention.
Fig. 1 is a first charge-discharge curve of a button cell provided in embodiment 8 of the present invention at 0.5C.
Fig. 2 is a cyclic discharge curve of the button cell battery provided in embodiment 8 of the present invention at a rate of 0.5C.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
This example provides a negative electrode material, which is a silane-crosslinked and modified d-Mxene, and which is crosslinked with siloxane through Si-O-Ti bonds, and the results of X-ray diffraction (XRD) measurement are shown in the following table:
as can be seen from the table, the negative electrode material was monoclinic, the space group of the negative electrode material was C2/m, and the cell volume of the negative electrode material was
Example 2
This example provides a negative electrode material, the negative electrode material is silane cross-linked and modified d-Mxene, the d-Mxene and siloxane form cross-linking through Si-O-Nb bonds, the negative electrode material is a monoclinic system, the space group of the negative electrode material is C2/m, and the cell volume of the negative electrode material is
Example 3
This example provides a negative electrode material, the negative electrode material is silane cross-linked and modified d-Mxene, the d-Mxene and siloxane form cross-linking through Si-O-V bond, the negative electrode material is monoclinic system, the space group of the negative electrode material is C2/m, the unit cell volume of the negative electrode material is
Example 4
This example provides a method of preparing the anode material of example 1, specifically as follows:
step one, 3-glycidoxypropyltrimethoxysilane is hydrolyzed and polymerized to prepare polysiloxane;
selectively etching an A atomic layer by using HF (hydrogen fluoride) in a ternary layered compound MAX to obtain a multilayer MXene agglomerated phase, wherein M represents transition group metal elements Ti and Ni, A represents main group element Al, and X represents a carbonaceous material capable of absorbing and desorbing lithium;
step three, carrying out ultrasonic dispersion treatment on the multilayer MXene agglomerated phase obtained in the step two to obtain a single-layer or few-layer d-MXene flaky two-dimensional material;
step four, uniformly mixing the two-dimensional flaky compound d-MXene obtained in the step three and the polysiloxane obtained in the step one according to the mass ratio of 1:2, then annealing at 100 ℃ for 4 hours, and standing to room temperature to obtain the negative electrode material.
Example 5
This example provides a method for preparing the negative electrode material of example 2, specifically as follows:
step one, 3-glycidoxypropyltrimethoxysilane is hydrolyzed and polymerized to prepare polysiloxane;
step two, the ternary laminar compound MAX passes through HNO3Selectively etching the A atomic layer to obtain a multilayer MXene agglomerated phase, wherein M represents a transition metal element V, A to represent a main group element Mg, and X represents nitrogen;
step three, carrying out ultrasonic dispersion treatment on the multilayer MXene agglomerated phase obtained in the step two to obtain a single-layer or few-layer d-MXene flaky two-dimensional material;
step four, uniformly mixing the two-dimensional flaky compound d-MXene obtained in the step three and the polysiloxane obtained in the step one according to the mass ratio of 1:3, then annealing at 150 ℃ for 5 hours, and standing to room temperature to obtain the negative electrode material.
Example 6
This example provides a method of preparing the anode material of example 3, specifically as follows:
step one, 3-glycidoxypropyltrimethoxysilane is hydrolyzed and polymerized to prepare polysiloxane;
selectively etching an A atomic layer by using HF (hydrogen fluoride) in a ternary layered compound MAX to obtain a multilayer MXene agglomerated phase, wherein M represents a transition metal element Nb, A represents a main group element Na, and X represents a carbonaceous material capable of absorbing and desorbing lithium;
step three, carrying out ultrasonic dispersion treatment on the multilayer MXene agglomerated phase obtained in the step two to obtain a single-layer or few-layer d-MXene flaky two-dimensional material;
step four, uniformly mixing the two-dimensional flaky compound d-MXene obtained in the step three and the polysiloxane obtained in the step one according to the mass ratio of 1:4, then annealing at 200 ℃ for 6 hours, and standing to room temperature to obtain the negative electrode material.
Example 7
The present embodiment provides a cylindrical lithium battery including a spirally wound electrode body including a strip-shaped positive electrode and a strip-shaped negative electrode, which are laminated and spirally wound with a separator therebetween in a substantially hollow cylindrical battery case.
The positive electrode includes a positive electrode active material layer disposed on both sides of a positive electrode current collector having a pair of opposing surfaces. The positive electrode collector is made of aluminum foil. The positive electrode active material layer includes a lithium-containing compound such as lithium cobaltate, lithium manganate, lithium nickel cobalt manganate or the like, and can attain a high voltage and a high energy density.
The negative electrode includes a negative electrode active material layer disposed on both sides of a negative electrode current collector having a pair of opposing surfaces. The negative electrode collector is made of copper foil.
The anode active material layer contains the anode material provided in example 1. The silane crosslinking modified d-Mxene can obviously improve the stability of a d-Mxene framework, simultaneously improve the conductivity and reduce the nucleation overpotential of lithium, and the cathode material provided by the embodiment 1 or the embodiment 2 or the embodiment 3 can improve the chemical stability of the cathode and prevent the decomposition of an electrolyte solution. Also, lithium can be smoothly inserted and extracted. Therefore, a high capacity and excellent charge and discharge efficiency can be obtained. The negative active material layer further contains an electrical conductor such as conductive carbon black, acetylene black, carbon nanotubes, or the like. Example 1 or example 2 or example 3 provides a ratio of the anode material and the electrical conductor in a range from 0.01 wt% to 10 wt% (inclusive).
The separator is isolated between the positive electrode and the negative electrode so that lithium ions pass while preventing a short circuit of current due to contact between the positive electrode and the negative electrode. The separator is made of, for example, a porous film of a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a ceramic porous film, and the separator may have a structure in which two or more porous films are laminated.
The electrolyte solution impregnating the separator contains a solvent and an electrolyte salt dissolved in the solvent. Examples of solvents include carbonates, esters, ethers, lactones, nitriles, amides, and sulfones. More specifically, nonaqueous solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, γ -butyrolactone, γ -valerolactone, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, acetate, butyrate, propionate, acetonitrile, glutaronitrile, adiponitrile, or methoxyacetonitrile are cited. As the solvent, only one or a mixture of plural kinds selected from them may be used.
The solvent preferably contains fluorinated carbonate because an excellent thin film can be formed on the surface of the electrode and decomposition of the electrolyte solution can be further prevented. As the above fluorinated carbonate, 4-fluoro-1, 3-dioxolan-2-one, 4, 5-difluoro-1, 3-dioxolan-2-one, fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate or difluoromethyl methyl carbonate is preferable because higher effects can be obtained. As the fluorinated carbonate, only one or a mixture of more selected from them may be used.
Examples of the electrolyte salt include lithium salts such as lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium tris (trifluoromethanesulfonyl) methide, lithium tris (pentafluoroethyl) trifluorophosphate, lithium (trifluoromethyl) trifluoroborate, lithium pentafluoroethyl trifluoroborate as the electrolyte salt, and a mixture of only one or more selected from them may be used.
Example 8
This example provides a button cell, in which lithium cobaltate is used as the positive electrode, the negative electrode material provided in example 1 is used as the negative electrode, and the button cell described in this example is a 2032 button cell. The specific manufacturing process of the button cell was identical to that of the existing 2032 type button cell except that the negative active material used in the existing 2032 type button cell was replaced with the negative material provided in example 1.
The first charge-discharge curve of the button cell at 0.5C is shown in figure 1, and the cyclic discharge curve at 0.5C rate is shown in figure 2. As can be seen from FIG. 1, the first charge-discharge specific capacity of the button cell at 0.5C is 174.5 mAh/g and 155.5mAh/g, and the first efficiency is 89.1%. As can be seen from FIG. 2, the button cell has a specific discharge capacity of 155.5mAh/g to 140.5mAh/g after 70 cycles at 0.5C rate, and the capacity retention rate is 90.4%.
The lithium battery using the anode material provided by the invention can obviously improve the cycle characteristics.
Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the embodiments and examples, and various modifications may be made. For example, in the embodiments and examples, batteries using lithium as an electrode reactant are described. However, the anode material provided in the present invention can also be applied to a battery using any other alkali metal such as sodium (Na) or potassium (K), alkaline earth metal such as magnesium or calcium (Ca), any other light metal such as aluminum as an electrode reactant.
In addition, in the embodiments and examples, the cylinder type secondary battery is described in detail, however, the anode material provided by the present invention may be applied to a secondary battery in any other shape such as a button type, a laminated film type, a coin type or a prism type, or a secondary battery having any other structure such as a layered structure. In addition, in the same manner, the invention provides an anode material suitable for not only a secondary battery but also any other battery such as a primary battery.
It will be appreciated by those skilled in the art that various modifications, combinations, sub-combinations, and alterations may be made in accordance with design requirements and other factors within the scope of the appended claims or their equivalents.
Claims (10)
1. An anode material, characterized in that: the negative electrode material is silane crosslinking modified d-Mxene, wherein M represents transition group metal elements, and X represents carbon or nitrogen.
2. The anode material according to claim 1, characterized in that: the crosslinking is formed between the d-MXene and the siloxane through Si-O-Ti bonds.
3. The anode material according to claim 2, characterized in that: the negative electrode material is monoclinic system, the space group of the negative electrode material is C2/m, and the unit cell volume of the negative electrode material is
4. The anode material according to claim 2, characterized in that: and X is a carbonaceous material capable of absorbing and desorbing lithium, and the carbonaceous material is at least one selected from non-graphitized carbon, graphitized carbon and graphite.
5. A method for preparing the negative electrode material according to any one of claims 1 to 4, comprising the steps of: selectively etching an A atomic layer of a ternary layered compound MAX to obtain a multilayer MXene agglomerated phase, and performing ultrasonic dispersion to obtain a single-layer or few-layer d-MXene flaky two-dimensional material, wherein A in the ternary layered compound MAX represents a main group element; and (3) uniformly mixing the two-dimensional flaky compound d-MXene and polysiloxane, and then carrying out annealing treatment.
6. The method of claim 5, wherein: the ternary layered compound MAX is prepared by HF or HNO3To selectively etch the a atomic layer.
7. The method of claim 5, wherein: the ternary layered compound MAX can be Ti3AlC2、Ti2AlC、Ta4AlC3、TiNbAlC、(V0.5Cr0.5)3AlC2、V2AlC、Nb2AlC、Nb4AlC3、Ti3AlCN、Ti3SiC2、Ti2SiC、Ta4SiC3、TiNbSiC、(V0.5Cr0.5)3SiC2、V2SiC、Nb2SiC、Nb4SiC3、Ti3One or more SiCN.
8. The method of claim 5, wherein: the annealing temperature of the two-dimensional flaky compound d-MXene and the polysiloxane is not lower than 100 ℃, and the annealing time is not less than 4 h.
9. The method of claim 8, wherein: the mass ratio of the two-dimensional flaky compound d-MXene to the polysiloxane is 1: 2.
10. a lithium battery, characterized in that: the negative electrode for a lithium battery includes the negative electrode material as set forth in any one of claims 1 to 4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113871725A (en) * | 2021-09-28 | 2021-12-31 | 洛阳储变电***有限公司 | Non-negative electrode lithium secondary battery |
| CN116154169A (en) * | 2023-01-13 | 2023-05-23 | 江苏正力新能电池技术有限公司 | MXene coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery |
| CN116154169B (en) * | 2023-01-13 | 2024-05-17 | 江苏正力新能电池技术有限公司 | MXene coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111293298A (en) * | 2020-02-27 | 2020-06-16 | 山东大学 | Flexible MXene/Si composite material and preparation method and application thereof |
| CN111384381A (en) * | 2020-03-23 | 2020-07-07 | 北京化工大学 | Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof |
-
2020
- 2020-12-04 CN CN202011406977.5A patent/CN112670501A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111293298A (en) * | 2020-02-27 | 2020-06-16 | 山东大学 | Flexible MXene/Si composite material and preparation method and application thereof |
| CN111384381A (en) * | 2020-03-23 | 2020-07-07 | 北京化工大学 | Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOJUAN QIAN ET AL.: ""Polysiloxane Cross-Linked Mechanically Stable MXene-Based Lithium Host for Ultrastable Lithium Metal Anodes with Ultrahigh Current Densities and Capacities"", 《ADV. FUNCT. MATER.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113871725A (en) * | 2021-09-28 | 2021-12-31 | 洛阳储变电***有限公司 | Non-negative electrode lithium secondary battery |
| CN116154169A (en) * | 2023-01-13 | 2023-05-23 | 江苏正力新能电池技术有限公司 | MXene coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery |
| CN116154169B (en) * | 2023-01-13 | 2024-05-17 | 江苏正力新能电池技术有限公司 | MXene coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery |
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