CN115763712A - Preparation method of electrochemical pre-lithiation MXene negative electrode - Google Patents
Preparation method of electrochemical pre-lithiation MXene negative electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of an electrochemical pre-lithiation MXene negative electrode, wherein MAX-phase ceramic powder is etched by using a mixed solution of hydrochloric acid and lithium fluoride to obtain a two-dimensional carbide MXene; the MXene negative electrode is prepared by adopting a blade coating method, and is pre-lithiated by using an electrochemical method, so that the preparation method is safe and low in cost; the pre-lithiation MXene negative electrode can make up for lithium ion loss caused by the formation of an SEI (solid electrolyte interphase) film in the first charging process of the lithium ion battery, improves the coulombic efficiency of first charging and discharging, and plays an important role in improving the multiplying power and the cycle performance; in addition, the preparation of the pre-lithiated MXene negative electrode can also be used for manufacturing a lithium ion battery without a lithium ion positive electrode, and a wider choice of positive electrode materials is developed.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathodes, and particularly relates to a preparation method of an electrochemical pre-lithiation MXene cathode.
Background
The performance of the negative electrode material has a great influence on the stable operation of the battery, and at present, people are searching for a novel negative electrode with higher capacity than a commercial carbon-based negative electrode, such as a lithium alloy material of silicon or tin, which has higher specific capacity, however, the materials have the defects of large volume change and poor cycle stability. Therefore, it is important to develop a novel negative electrode having high capacity and high stability.
The MAX phase is a general name of a ternary layered cermet material and has a chemical formula: m n+1 AX n Wherein M is an early transition metal, A is a group III, IV element, X is C or N, and N represents 1,2,3, etc. To emphasize the exfoliation of the a elements from the MAX phase and to highlight their similar properties to the two-dimensional structure of Graphene (Graphene), one names this new class of materials as MXene. MXene has good lithium ion storage capacity, the theoretical specific capacity reaches 320mAh/g and is close to that of a commercial graphite electrode, and MXene has the advantages of high specific surface area, high conductivity, high mechanical strength and the like, and has huge potential to be applied to a battery cathode.
For the whole battery, the SEI film formed on the interface of the negative electrode consumes lithium ions deintercalated from the positive electrode and reduces the capacity of the battery, and by providing an external lithium source, the SEI film consumes the lithium ions of the external lithium source, so that the waste of the lithium ions of the positive electrode is reduced, and finally the capacity of the whole battery can be improved, wherein the process of providing the external lithium source is pre-lithiation.
Patent CN112928258A discloses a method for preparing pre-lithiated MXene by using self-discharge principle, although the negative electrode pre-lithiation can be realized by directly contacting with lithium foil, the degree of pre-lithiation is not easy to be precisely controlled, insufficient lithiation may be caused, and when lithium is excessively supplemented, a metal lithium plating layer may be formed on the surface of the negative electrode.
Disclosure of Invention
In order to solve the problems in the prior art, the invention mainly aims to provide a preparation method of an electrochemical pre-lithiation MXene negative electrode, and the preparation method is simple in process and environment-friendly.
The second purpose of the invention is to provide the pre-lithiated MXene negative electrode prepared by the preparation method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an electrochemical prelithiation MXene negative electrode comprises the following steps:
step one, preparing MXene materials:
(1) Dissolving MAX phase in mixed solution of hydrochloric acid and lithium fluoride according to the solid-liquid mass ratio of 1: 20, and stirring for 24-48h at 40-60 ℃; after the mixed solution is cooled, putting the mixed solution into a centrifuge tube, and carrying out centrifugal washing by using absolute ethyl alcohol and deionized water until the pH value of supernatant liquor in the centrifuge tube reaches 7;
(2) Dissolving the lower precipitate in deionized water, and performing ultrasonic dispersion; and (3) putting the dispersion liquid after ultrasonic dispersion into a centrifuge tube, further centrifuging, collecting supernatant in the centrifuge tube, putting the supernatant into a freeze dryer for drying, and obtaining the accordion-shaped material MXene after drying.
Step two, preparing the MXene negative electrode by using the MXene material prepared in the step one:
(1) Mixing MXene, conductive carbon black and a binder, grinding the mixture into electrode slurry by taking N-methyl pyrrolidone as a solvent, and uniformly coating the electrode slurry on an electrolytic copper foil;
(2) Putting the pole piece into a vacuum drying oven, and carrying out vacuum drying for 12h at the temperature of 100-120 ℃, wherein the pole piece obtained after drying is an MXene negative pole;
(3) The negative electrode was cut into a circular pole piece having a diameter of 16mm in a glove box using a cutter.
Step three, preparing a pre-lithiated MXene negative electrode by using the MXene negative electrode prepared in the step two through an electrochemical method:
(1) The cut MXene pole piece is assembled into a 2032 coin cell in a glove box by using a metal lithium piece with the diameter of 16mm as a counter electrode, a Celgard2400 diaphragm as an electrolyte diaphragm and 1mol/L LiTFSI dissolved in tetraethylene glycol dimethyl ether as electrolyte;
(2) After the battery is assembled, standing for 12 hours, then performing charging and discharging activation for 3 times within the voltage range of 0.05V-2.5V, and then performing constant current discharge;
(3) And finally, disassembling the battery in a glove box, and cleaning the surface of the MXene negative electrode by using tetraglyme, wherein the pole piece obtained in the step is the electrochemical pre-lithiation MXene negative electrode.
The electrochemical pre-lithiation MXene negative electrode prepared by the steps is provided with an external lithium source, so that the formation of a negative electrode interface SEI film consumes lithium ions of the external lithium source, the waste of positive lithium ions is reduced, and the capacity of the full battery can be improved finally.
The invention has the following advantages:
(1) The prelithiation process is carried out at room temperature, the process method is simple, the cost is low, special process equipment is not needed, and the prelithiation process is convenient and efficient;
(2) The controllability of the prelithiation process is improved through the charging and discharging process;
(3) According to the electrochemical pre-lithiation MXene negative electrode prepared by the method, an external lithium source is provided, so that a negative electrode interface SEI film is formed to consume lithium ions of the external lithium source, and finally the capacity of a full battery can be improved.
Drawings
Fig. 1 is an X-ray diffraction pattern of MXene prepared in accordance with the present invention.
Fig. 2 is a transmission electron microscope image of the MXene material prepared by the invention.
Fig. 3 is a scanning electron microscope image of the MXene material prepared by the invention.
Fig. 4 is a diagram of electrochemical impedance of half cell assembled by MXene negative electrode prepared in accordance with the present invention and lithium metal.
Fig. 5 is a cyclic voltammetry scan curve of MXene negative electrode prepared in accordance with the present invention.
Fig. 6 is a rate performance diagram of a half-cell assembled by an MXene negative electrode and lithium metal prepared by the method.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified.
Those skilled in the art who do not specify any particular technique or condition in the examples can follow the techniques or conditions described in the literature in this field or follow the product specification.
MXene material Ti 3 C 2 Preparation method of (2)
1gTi with the grain diameter of 400 meshes 3 AlC 2 The powder was dissolved in 20ml hydrochloric acid of 6mol/L concentrationStirring the mixed solution with lithium fluoride at 50 ℃ for 48 hours, cooling the mixed solution, putting the cooled mixed solution into a centrifuge tube, performing centrifugal washing by using absolute ethyl alcohol and deionized water until the pH value of supernatant in the centrifuge tube reaches 7, dissolving lower-layer precipitate in the deionized water, and performing ultrasonic dispersion for 30min; putting the dispersion liquid after ultrasonic dispersion into a centrifuge tube, further centrifuging, collecting supernatant in the centrifuge tube, putting into a refrigerator for freezing for 12h, putting the centrifuge tube into a freeze dryer for freeze drying for 48h after the solution is completely frozen, and drying to obtain the accordion-shaped material Ti 3 C 2 。
Example 1
Prelithiation of Ti 3 C 2 The preparation of the negative electrode comprises the following steps:
(1) Preparation of the binder: dissolving polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone, wherein the mass ratio of the PVDF is 2.5%, heating to 50 ℃, and stirring for 12 hours for later use;
(2) Preparation of electrode paste by mixing Ti 3 C 2 Mixing the conductive carbon black with PVDF serving as a binder according to the mass ratio of 8: 1; fully grinding the slurry until black ink slurry is obtained;
(3) And (3) an electrode coating and drying process: uniformly coating the slurry on the electrolytic copper foil by using a scraper, wherein the coating thickness is determined according to the viscosity of the slurry, and finally, the Ti pole piece is obtained 3 C 2 The unit load is 2mg/cm 2 After finishing, putting the pole piece into a vacuum drying oven, and carrying out vacuum drying for 12h at the temperature of 100 ℃;
(4) Electrochemical prelithiation of Ti 3 C 2 And (3) a negative electrode process: ti to be prepared 3 C 2 Cutting a pole piece into a circular negative pole with the diameter of 16mm, taking a metal lithium piece with the diameter of 16mm as a counter electrode, taking a Celgard2400 diaphragm as an electrolyte diaphragm, dissolving 1mol/L LiTFSI in tetraethylene glycol dimethyl ether as electrolyte, dropwise adding 50 microliter of electrolyte, assembling 2032 button cells in a glove box, standing for 12h after the cell is assembled, then performing charging and discharging activation for 3 times in the voltage range of 0.05V-2.5V, then performing constant current discharge to 0.05V, finally disassembling the cell in the glove box, and using tetraethylene glycolAnd cleaning the surface of the MXene negative electrode by dimethyl ether, wherein the pole piece obtained in the step is the electrochemical pre-lithiation MXene negative electrode.
Ti 3 C 2 Half cell composed of negative electrode and lithium metal
Ti prepared in example 1 3 C 2 The pole piece is cut into a circular negative pole with the diameter of 16mm, 50 mu L of electrolyte is dripped into the pole piece, and the pole piece and lithium metal are assembled into a half cell for testing, wherein an electrochemical impedance diagram is shown in figure 4, a cyclic voltammetry scanning curve is shown in figure 5, and a complete charging and discharging performance diagram is shown in figure 6.
Example 2
Prelithiated Ti 3 C 2 The preparation of the negative electrode comprises the following steps:
(1) Preparation of the binder: dissolving polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone, wherein the mass ratio of the PVDF is 2.5%, heating to 50 ℃, and stirring for 12 hours for later use;
(2) Preparation of electrode paste, mixing Ti 3 C 2 Mixing the carbon black with conductive carbon black and a binder PVDF according to the mass ratio of 4: 2; fully grinding the slurry until black ink slurry is obtained;
(3) And (3) electrode coating and drying process: uniformly coating the slurry on the electrolytic copper foil by using a scraper, wherein the coating thickness is determined according to the viscosity of the slurry, and finally, the Ti electrode plate is obtained 3 C 2 The unit load is 2mg/cm 2 After finishing, putting the pole piece into a vacuum drying oven, and carrying out vacuum drying for 12h at the temperature of 100 ℃;
(4) Electrochemical prelithiation of Ti 3 C 2 And (3) a negative electrode process: ti to be prepared 3 C 2 Cutting a pole piece into a circular negative pole with the diameter of 16mm, taking a metal lithium piece with the diameter of 16mm as a counter electrode, taking a Celgard2400 diaphragm as an electrolyte diaphragm, dissolving 1mol/L LiTFSI in tetraethylene glycol dimethyl ether as an electrolyte, dropwise adding 50 mu L of the electrolyte, assembling 2032 button cells in a glove box, standing for 12h after the cell assembly is finished, then performing charging and discharging activation for 3 times in the voltage range of 0.05V-2.5V, then performing constant current discharge to 0.05V, finally disassembling the cell in the glove box, cleaning the surface of the MXene negative pole by using tetraethylene glycol dimethyl ether, and taking the pole piece obtained in the step as an electric pole pieceChemically prelithiating MXene negative electrodes.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. The preparation method of the electrochemical prelithiation MXene negative electrode is characterized by comprising the following steps:
(1) Dissolving MAX phase in mixed solution of hydrochloric acid and lithium fluoride according to the solid-liquid mass ratio of 1: 20, and stirring for 24-48h at 40-60 ℃; after the mixed solution is cooled, putting the mixed solution into a centrifuge tube, and carrying out centrifugal washing by using absolute ethyl alcohol and deionized water until the pH value of supernatant liquor in the centrifuge tube reaches 7; dissolving the lower-layer precipitate in deionized water, and performing ultrasonic dispersion; and (3) putting the dispersion liquid after ultrasonic dispersion into a centrifuge tube, further centrifuging, collecting supernatant in the centrifuge tube, putting the supernatant into a freeze dryer for drying, and obtaining the MXene as the accordion-shaped material after drying.
(2) Mixing MXene, conductive carbon black and a binder, grinding the mixture into electrode slurry by taking N-methyl pyrrolidone as a solvent, and uniformly coating the electrode slurry on an electrolytic copper foil; putting the pole piece into a vacuum drying oven, and carrying out vacuum drying for 12h at the temperature of 100-120 ℃, wherein the pole piece obtained after drying is an MXene negative pole; cutting the negative electrode into a circular pole piece with the diameter of 16mm by using a cutting machine in a glove box;
(3) The cut MXene pole piece is assembled into a 2032 coin cell in a glove box by using a metal lithium piece with the diameter of 16mm as a counter electrode, a Celgard2400 diaphragm as an electrolyte diaphragm and 1mol/L LiTFSI dissolved in tetraethylene glycol dimethyl ether as electrolyte; after the battery is assembled, standing for 12h, then performing charging and discharging activation for 3 times in a voltage range of 0.05V-2.5V, and then performing constant current discharge to 0.05V; and finally, disassembling the battery in a glove box, and cleaning the surface of the MXene negative electrode by using tetraglyme, wherein the pole piece obtained in the step is the electrochemical pre-lithiation MXene negative electrode.
2. The method for preparing the electrochemically prelithiated MXene negative electrode according to claim 1, wherein in the step (1), the mixed solution of hydrochloric acid and lithium fluoride is 20ml of mixed solution of hydrochloric acid with a concentration of 6mol/L and lithium fluoride with a concentration of 1mol/L, the rotation speed of the supernatant collected by centrifugation is 4000rpm, and the centrifugation time is 10min.
3. The method of claim 1, wherein the mass ratio of MXene, conductive carbon black and binder in step (2) is 8: 1 and 4: 2, and the pole piece Ti is 3 C 2 The unit load is 2mg/cm 2 。
4. The method as claimed in claim 1, wherein the electrochemical prelithiation method in step (3) is to perform constant current discharge to 0.05V after 3 times of charge-discharge activation in the voltage range of 0.05V-2.5V.
5. An electrochemical prelithiated MXene negative electrode is prepared according to the preparation method of claims 1-4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102644602B1 (en) | 2023-09-26 | 2024-03-07 | 주식회사 나인테크 | MXene-coated active material, MXene-coated positive electrode active material, positive electrode, and supercapacitor |
| KR102673074B1 (en) | 2023-09-19 | 2024-06-07 | 주식회사 나인테크 | Metal foil current collector combined with MXene, cathode, anode and supercapacitor having the MX collector |
| KR102692340B1 (en) | 2023-11-09 | 2024-08-06 | 주식회사 나인테크 | Catechol-containing polymer surface-modified MXene, MXene conductive material, and surface-modified MXene conductive material |
-
2022
- 2022-12-05 CN CN202211553127.7A patent/CN115763712A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102673074B1 (en) | 2023-09-19 | 2024-06-07 | 주식회사 나인테크 | Metal foil current collector combined with MXene, cathode, anode and supercapacitor having the MX collector |
| KR102644602B1 (en) | 2023-09-26 | 2024-03-07 | 주식회사 나인테크 | MXene-coated active material, MXene-coated positive electrode active material, positive electrode, and supercapacitor |
| KR102692340B1 (en) | 2023-11-09 | 2024-08-06 | 주식회사 나인테크 | Catechol-containing polymer surface-modified MXene, MXene conductive material, and surface-modified MXene conductive material |
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