CN113937295B - Self-assembled MXene/chitosan composite membrane and preparation method and application thereof - Google Patents
Self-assembled MXene/chitosan composite membrane and preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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Abstract
The invention belongs to the technical field of composite material preparation, and particularly relates to a self-assembled MXene/chitosan composite film, and a preparation method and application thereof. The self-assembly of chitosan on the surface of MXene nanosheets weakens the stacking among the nanosheets, realizes the high regularity of the composite membrane, directly uses the composite membrane as a current collector of a lithium ion battery, induces the deposition of a metal plane by utilizing the high conductivity and a large amount of metal-philic groups (hydroxyl, amido and the like) on the surface of the composite membrane, and inhibits the growth of dendritic crystals in the operation process of the battery, thereby ensuring the safe, stable and efficient operation of the metal cathode secondary battery. The chitosan adopted in the invention is used as natural green polysaccharide, is safe and environment-friendly, and the preparation method of the composite membrane is simple and controllable, and is suitable for expanded production.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a self-assembled MXene/chitosan composite membrane as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Lithium ion batteries have dominated the energy storage market over the last decades due to relatively high energy density, low self-discharge. However, with the continuous progress of society, the energy density of lithium ion batteries cannot meet the demand of advanced rechargeable devices, so that a metal negative electrode (lithium, sodium, potassium, zinc, magnesium, etc.) secondary battery with high theoretical specific capacity and low electrochemical potential becomes one of the ideal choices for next-generation energy storage devices. However, the high reactivity of the metallic negative electrode and the extreme expansion of volume during cycling can lead to uncontrolled dendrite growth and fragmentation of the Solid Electrolyte Interface (SEI) film, which not only causes rapid degradation of the performance of the metal battery, but even dendrites can puncture the separator causing short circuits and can cause serious safety problems. In order to inhibit dendritic crystals and improve the cycle stability and safety performance of a metal negative electrode, researchers have proposed various strategies, such as the adoption of a porous current collector, an electrolyte additive, a composite metal negative electrode and the like, but the actual application requirements of a metal negative electrode secondary battery cannot be met by the current work.
The graphene-like transition metal carbide (nitride) two-dimensional material MXene has the advantages of good mechanical flexibility, high specific surface area, conductivity, hydrophilicity and the like, a colloid solution of the two-dimensional few-layer MXene can be formed into a self-supporting flexible conductive film through simple suction filtration and self-assembly, the MXene is widely researched in the fields of energy storage, catalysis, electromagnetic shielding and the like, and the MXene also has great potential as a battery electrode material and a current collector. However, the inventor finds that severe stacking exists among MXene nanosheets, and a self-supporting MXene film prepared by suction filtration has a large number of defects of folding, even chapping and the like, so that the application of the self-supporting MXene film in a secondary battery is limited.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a self-assembled MXene/chitosan composite membrane and a preparation method and application thereof, wherein the self-assembly of chitosan on the surface of MXene nanosheets is utilized to weaken the stacking among the nanosheets and realize the high regularity of the composite membrane, the composite membrane is directly used as a current collector of a lithium ion battery, the high conductivity of the composite membrane and a large amount of metal-philic groups (hydroxyl, amido and the like) on the surface are utilized to induce the metal plane deposition and inhibit the dendritic crystal growth in the battery operation process, so that the safe, stable and efficient operation of the metal cathode secondary battery is ensured. The chitosan adopted in the invention is used as natural green polysaccharide, is safe and environment-friendly, and the preparation method of the composite membrane is simple and controllable, and is suitable for expanded production.
Specifically, the invention is realized by the following technical scheme:
in the first aspect of the invention, the self-assembled MXene/chitosan composite film is formed by stacking layered MXene nanosheets layer by layer, and the surfaces of the layered MXene nanosheets are self-assembled and coated with chitosan.
In a second aspect of the invention, a battery negative electrode current collector is a self-assembled MXene/chitosan composite film.
In a third aspect of the present invention, a battery negative electrode is based on the battery negative electrode current collector, and a metal is loaded on the current collector.
In a fourth aspect of the present invention, a method for preparing a self-assembled MXene/chitosan composite film comprises: preparing an MXene colloidal solution and a chitosan solution, adding the chitosan solution into the few-layer MXene nanosheet colloidal solution, uniformly mixing, performing suction filtration, and drying to obtain a self-assembled composite membrane; the MXene colloidal solution is an aqueous solution of few-layer MXene nanosheets, and the chitosan solution is an acid solution of chitosan.
In a fifth aspect of the present invention, a metal negative secondary battery comprising the self-assembled MXene/chitosan composite film and/or the battery negative current collector.
In a sixth aspect of the present invention, the self-assembled MXene/chitosan composite membrane and/or the battery negative electrode current collector and/or the battery negative electrode and/or the metal negative electrode secondary battery are applied in the field of new energy industry.
One or more embodiments of the present invention have the following advantageous effects:
(1) The natural polysaccharide-chitosan and MXene are adopted for self-assembly, the raw materials are green and environment-friendly, and the sustainable development concept is met.
(2) The method can form a microscopic three-dimensional structure surface on the surface of the composite membrane, improve the specific surface area, increase the wettability to electrolyte, reduce the interface impedance, homogenize the surface electric field and inhibit the generation of metal dendrites.
(3) The nucleation overpotential can be reduced, the metal is induced to grow transversely, and the dendrite-free planar metal deposition is realized.
(4) The battery circulation stability can be obviously prolonged, the battery coulombic efficiency is improved, and the safety problem possibly caused by dendritic crystal growth is avoided.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a comparison of scanning electron microscope images of the surfaces of an MXene/chitosan composite film prepared by the method of example 1 of the present invention and a pure MXene film.
Fig. 2 is a comparison of cross-sectional scanning electron microscope images of the MXene/chitosan composite film prepared by the method of example 1 of the present invention and a pure MXene film.
Fig. 3 is a plot of the coulombic efficiencies of the current collector-lithium half cells of example 1 of the present invention and comparative example 1.
Fig. 4 is a long cycle chart of a lithium symmetrical battery according to example 1 and comparative example of the present invention.
Figure 5 is a comparison of voltage curves during cycling for sodium symmetric cells of example 2 of the present invention and comparative example.
Fig. 6 is a scanning electron micrograph of a commercial copper foil current collector after lithium deposition according to a comparative example of the present invention.
Fig. 7 is a scanning electron microscope image of the MXene/chitosan composite film current collector after lithium deposition in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
At present, in the operation process of a metal cathode secondary battery, the uncontrolled growth of metal dendrites can be caused by the uneven deposition of metal and an unstable SEI film, so that the battery efficiency is reduced and the cycle life is severely reduced, more seriously, the dendrites which continuously grow can pierce through a diaphragm, the battery is short-circuited, and the safety problems of thermal runaway and even explosion are caused. Based on the self-assembly MXene/chitosan composite membrane, the preparation method and the application thereof are provided by the invention.
In one or more embodiments of the invention, the self-assembled MXene/chitosan composite film is formed by stacking layered MXene nanosheets layer by layer, and the surfaces of the layered MXene nanosheets are self-assembled and coated with chitosan.
The natural polysaccharide-chitosan with positive charges is self-assembled on the surface of the MXene nanosheet with negative charges through electrostatic interaction, so that the serious accumulation of the MXene nanosheet in the suction filtration film forming process is improved. The composite film layered MXene nanosheet has high integrity, the nanosheet layer is complete, and the stacking condition cannot occur. The high-regularity flexible self-supporting MXene/chitosan composite membrane is obtained and used as a metal battery current collector, so that metal plane deposition can be induced, and dendritic crystal growth is inhibited. The reasons include: (1) The chitosan self-assembled on the surface of the MXene nanosheets weakens the interaction among the MXene nanosheets, reduces the stacking among the MXene nanosheets in the suction filtration process, obtains a composite membrane with high regularity, and can avoid the defects of chapping of the MXene membrane and the like. (2) After the MXene surface is self-assembled with chitosan, the abundant polar groups (such as amino groups, hydroxyl groups and the like) on the surface of the chitosan and the formed microscopic three-dimensional surface can increase the wettability and the specific surface area to the electrolyte, reduce the interface impedance and homogenize the surface electric field. (3) The amido and the hydroxyl on the chitosan molecule have extremely strong adsorption effect on metal cations, reduce the metal nucleation overpotential, and can be used as a deposition anchor point to promote the uniform and planar deposition of metal and effectively inhibit the generation of dendritic crystals.
The invention aims to solve the serious problem existing in the suction filtration film-forming process, and does not belong to the real problem that the current collector preparation process by suction filtration film-forming cannot be known in the prior art. The composite film can play a good role in inhibiting dendritic crystal growth when being used as a current collector, is simple in preparation process, environment-friendly in material, capable of expanding production, and has high scientific research and application prospects.
Further, the MXene nanosheets are obtained by etching and stripping MAX powder through LiF and hydrochloric acid, and the few-layer MXene nanosheets are obtained, wherein the few-layer MXene nanosheets are MXene nanosheets with the number of layers being less than 5. In general, in the process of film formation of MXene nanosheets by suction filtration, the MXene nanosheet layers are stacked very seriously and are easy to break, and the completeness of the nanosheets is greatly reduced.
In the prior art, MXene nanosheets are used for preparing an adsorbing material, and chitosan is added, but the current collector is not prepared by adopting suction filtration film forming in the technology, so that the problems of serious stacking of a layered structure, structural fracture and the like in the suction filtration film forming process are not shown. Moreover, the adsorbing material prepared by the technology has serious MXene nanosheet stacking and cracking, and cannot maintain a clear layered nanosheet structure, which obviously does not meet the original purpose of the invention.
Further, the MAX powder is Ti 3 AlC 2 、Ti 2 AlC、Ta 4 AlC 3 、TiNbAlC、(V 0.5 Cr 0.5 ) 3 AlC 2 、V 2 AlC、Nb 2 AlC、Nb 4 AlC 3 、Ti 3 AlCN、Ti 3 SiC 2 、Ti 2 SiC、Ta 4 SiC 3 、TiNbSiC、(V 0.5 Cr 0.5 ) 3 SiC 2 、V 2 SiC、Nb 2 SiC、Nb 4 SiC 3 Or Ti 3 One of SiCN; preferably, it is Ti 3 AlC 2 。
Further, the chitosan is medium-high deacetylation degree chitosan, the deacetylation degree is more than or equal to 75%, and preferably the deacetylation degree is more than or equal to 90%. Wherein the chitosan with medium and high deacetylation degree refers to chitosan with deacetylation degree of more than or equal to 75%. The chitosan with positive charges realizes self-assembly on the MXene nanosheets, can greatly avoid the accumulation of layered MXene nanosheets, and further improves the electrochemical activity.
Wherein the mass ratio of the layered MXene nanosheet to the chitosan is 5-20; preferably, 10.
In one or more embodiments of the invention, a battery negative electrode current collector is the self-assembled MXene/chitosan composite film. The self-assembled MXene/chitosan composite membrane is used as a negative current collector of the metal negative secondary battery, so that the wettability and the specific surface area of electrolyte can be increased, the interface impedance is reduced, and the surface electric field is uniform. The metal nucleation overpotential is reduced, and the metal nucleation overpotential can be used as a deposition anchor point, so that the uniform and planar deposition of metal is promoted, and the generation of dendritic crystals is effectively inhibited.
In one or more embodiments of the invention, a battery negative electrode is based on a battery negative electrode current collector, and metal is loaded on the current collector; further, the supported metal includes lithium, sodium, potassium, zinc, aluminum or magnesium; preferably, it is lithium.
In one or more embodiments of the present invention, a method for preparing a self-assembled MXene/chitosan composite film includes: preparing an MXene colloidal solution and a chitosan solution, adding the chitosan solution into the few-layer MXene nanosheet colloidal solution, uniformly mixing, performing suction filtration, and drying to obtain a self-assembled composite membrane; the MXene colloidal solution is an aqueous solution of few-layer MXene nanosheets, and the chitosan solution is an acid solution of chitosan.
The chitosan is dissolved in acid to obtain an acid solution of the chitosan, which is beneficial to the positive charge of the amino combined with the proton in the acid solution in chitosan molecules, and then the surface of the MXene nanosheet with the negative charge is subjected to self-assembly. The acid is one of hydrochloric acid, formic acid, acetic acid, lactic acid, malic acid or ascorbic acid, and is preferably acetic acid. Reasonable acid concentration has the promotion effect of improving the uniformity of the chitosan, and the acid solution concentration is preferably 1% acetic acid aqueous solution.
Specifically, the chitosan solution is obtained by adding chitosan powder into dilute acid aqueous solution and then stirring and dissolving.
Or the stirring mode is mechanical stirring or magnetic stirring.
Or the dissolving temperature is 10-60 ℃.
Or the dissolving time is 5-10h.
Or the concentration of the chitosan solution is 0.2-2%, preferably 0.5-1%.
Further, after the MXene nanosheet colloidal solution is added into the chitosan solution, the stirring mode is mechanical stirring or magnetic stirring, the stirring time is 0.5-2h, and the mixing temperature is 0-30 ℃.
In one or more embodiments of the present invention, a metal negative secondary battery comprising the self-assembled MXene/chitosan composite film and/or the battery negative current collector; further, the battery is selected from a lithium battery, a sodium battery, a potassium battery, a zinc battery, an aluminum battery or a magnesium battery; further, the battery is a symmetrical battery or a full battery.
The metal negative electrode secondary battery is a battery in which a negative electrode material is a metal such as lithium, sodium, potassium, zinc, aluminum, magnesium, or the like, and charge and discharge are performed by transfer of metal ions.
Further, the battery comprises a current collector, a metal negative electrode, a positive electrode, a diaphragm and an electrolyte; further, the current collector is the self-assembled MXene/chitosan composite film; the metal cathode is obtained by electroplating metal on the composite film; further, the electrolyte is an ester or ether organic electrolyte or an aqueous inorganic electrolyte.
In one or more embodiments of the present invention, the self-assembled MXene/chitosan composite film and/or the battery negative electrode current collector and/or the battery negative electrode and/or the metal negative electrode secondary battery are applied in the field of new energy industry; further, the application includes an application in a drone, an electric vehicle, or an energy storage device.
In one or more embodiments of the invention, the method for preparing the large-size single-crystal two-dimensional material and/or the application of the large-size single-crystal two-dimensional material in the fields of semiconductor devices, capacitors, sensors and catalysis are provided.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
(1) Take 0.5gTi 3 AlC 2 And putting the powder into a mixed solution of 0.5g LiF and 10mL of 6M hydrochloric acid, adding 2.5mL of water, stirring for 24 hours, centrifuging, washing until the pH value is 6, and then carrying out ultrasonic stripping to obtain a few-layer MXene colloidal solution.
(2) Dissolving chitosan powder with deacetylation degree of 90% in 1% acetic acid to prepare a solution with chitosan mass fraction of 0.5%.
(3) Adding the MXene colloidal solution obtained in the step (1) into the chitosan solution obtained in the step (2), and magnetically stirring for 2h, wherein the mass ratio of MXene to chitosan is 10:1.
(4) And (4) filtering and drying the mixed solution obtained in the step (3) to obtain the MXene/chitosan composite membrane.
(5) The MXene/chitosan composite film obtained in step (4) was used as a working electrode and a lithium metal foil as a counter electrode, and an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) was used in an inert atmosphere at 0.5mA cm/DEC (1 -2 And (4) performing constant current pre-deposition for 10 hours to obtain the composite lithium metal cathode loaded with lithium on the MXene/chitosan composite membrane.
(6) The composite lithium metal negative electrode assembled battery obtained in step (5) was assembled into a 2032 type coin cell using an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) in a glove box.
Example 2
(1) Take 0.5gTi 3 AlC 2 And putting the powder into a mixed solution of 0.5g of LiF and 10mL of 6M hydrochloric acid, adding 2.5mL of water, stirring for 24 hours, centrifuging, washing until the pH value is 6, and then carrying out ultrasonic stripping to obtain a small-layer MXene colloidal solution.
(2) Dissolving chitosan powder with deacetylation degree of 90% in 1% acetic acid to prepare a solution with chitosan mass fraction of 0.5%.
(3) Adding the MXene colloidal solution obtained in the step (1) into the chitosan solution obtained in the step (2), and magnetically stirring for 2h, wherein the mass ratio of MXene to chitosan is 10:1.
(4) And (4) filtering and drying the mixed solution obtained in the step (3) to obtain the MXene/chitosan composite membrane.
(5) The MXene/chitosan composite film obtained in step (4) was used as a working electrode and a sodium metal foil as a counter electrode, and the MXene/chitosan composite film was subjected to treatment with an ester electrolyte 1M NaPF6 EC/DEC (1, v/v,5% fec) under an inert atmosphere at 0.5mA cm -2 And (5) performing constant current pre-deposition for 10 hours to obtain the composite sodium metal cathode.
(6) The composite sodium metal negative electrode assembly cell obtained in step (5) was assembled into a 2032 type button cell using an ester electrolyte 1M napfc 6 EC/DEC (1, v/v,5% fec) in a glove box.
Example 3
(1) Take 0.5g0.5gTi 3 AlC 2 And putting the powder into a mixed solution of 0.5g of LiF and 10mL of 6M hydrochloric acid, adding 2.5mL of water, stirring for 24 hours, centrifuging, washing until the pH value is 6, and then carrying out ultrasonic stripping to obtain a small-layer MXene colloidal solution.
(2) Dissolving chitosan powder with deacetylation degree of 90% in 1% acetic acid to prepare a solution with chitosan mass fraction of 0.5%.
(3) Adding the MXene colloidal solution obtained in the step (1) into the chitosan solution obtained in the step (2), and magnetically stirring for 2h, wherein the mass ratio of MXene to chitosan is 10:1.
(4) And (4) carrying out suction filtration and drying on the mixed solution obtained in the step (3) to obtain the MXene/chitosan composite membrane.
(5) Using the MXene/chitosan composite membrane obtained in the step (4) as a working electrode, using a potassium metal foil as a counter electrode, and adopting ether electrolyte 3M KFSI DME in an inert atmosphere at 0.5mA cm -2 And (5) performing constant current pre-deposition for 10 hours to obtain the composite potassium metal cathode.
(6) And (3) assembling the battery with the composite sodium metal cathode obtained in the step (5) in a glove box, and assembling the battery into a 2032 type button battery by adopting ether electrolyte 3M KFSI DME.
Example 4
(1) Take 0.5g0.5gTi 3 AlC 2 The powder was put into a mixed solution of 0.5g LiF and 10mL of 6M hydrochloric acidAdding 2.5mL of water, stirring for 24h, centrifuging, washing to pH 6, and then ultrasonically stripping to obtain a small-layer MXene colloidal solution.
(2) Dissolving chitosan powder with deacetylation degree of 90% in 1% acetic acid to prepare a solution with chitosan mass fraction of 0.5%.
(3) Adding the MXene colloidal solution obtained in the step (1) into the chitosan solution obtained in the step (2), and magnetically stirring for 2h, wherein the mass ratio of MXene to chitosan is 10:1.
(4) And (4) carrying out suction filtration and drying on the mixed solution obtained in the step (3) to obtain the MXene/chitosan composite membrane.
(5) Taking the MXene/chitosan composite membrane obtained in the step (4) as a working electrode, taking a zinc metal foil as a counter electrode, and adopting 2M ZnSO of an aqueous electrolyte 4 The aqueous solution was heated at 0.5mA cm under an inert atmosphere -2 And (5) performing constant current pre-deposition for 10 hours to obtain the composite zinc metal cathode.
(6) Assembling the battery with the composite sodium metal cathode obtained in the step (5) in a glove box by adopting 2M ZnSO aqueous electrolyte 4 Assembling to obtain a 2032 type button cell.
Example 5
(1) Take 0.5gV 2 And (3) putting the AlC powder into a mixed solution of 0.5g of LiF and 10mL of 6M hydrochloric acid, adding 2.5mL of water, stirring for 24 hours, centrifuging, washing until the pH value is 6, and then carrying out ultrasonic stripping to obtain a small-layer MXene colloidal solution.
(2) Chitosan powder with deacetylation degree of 90% is dissolved in 1% acetic acid to prepare a solution with chitosan mass fraction of 0.5%.
(3) Adding the MXene colloidal solution obtained in the step (1) into the chitosan solution obtained in the step (2), and magnetically stirring for 2h, wherein the mass ratio of MXene to chitosan is 10:1.
(4) And (4) filtering and drying the mixed solution obtained in the step (3) to obtain the MXene/chitosan composite membrane.
(5) The MXene/chitosan composite film obtained in step (4) was used as a working electrode and a lithium metal foil was used as a counter electrode, and the MXene/chitosan composite film was subjected to reaction with an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) in an inert atmosphere at 0.5mA cm -2 Constant current pre-deposition for 10h to obtain compositeA lithium metal negative electrode.
(6) The composite lithium metal negative electrode assembled battery obtained in step (5) was assembled into a 2032 type coin cell using an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) in a glove box.
Example 6
(1) Take 0.5gTi 3 AlC 2 And putting the powder into a mixed solution of 0.5g of LiF and 10mL of 6M hydrochloric acid, adding 2.5mL of water, stirring for 24 hours, centrifuging, washing until the pH value is 6, and then carrying out ultrasonic stripping to obtain a small-layer MXene colloidal solution.
(2) Dissolving chitosan powder with deacetylation degree of 90% in 1% acetic acid to prepare a solution with chitosan mass fraction of 1%.
(3) Adding the MXene colloidal solution obtained in the step (1) into the chitosan solution obtained in the step (2), and magnetically stirring for 2h, wherein the mass ratio of MXene to chitosan is 10:1.
(4) And (4) carrying out suction filtration and drying on the mixed solution obtained in the step (3) to obtain the MXene/chitosan composite membrane.
(5) The MXene/chitosan composite film obtained in step (4) was used as a working electrode and a lithium metal foil was used as a counter electrode, and the MXene/chitosan composite film was subjected to reaction with an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) in an inert atmosphere at 0.5mA cm -2 And (5) performing constant current pre-deposition for 10 hours to obtain the composite lithium metal negative electrode.
(6) The assembled battery with the composite lithium metal negative electrode obtained in step (5) was assembled into a 2032 type button cell using an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) in a glove box.
Example 7
(1) Take 0.5g Ti 3 AlC 2 And putting the powder into a mixed solution of 0.5g of LiF and 10mL of 6M hydrochloric acid, adding 2.5mL of water, stirring for 24 hours, centrifuging, washing until the pH value is 6, and then carrying out ultrasonic stripping to obtain a small-layer MXene colloidal solution.
(2) Dissolving chitosan powder with deacetylation degree of 90% in 1% acetic acid to prepare a solution with chitosan mass fraction of 0.5%.
(3) Adding the MXene colloidal solution obtained in the step (1) into the chitosan solution obtained in the step (2), and magnetically stirring for 2h, wherein the mass ratio of MXene to chitosan is 15:1.
(4) And (4) carrying out suction filtration and drying on the mixed solution obtained in the step (3) to obtain the MXene/chitosan composite membrane.
(5) The MXene/chitosan composite film obtained in step (4) was used as a working electrode and a lithium metal foil as a counter electrode, and an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) was used in an inert atmosphere at 0.5mA cm/DEC (1 -2 And (5) performing constant current pre-deposition for 10 hours to obtain the composite lithium metal cathode.
(6) The assembled battery with the composite lithium metal negative electrode obtained in step (5) was assembled into a 2032 type button cell using an ester electrolyte 1M lipff 6 EC/DEC (1, v/v,10% fec) in a glove box.
Comparative example
A method of making a lithium/sodium battery using a commercial copper foil current collector comprising the steps of:
commercial copper foil is used as a working electrode, lithium/sodium metal foil is used as a counter electrode, and ester electrolyte is adopted at 0.5mA cm in inert atmosphere -2 And (5) performing constant current pre-deposition for 10 hours to obtain the composite lithium/sodium metal cathode. And then, assembling the obtained composite lithium/sodium metal cathode into a 2032 type button cell by adopting an ester electrolyte in a glove box.
Performance testing
(1) Characterization of morphology of self-assembled MXene/chitosan composite membrane
The self-assembled MXene/chitosan composite film prepared in example 1 and the pure MXene film obtained by separately pumping the few-layer MXene colloidal solution prepared in example 1 were observed by scanning electron microscopy, and the surface scanning electron microscopy image is shown in fig. 1, and the cross-sectional scanning electron microscopy image is shown in fig. 2. As can be seen from fig. 1, the MXene/chitosan composite film has a relatively flat surface and a micro three-dimensional wrinkle structure, which can increase the specific surface area and improve the wettability, while the pure MXene film has a deep gully or even chaps. As can be seen from FIG. 2, the MXene/chitosan composite membrane has high regularity, the arrangement of the internal MXene nanosheets is relatively regular, and for the pure MXene membrane, the MXene nanosheets in the MXene after the pumping filtration are seriously distorted and deformed due to the serious stacking effect among the MXene nanosheets, so that a great number of defects exist.
(1) The electrochemical performance of the 2032 type button cell batteries prepared in examples 1 and 2 was evaluated using a charge and discharge device (novacar CT-4008). Meanwhile, as a comparison, the above-described performance of the battery (comparative example) assembled using the commercial copper foil current collector was also tested, and the results are shown in fig. 3 to 4.
First, at a current density of 0.5mA/cm 2 The capacity is 0.5mAh/cm 2 The coulombic efficiency of the two groups of lithium half batteries of the example 1 and the comparative example is tested under the condition, and the result is shown in fig. 3, it can be seen that the coulombic efficiency is still as high as 96% after the circulation of 300 circles by adopting the composite film current collector, and the coulombic efficiency is reduced to 45% after the circulation of 120 circles by adopting the copper current collector, and the coulombic efficiency is obviously improved after the composite film current collector is adopted.
Next, at a current density of 1.0mA/cm 2 The capacity is 1.0mAh/cm 2 The cycling stability of the two groups of lithium symmetric batteries of example 1 and the comparative example was tested under the conditions, and the results are shown in fig. 4, and it can be seen that after the modified diaphragm was used, the symmetric batteries can stably cycle for more than 1000h, the polarization voltage is only 27.1mV, and the cycling stability of the lithium symmetric batteries is significantly improved compared with the commercial PE diaphragm which has a polarization voltage of less than 700h, i.e., as high as 80 mV.
Finally, at a current density of 1.0mA/cm 2 The capacity is 1.0mAh/cm 2 The cycle performance of the two sodium symmetrical batteries of the example 2 and the comparative example is tested under the conditions, and the result is shown in fig. 5, it can be seen that after the composite film current collector is adopted, the polarization voltage of the symmetrical battery is far lower than that of the commercial copper foil current collector, and the sodium symmetrical battery has better cycle stability.
(2) Characterization of lithium deposition morphology:
the cells prepared according to the method of example 1 and comparative example were operated at 0.5mA/cm 2 To deposit lithium onto a composite film or commercial copper foil current collector. Then the battery is disassembled in the argon atmosphere to obtain the lithium-deposited collectorAnd then observing the appearance of lithium on the surface of the current collector by using a scanning electron microscope. The results are shown in FIG. 6 (comparative example) and FIG. 7 (example 1). As can be seen in fig. 6, commercial copper foil current collectors have numerous dendritic lithium dendrites thereon. As can be seen from fig. 7, dendritic lithium dendrites were not found on the composite film current collector. The result shows that the self-assembled MXene/chitosan composite membrane serving as the current collector can inhibit the generation of lithium dendrites and induce the transverse growth of lithium, so that the circulation stability and the coulombic efficiency of the battery can be improved, and the safety problem of a lithium dendrite growth assembly can be effectively avoided.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (21)
1. A battery negative current collector is characterized in that the battery negative current collector is a self-assembled MXene/chitosan composite membrane, the composite membrane is formed by stacking layered MXene nanosheets layer by layer, and the surfaces of the layered MXene nanosheets are self-assembled and coated with chitosan;
the chitosan is chitosan with medium and high deacetylation degree, and the deacetylation degree is more than or equal to 75 percent;
the mass ratio of the layered MXene nanosheet to the chitosan is 5 to 20;
the preparation method of the self-assembled MXene/chitosan composite membrane comprises the following steps: preparing an MXene colloidal solution and a chitosan solution, adding the chitosan solution into the few-layer MXene nanosheet colloidal solution, uniformly mixing, performing suction filtration, and drying to obtain a self-assembled composite membrane; the MXene colloidal solution is an aqueous solution of few-layer MXene nanosheets, and the chitosan solution is an acid solution of chitosan.
2. The battery negative electrode current collector of claim 1, wherein the MXene nanosheets are few-layer MXene nanosheets obtained by etching and stripping MAX powder through LiF and hydrochloric acid.
3. The battery negative electrode current collector of claim 2, wherein said MAX powder is Ti 3 AlC 2 、Ti 2 AlC、Ta 4 AlC 3 、TiNbAlC、(V 0.5 Cr 0.5 ) 3 AlC 2 、V 2 AlC、Nb 2 AlC、Nb 4 AlC 3 、Ti 3 AlCN、Ti 3 SiC 2 、Ti 2 SiC、Ta 4 SiC 3 、TiNbSiC、(V 0.5 Cr 0.5 ) 3 SiC 2 、V 2 SiC、Nb 2 SiC、Nb 4 SiC 3 Or Ti 3 One of SiCN;
the mass ratio of the layered MXene nanosheet to chitosan is 10.
4. The negative current collector of claim 3, wherein said MAX powder is Ti 3 AlC 2 。
5. The battery negative electrode current collector of claim 1, wherein the preparation method of the self-assembled MXene/chitosan composite membrane comprises: the acid is one of hydrochloric acid, formic acid, acetic acid, lactic acid, malic acid or ascorbic acid.
6. The battery negative electrode current collector of claim 5, wherein the preparation method of the self-assembled MXene/chitosan composite membrane comprises: the acid is acetic acid.
7. The battery negative electrode current collector of claim 6, wherein the preparation method of the self-assembled MXene/chitosan composite film comprises the following steps: the acid solution is 1% acetic acid in water.
8. The battery negative electrode current collector of claim 1, wherein the preparation method of the self-assembled MXene/chitosan composite membrane comprises: the chitosan solution is obtained by adding chitosan powder into dilute acid aqueous solution and then stirring and dissolving.
9. The battery negative electrode current collector of claim 8, wherein the self-assembled MXene/chitosan composite membrane is prepared by a method comprising: the stirring mode is mechanical stirring or magnetic stirring;
the dissolving temperature is 10-60 ℃;
the dissolving time is 5-10h;
the concentration of the chitosan solution is 0.2-2%.
10. The battery negative electrode current collector of claim 9, wherein the self-assembled MXene/chitosan composite membrane is prepared by a method comprising: the concentration of the chitosan solution is 0.5-1%;
after the MXene nanosheet colloidal solution is added into the chitosan solution, the stirring mode is mechanical stirring or magnetic stirring, the stirring time is 0.5-2h, and the mixing temperature is 0-30 ℃.
11. A battery negative electrode characterized in that a metal is supported on a current collector based on the battery negative electrode current collector as claimed in any one of claims 1 to 10.
12. The battery negative electrode of claim 11, wherein the supported metal comprises lithium, sodium, potassium, zinc, aluminum, or magnesium.
13. The battery negative electrode of claim 11, wherein the supported metal is lithium.
14. A metal negative electrode secondary battery, characterized in that the battery comprises the battery negative electrode current collector of any one of claims 1 to 10.
15. The metal negative electrode secondary battery according to claim 14, wherein the battery is selected from a lithium battery, a sodium battery, a potassium battery, a zinc battery, an aluminum battery, or a magnesium battery.
16. The metal negative electrode secondary battery according to claim 15, wherein the battery is a symmetrical battery.
17. The metal negative electrode secondary battery according to claim 15, wherein the battery is a full battery.
18. The metal negative electrode secondary battery according to claim 14, wherein the battery comprises a current collector, a metal negative electrode, a positive electrode, a separator and an electrolyte.
19. The metal negative electrode secondary battery according to claim 18, wherein the metal negative electrode is obtained by plating a metal on the composite film; the electrolyte is ester or ether organic electrolyte or water-system inorganic electrolyte.
20. Use of the battery negative electrode current collector of any one of claims 1 to 10 and/or the battery negative electrode of any one of claims 11 to 13 and/or the metal negative electrode secondary battery of any one of claims 14 to 19 in the field of new energy industries.
21. Use according to claim 20, wherein the use comprises use in a drone, an electric vehicle or an energy storage device.
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| CN114944489B (en) * | 2022-06-15 | 2023-08-01 | 北京航空航天大学 | Thin film layer with accordion MXene array, preparation method of thin film layer, current collector, electrode and battery |
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