CN110165209A - A kind of organic alkali expands layer Mxene material and preparation method thereof, application - Google Patents

A kind of organic alkali expands layer Mxene material and preparation method thereof, application Download PDF

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Publication number
CN110165209A
CN110165209A CN201910379290.8A CN201910379290A CN110165209A CN 110165209 A CN110165209 A CN 110165209A CN 201910379290 A CN201910379290 A CN 201910379290A CN 110165209 A CN110165209 A CN 110165209A
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China
Prior art keywords
mxene material
organic alkali
preparation
layer
layer mxene
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CN201910379290.8A
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Chinese (zh)
Inventor
刘汉康
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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 the preparation methods that a kind of organic alkali expands layer Mxene material, include the following steps: for Mxene material to be added in organic alkali aqueous solution and stir, being washed out to pH is neutrality, then ultrasound is uniformly, and freeze-drying obtains organic alkali and expands layer Mxene material.The invention also discloses a kind of organic alkalis to expand layer Mxene material, is prepared according to the method described above.Expand layer Mxene material the invention also discloses above-mentioned organic alkali and prepares the application in lithium ion battery and sodium-ion battery.The method of the present invention is simple, low energy consumption, organic alkali is selected to realize the expansion layer to Mxene material, and bigger cation radius obtains bigger interlamellar spacing, not only accelerate lithium ion transport, and be very beneficial to the storage of sodium ion, it is applied well in lithium ion battery and sodium-ion battery.

Description

A kind of organic alkali expands layer Mxene material and preparation method thereof, application
Technical field
The present invention relates to electrochemical technology fields more particularly to a kind of organic alkali to expand layer Mxene material and its preparation side Method, application.
Background technique
Mxene (Chinese: two-dimentional transition metal carbon (nitrogen) compound) is the two-dimensional layer material of discovery in a kind of 2011, Excellent electronic conductivity, surface hydrophilic ability and good stability are presented, the Mxene of layer structure has been applied in storage The fields such as energy, photocatalysis, hydrogen storage and absorption.
But due to being limited with the interlamellar spacing for preparing Mxene material after HF acid etch, surface also remains-F/-OH Functional group, therefore embedding lithium ability is poor；The radius of sodium ion is greater than lithium ion, to obtain good embedding sodium performance, to Mxene The expansion layer of material is very important.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of organic alkali expand layer Mxene material and its Preparation method, application, the method for the present invention is simple, low energy consumption, selects organic alkali to realize the expansion layer to Mxene material, and bigger Cation radius obtain bigger interlamellar spacing, not only accelerate lithium ion transport, but also be very beneficial to the storage of sodium ion, It is applied well in lithium ion battery and sodium-ion battery.
A kind of organic alkali proposed by the present invention expands the preparation method of layer Mxene material, includes the following steps: Mxene Material is added in organic alkali aqueous solution and stirs, and being washed out to pH is neutrality, then ultrasound is uniformly, and freeze-drying obtains organic strong Alkali expands layer Mxene material.
Preferably, organic alkali is tetrabutylammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, benzyl three Ammonium hydroxide, tetrapropylammonium hydroxide, front three adamantyl ammonium hydroxide, trimethylethyl ammonium hydroxide, phenyl three At least one of ammonium hydroxide, phenyl triethylammonium ammonium hydroxide.
Preferably, the mass fraction of organic alkali aqueous solution is 5-40wt%.
Preferably, whipping temp is 25-80 DEG C.
Preferably, mixing time 2-48h.
Preferably, speed of agitator 200-1200rpm.
Preferably, supersonic frequency 28-100kHz.
Preferably, ultrasonic time 20-120min.
Preferably, Mxene material is Ti3C2、Ti2C、Ti2N、Nb2C、Nb4C3、Ta2C、Ta4C3、V2C、V3C2、Cr2C、 Cr3C2、(Ti0.5Nb0.5)2C、Ti3(C0.5N0.5)2、Mo2C or Mo3C2。
Above-mentioned Mxene material can be prepared by conventional method in that art, for example, can be handled with HF aqueous solution MAX material obtains Mxene material.
Above-mentioned water is deionized water.
The invention also provides a kind of organic alkalis to expand layer Mxene material, expands layer Mxene material according to above-mentioned organic alkali Preparation method be prepared.
The invention also provides above-mentioned organic alkalis to expand layer Mxene material in preparing lithium ion battery and sodium-ion battery Application.
Inventors discovered through research that overbased materials to Mxene material have expand layer effect, wherein strong base material middle-jiao yang, function of the spleen and stomach from Sub- radius is bigger, and it is better to expand layer effect.Relative to inorganic strong alkali, organic alkali can be realized bigger by the substitution of functional group Cation radius, so that Mxene material obtains bigger interlamellar spacing after expanding layer, so as to accelerate the transmission of lithium ion, Be conducive to the storage of sodium ion.
In expanding layer reaction process, negatively charged-F/-OH official is contained on the Mxene material obtained through HF acid etch, surface It can roll into a ball, after organic alkali is added, be reacted by Electrostatic Absorption, the cation and negatively charged anion in organic alkali are spontaneous In conjunction with therefore interlamellar spacing is also gradually expanded, finally obtain organic alkali and expand layer Mxene material；The interlamellar spacing of the material becomes larger, and has Conducive to the transmission of ion, the transmission of lithium sodium ion is accelerated, and Mxene material possesses excellent electronic conductivity and good in addition Stability, therefore organic alkali expands layer Mxene material and has good application prospect in energy storage field.
Preparation method of the present invention is simple, low energy consumption, realizes the expansion layer to Mxene material by organic alkali, and bigger Cation radius obtains bigger interlamellar spacing, not only accelerates lithium ion transport, but also be very beneficial to the storage of sodium ion, It is applied well in lithium ion battery and sodium-ion battery.
Detailed description of the invention
Fig. 1 is that organic alkali made from embodiment 1 expands layer Mxene scanning of materials electron microscopic picture.
Fig. 2 is the stereoscan photograph of Mxene material before expanding layer.
Fig. 3 is the storage lithium performance map of Mxene electrode slice before and after expanding layer.
Fig. 4 is the storage sodium performance map of Mxene electrode slice before and after expanding layer.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of organic alkali expands the preparation method of layer Mxene material, includes the following steps: that with mass fraction be 40wt%HF Aqueous solution handles MAX material Ti3AlC2For 24 hours, it is centrifuged, washing is dried to obtain Mxene material Ti3C2；
The tetrabutylammonium hydroxide aqueous solution that mass fraction is 40wt% is diluted with water and is uniformly mixed so as to obtain mass fraction and is 25wt% tetrabutylammonium hydroxide aqueous solution；
By 1g Mxene material Ti3C2It is in 25wt% tetrabutylammonium hydroxide aqueous solution, in 30 that 10mL mass fraction, which is added, DEG C, for 24 hours with the revolving speed stirring of 800rpm, it is neutral for then being washed repeatedly with water to pH value of solution, then with the frequency ultrasound of 50kHz 30min, freeze-drying obtain organic alkali and expand layer Mxene material.
Test example 1
The organic alkali of Example 1 expands layer Mxene material, Mxene material Ti3C2Electron-microscope scanning is carried out, as a result referring to figure 1-2, Fig. 1 are that organic alkali made from embodiment 1 expands layer Mxene scanning of materials electron microscopic picture；Fig. 2 is to expand Mxene material before layer Stereoscan photograph；By Fig. 1-2 it can be seen that the interlamellar spacing of Mxene material significantly increases after organic alkali expands layer.
Test example 2
The organic alkali of embodiment 1 is expanded into layer Mxene material, Mxene material is mixed with conductive agent, binder by matter respectively Amount is mixed than 8:1:1, and solubilizer is modulated into the uniform sizing material with mobility, which is coated on to the base cleaned out in advance Body places 12h in 60 DEG C of constant temperature ovens, then the dry 2h dry out solvent in 60 DEG C of vacuum ovens, by coating slurry Matrix is wrapped up with template, is prevented from polluting, is compacted with roll squeezer, is then placed in 60 DEG C of vacuum drying ovens dry 2h and is obtained after expanding layer Mxene electrode slice before Mxene electrode slice and expansion layer；
Wherein, the solvent is not particularly limited, as long as not decomposing in its drying course, is not remained after drying, Solvent is N-Methyl pyrrolidone herein；Matrix is copper foil, and the conductive materials such as aluminium foil are herein copper foil；Conductive agent is conductive charcoal At least one of black, electrically conductive graphite, carbon fiber (VGCF), carbon nanotube (CNTs), graphene；Binder is Kynoar (PVDF), at least one of styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE) (PTFE), polyvinyl alcohol (PVA), this Place is Kynoar (PVDF).
Performance detection is carried out to Mxene electrode slice before Mxene electrode slice, expansion layer after above-mentioned expansion layer, is come with button half-cell Evaluation and test.It as a result is the storage lithium performance map of Mxene electrode slice before and after expanding layer referring to Fig. 3-4, Fig. 3；Fig. 4 is Mxene electricity before and after expanding layer The storage sodium performance map of pole piece, the high rate performance of Mxene electrode slice significantly improves after expansion layer it can be seen from Fig. 3-4, through organic strong The storage lithium of Mxene material, storage sodium are significantly increased after alkali expansion layer.
Embodiment 2
MAX material is Ti2AlC, gained Mxene material are Ti2C, 1g Ti2It is 10wt% that C, which is added with 30mL mass fraction, In tetraethyl ammonium hydroxide aqueous solution, whipping temp is 45 DEG C, other are the same as embodiment 1.
Embodiment 3
MAX material is V3AlC2, gained Mxene material is V3C2, 1g Ti2C is added with 10mL mass fraction as 30wt% tetra- In ammonium hydroxide aqueous solution, whipping temp is 25 DEG C, and supersonic frequency 100kHz, other are the same as embodiment 1.
Embodiment 4
1g Ti3C2Being added with 25mL mass fraction is mixing time in 10wt% phenyl trimethicone ammonium hydroxide aqueous solution For 48h, supersonic frequency 30kHz, ultrasonic time 60min, other are the same as embodiment 1.
Embodiment 5
MAX material is Mo2AlC, gained Mxene material are Mo2C, 1g Mo2It is 25wt% that C, which is added with 10mL mass fraction, In tetrapropylammonium hydroxide solution, whipping temp is 60 DEG C, speed of agitator 1000rpm, mixing time 12h, other are same Embodiment 1.
Embodiment 6
MAX material is Nb3AlC2, gained Mxene material is Nb3C2, 1g Nb3C2Being added with 50mL mass fraction is 5wt% In tetrabutylammonium hydroxide aqueous solution, speed of agitator 1000rpm, supersonic frequency 80kHz, other are the same as embodiment 1.
Embodiment 7
MAX material is Ti2AlC, gained Mxene material are Ti2C, speed of agitator 400rpm, mixing time 36h, He is the same as embodiment 1.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (10)

1. the preparation method that a kind of organic alkali expands layer Mxene material, which comprises the steps of: by Mxene material It is added in organic alkali aqueous solution and stirs, being washed out to pH is neutrality, then ultrasound is uniformly, and freeze-drying obtains organic alkali expansion Layer Mxene material.
2. organic alkali expands the preparation method of layer Mxene material according to claim 1, which is characterized in that organic alkali is Tetrabutylammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, tetrapropyl hydroxide Ammonium, front three adamantyl ammonium hydroxide, trimethylethyl ammonium hydroxide, phenyl trimethicone ammonium hydroxide, phenyl triethylammonium hydrogen At least one of amine-oxides.
3. the preparation method that organic alkali according to claim 1 or claim 2 expands layer Mxene material, which is characterized in that organic alkali The mass fraction of aqueous solution is 5-40wt%.
4. any one of -3 organic alkalis expand the preparation method of layer Mxene material according to claim 1, which is characterized in that stir Mixing temperature is 25-80 DEG C.
5. any one of -4 organic alkalis expand the preparation method of layer Mxene material according to claim 1, which is characterized in that stir Mixing the time is 2-48h.
6. any one of -5 organic alkalis expand the preparation method of layer Mxene material according to claim 1, which is characterized in that stir Mixing revolving speed is 200-1200rpm.
7. any one of -6 organic alkalis expand the preparation method of layer Mxene material according to claim 1, which is characterized in that super Acoustic frequency is 28-100kHz；Preferably, ultrasonic time 20-120min.
8. any one of -7 organic alkalis expand the preparation method of layer Mxene material according to claim 1, which is characterized in that Mxene material is Ti3C2、Ti2C、Ti2N、Nb2C、Nb4C3、Ta2C、Ta4C3、V2C、V3C2、Cr2C、Cr3C2、(Ti0.5Nb0.5)2C、 Ti3(C0.5N0.5)2、Mo2C or Mo3C2。
9. a kind of organic alkali expands layer Mxene material, which is characterized in that prepared according to any one of claim 1-8 the method It obtains.
10. a kind of organic alkali as claimed in claim 9 expands layer Mxene material in preparing lithium ion battery and sodium-ion battery Application.
CN201910379290.8A 2019-05-08 2019-05-08 A kind of organic alkali expands layer Mxene material and preparation method thereof, application Pending CN110165209A (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN110694581A (en) * 2019-10-22 2020-01-17 安庆北化大科技园有限公司 Preparation method, stability testing method and application of carbon-based material
CN110767465A (en) * 2019-09-25 2020-02-07 洛阳师范学院 Preparation method of supercapacitor based on two-dimensional niobium carbide nano composite material
CN111799464A (en) * 2020-07-08 2020-10-20 中国科学院电工研究所 MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof
CN111883745A (en) * 2020-06-15 2020-11-03 辽宁科技大学 MOF/MXene/CF composite nanosheet and synthesis method thereof
CN113451590A (en) * 2021-06-29 2021-09-28 合肥工业大学 Preparation method of MXene-based catalyst with ion/electron double transmission

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CN108298541A (en) * 2018-02-05 2018-07-20 中国科学院电工研究所 A kind of preparation method of two-dimensional layer MXene nanometer sheets
CN109437172A (en) * 2018-10-09 2019-03-08 武汉科技大学 A kind of sodium ion intercalation Ti3C2MXene material and preparation method thereof

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KR20130109785A (en) * 2012-03-28 2013-10-08 삼성에스디아이 주식회사 Composite electrode active material, electrode and lithium battery containing the same, and preparation method thereof
CN108298541A (en) * 2018-02-05 2018-07-20 中国科学院电工研究所 A kind of preparation method of two-dimensional layer MXene nanometer sheets
CN109437172A (en) * 2018-10-09 2019-03-08 武汉科技大学 A kind of sodium ion intercalation Ti3C2MXene material and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110767465A (en) * 2019-09-25 2020-02-07 洛阳师范学院 Preparation method of supercapacitor based on two-dimensional niobium carbide nano composite material
CN110767465B (en) * 2019-09-25 2021-05-28 洛阳师范学院 Preparation method of supercapacitor based on two-dimensional niobium carbide nano composite material
CN110694581A (en) * 2019-10-22 2020-01-17 安庆北化大科技园有限公司 Preparation method, stability testing method and application of carbon-based material
CN111883745A (en) * 2020-06-15 2020-11-03 辽宁科技大学 MOF/MXene/CF composite nanosheet and synthesis method thereof
CN111883745B (en) * 2020-06-15 2023-10-17 辽宁科技大学 MOF/MXene/CF composite nano-sheet and synthesis method thereof
CN111799464A (en) * 2020-07-08 2020-10-20 中国科学院电工研究所 MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof
CN111799464B (en) * 2020-07-08 2021-08-27 中国科学院电工研究所 MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof
CN113451590A (en) * 2021-06-29 2021-09-28 合肥工业大学 Preparation method of MXene-based catalyst with ion/electron double transmission

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Application publication date: 20190823