CN106328890A - Carbon-pillared MXene composite material and application thereof - Google Patents
Carbon-pillared MXene composite material and application thereof Download PDFInfo
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- CN106328890A CN106328890A CN201610733990.9A CN201610733990A CN106328890A CN 106328890 A CN106328890 A CN 106328890A CN 201610733990 A CN201610733990 A CN 201610733990A CN 106328890 A CN106328890 A CN 106328890A
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- carbon
- mxene
- pillared
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- mxene composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003990 capacitor Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910019762 Nb4C3 Inorganic materials 0.000 claims description 2
- 229910004448 Ta2C Inorganic materials 0.000 claims description 2
- 229910004472 Ta4C3 Inorganic materials 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229920005615 natural polymer Polymers 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 229910003470 tongbaite Inorganic materials 0.000 claims description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims 1
- 210000000952 spleen Anatomy 0.000 claims 1
- 210000002784 stomach Anatomy 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract description 2
- 239000007833 carbon precursor Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000011229 interlayer Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910019637 Nb2AlC Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229960001040 ammonium chloride Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a carbon-pillared MXene composite material and an application thereof. The carbon-pillared MXene composite material comprises a two-dimensional layered MXene carrier and a carbon nanosheet loaded between MXene layers; and a preparation method comprises the following steps of (1) processing a taken MAX raw material in an HF solution to obtain an MXene material; (2) soaking the MXene material obtained in the step (1) into a solution of which the cationic carbon precursor content is 0.005-20g/mL, stirring at 30-100 DEG C for 0.5-72 hours and centrifuging, washing and drying a product to obtain a pre-pillared MXene material; and (3) heating the pre-pillared MXene material in a protective atmosphere to 300-800 DEG C at the rate of 2-10 DEG C/min and carrying out insulating calcination treatment for 0.5-4 hours to obtain the carbon-pillared MXene material. The invention provides an application of the carbon-pillared MXene composite material as an electrode material of a lithium-ion battery or a super capacitor. The capacity of the electrode material can be greatly improved and the cycle performance is good, so that the operating requirements in the field of high energy and high power are met.
Description
(1) technical field
The present invention relates to a kind of carbon pillared MXene composite and as lithium ion battery or electrode of super capacitor material
The application of material.
(2) background technology
MXene material is a class New Two Dimensional stratiform transition metal C/N compound-material.This two dimension MXene material has
The features such as excellent electric conductivity, chemical stability.Up to the present prepare MXene material to be mainly by HF solution etches MAX
Raw material and obtain.Up to now, MXene has been applied to multiple field, such as: lithium ion battery, ultracapacitor, light
The fields such as catalysis, hydrogen storage.Although MXene material has the electric conductivity of excellence, excellent chemical stability, but it is at lithium ion
Battery is applied capacity relatively low (50-200mAh/g), hence it is evident that less than the capacity (372mAh/g) of commercialization graphite material.This is very
MXene application prospect in lithium ion battery is limited in big degree.Although it addition, MXene material is led at ultracapacitor
Territory application has high capacity (～360F/cm3), but its potential interlayer energy storing space is not fully used.If
The interlayer energy storing space of MXene material is exploited further, and it is as lithium ion battery material, the capacity of ultracapacitor
It is expected to promote further.
(3) summary of the invention
The goal of the invention of the present invention is to provide a kind of carbon pillared MXene composite and as lithium ion battery or super
The application of electrode material in capacitor.
Technical scheme is specifically described below.
The invention provides a kind of carbon pillared MXene composite, including two-dimensional layer MXene carrier and be supported on
The carbon nanosheet of MXene interlayer；Its preparation method comprises the steps:
(1) take MAX raw material, process in HF solution and obtain MXene material；
(2) the MXene material that step (1) obtains being immersed in cationic carbon matrix precursor content is 0.005-20g/mL's
In solution, at 30-100 DEG C, stir 0.5～72h, be then centrifuged for, wash, be dried to obtain pre-pillared MXene material；
(3) by pre-pillared MXene material under protective atmosphere with the ramp of 2～10 DEG C/min to 300-800 DEG C, protect
Temperature calcination processing 0.5～4h, obtains carbon pillared MXene material.
In step of the present invention (1), described MXene material is Ti3C2、Ti2C、Ti2N、Nb2C、Nb4C3、Ta2C、Ta4C3、
V2C、V3C2、Cr2C、Cr3C2、(Ti0.5Nb0.5)2C or Ti3(C0.5N0.5)2.Those skilled in the art can be according to required preparation
MXene material, selects suitable MAX raw material, and the method reported by document prepares MXene material.Preferably, step
(1) concrete operations are: weigh MAX raw material, add in the HF solution that mass fraction is 10%～50%, wherein HF solution
Inventory is calculated as 3～50mL/g with the raw-material quality of MAX, under room temperature soak 2～56h, be then centrifuged for, be washed to pH=6～
7, MXene powder it is dried to obtain.
In step of the present invention (2), described cationic carbon matrix precursor can be cationic natural polymer, as bright
Glue, chitosan, chitin etc.；Can also be cationic polyelectrolyte, such as diallyl dimethyl ammoniumchloride, polydiene diformazan
Ammonium chloride, polymine, polyvinylamine etc.；Preferably its purity is more than 90%.The solvent of described solution can be water, second
The common solvents, preferably its purity such as alcohol, methanol, acetone are more than 90%.Anions in solution type carbon matrix precursor content is preferably
0.05-15g/mL, more preferably 0.05～10g/mL.The inventory of the solution containing cationic carbon matrix precursor is with MXene material
The quality of material is calculated as 5～1000mL/g.
In step of the present invention (2), stirring, preferably at 30-80 DEG C, is carried out at more preferably 40-80 DEG C, and mixing time is preferably
1-48h, more preferably 3～36h.
In step of the present invention (3), the group of one or both arbitrary proportions during protective atmosphere is argon, nitrogen during calcining
Closing, preferably its purity is more than 90%.Calcining heat is preferably 400～700 DEG C, and calcination time is preferably 1～4 hour.
The present invention provides a kind of carbon pillared MXene composite as lithium ion battery or electrode material for super capacitor
Application.
Compared with prior art, the beneficial effects are mainly as follows: preparation method of the present invention is simple, utilize
The electronegative characteristic of MXene material surfaces externally and internally after acid etch, allows the cationic carbon matrix precursor of positively charged pass through electrostatic
Adsorption inserts MXene material interlayer, effectively struts MXene material interlayer；Afterwards through a step carbonization, obtain carbon pillared
MXene material.This material is as lithium ion battery, super capacitor material, and in charge and discharge process, carbon nanosheet itself provides
Capacity, and it can effectively strut MXene interlayer, gives the energy storing space that material is bigger, it is provided that more capacity, significantly
MXene is as lithium ion battery, the capacity of ultracapacitor in lifting, and stable cycle performance, thus meet and use requirement.
(4) accompanying drawing explanation
Fig. 1 is the embodiment 1 pillared Ti of carbon3C2XRD comparison diagram before and after MXene.According to Bragg equation, the angle in XRD peak
θ is the least for degree, and just explanation interlamellar spacing d is the biggest, so from comparison diagram, after carbon is pillared, interlamellar spacing becomes big, just illustrates that carbon is received
Rice sheet enters into Ti3C2MXene interlayer.
Fig. 2 is the embodiment 1 pillared Ti of carbon3C2The SEM figure of MXene.
Fig. 3 is the pillared Ti of the carbon prepared by embodiment 13C2The cycle performance of lithium ion battery figure of MXene.
Fig. 4 is the pillared Ti of the carbon prepared by embodiment 13C2The ultracapacitor cycle performance figure of MXene.
(5) detailed description of the invention
With specific embodiment, technical scheme is described further below, but protection scope of the present invention does not limits
In this.
Embodiment 1
Take 3g Ti3AlC2Powder (MAX), in beaker, adds the HF solution that 10ml mass fraction is 40%, stirring, room temperature
Lower etching 16h.Then by the Ti after etching3C2MXene powder is centrifuged out, and spends Ion Cleaning to PH=6～7, at 80 DEG C
Convection oven in dry 12h.0.1g Ti after drying3C2MXene powder, at 40mL, containing 0.05g/mL gelatin, (Aladdin tries
Agent, chemical pure) aqueous solution in 50 DEG C of stirring 5h, centrifugal, spend Ion Cleaning, dry, after in nitrogen atmosphere with 10 DEG C/
It is incubated 2h at the heating rate of min 500 DEG C and obtains the pillared Ti of carbon3C2MXene material.
With the pillared Ti of carbon obtained by embodiment 13C2MXene material powder makes electrode as follows.
The pillared Ti of carbon is weighed respectively with the mass ratio of 80:10:103C2MXene material: super-P:PVDF, after grinding uniformly
Making electrode, metal lithium sheet is to electrode, and electrolyte is 1mol/L LiPF6/ EC:DMC (1:1), polypropylene microporous film be every
Film, is assembled into simulation lithium ion battery.Fig. 3 be respective battery under 100mA/g electric current density, the voltage range of 0.01 3.0V
Interior cycle performance curve, shows that surveyed battery has higher capacity, good cycle performance under 100mA/g electric current density
With high coulombic efficiency, it can be seen that the pillared Ti of carbon prepared by embodiment 13C2MXene material is under 100mA/g electric current density
Circulate the discharge capacity after 50 times close to 520mAh/g (Fig. 3), compared to the Ti of the most pillared process3C2The capacity of MXene (～
120mAh/g), capacity has had and has significantly promoted, and cycle performance is excellent.
The pillared Ti of carbon is weighed respectively with the mass ratio of 85:10:53C2MXene material: super-P:PTFE, drips the most different
Propanol, after grinding uniformly, rolls film, tabletting, engraved film, makes circular membrane, and the electrode material membrane made is dry in vacuum drying oven
Dry a whole night, weigh film quality, use the pressure of 14Mpa to be pressed in by thin film on the stainless (steel) wire made in advance afterwards and be used for surveying
The chemical property of examination material.In three-electrode system, with 1mol/L H2SO4Solution is electrolyte solution, with the electrode made
Material is working electrode, and saturated calomel electrode is reference electrode, and platinized platinum is auxiliary electrode, and electrochemical workstation is circulated volt-ampere
Curve, constant current charge-discharge are tested.Test voltage scope is-0.8-0.1V.Fig. 4 be respective battery under 5A/g electric current density ,-
Cycle performance curve in the voltage range of 0.8-0.1V, the ultracapacitor that surface is surveyed circulates the discharge capacity after 5000 times
Close to 285F/g (Fig. 4), compared to the Ti of the most pillared process3C2The capacity (～100F/g) of MXene, capacity has had and has significantly carried
Rising, cycle performance is excellent.
Embodiment 2
Take 2.5g Ti2AlC powder, in beaker, adds the HF solution that 30ml mass fraction is 40%, and stirring, under room temperature
Etching 8h.Then etching powder is centrifuged out Ti2C MXene powder, spends Ion Cleaning to PH=6～7, the air blast of 80 DEG C
Baking oven dries 12h.Ti after 0.2g is dried2C MXene powder, in 50mL diallyl dimethyl chlorination Han 0.5g/mL
In the aqueous solution (Aladdin reagent, Mw 100000-200000,20wt.% aqueous solution, CP) of ammonium, 60 DEG C of stirring 4h, centrifugal, uses
Deionization clean, dry, after in argon gas atmosphere with at the heating rate 500 DEG C of 5 DEG C/min be incubated 2h obtain the pillared Ti of carbon2C
MXene material.With the obtained pillared Ti of carbon2Electrode made as described in Example 1 by C MXene material, be assembled into mould lithium from
Sub-battery, circulates the discharge capacity after 50 times close to 485mAh/g, compared to the most pillared process under 100mA/g electric current density
Ti2The capacity (～135mAh/g) of CMXene, capacity has had and has significantly promoted, and cycle performance is good.
Embodiment 3
Take 2.8g Nb2AlC powder, in beaker, adds the HF solution that 20ml mass fraction is 35%, and stirring, under room temperature
Etching 18h.Then etching powder is centrifuged out Nb2C MXene powder, spends Ion Cleaning to PH=6～7, at the drum of 80 DEG C
Wind baking oven dries 8h.Nb after 0.15g is dried2C MXene powder, 60mL contain 2g/mL chitosan (Aladdin reagent,
Middle viscosity, 200-400mPa.s) solution in 60 DEG C of stirring 8h, centrifugal, spend Ion Cleaning, dry, after in argon gas atmosphere
The pillared Nb of carbon is obtained with insulation 2h at the heating rate 600 DEG C of 3 DEG C/min2C MXene material.With the obtained pillared Nb of carbon2C
Electrode made as described in Example 1 by MXene material, is assembled into simulation ultracapacitor, circulates under 10A/g electric current density
Discharge capacity after 3000 times is close to 275F/g, compared to the Nb of the most pillared process2The capacity (～95F/g) of C MXene, capacity
Having had and significantly promoted, cycle performance is good.
Embodiment 4
Take 4g V2AlC powder, in plastic beaker, adds the HF solution that 40ml mass fraction is 20%, soaks under room temperature
16h.Then the powder after soaking is centrifuged out, and is washed with deionized water to PH=6～7, dries in the convection oven of 80 DEG C
20h.V after 0.25g is dried2C MXene powder, 50mL containing 1g/mL polymine (Aladdin reagent, Mw 10000,
99%) in ethanol solution, 40 DEG C of stirring 6h, centrifugal, spends Ion Cleaning, dries, after in argon gas atmosphere with 6 DEG C/min's
It is incubated 4h at heating rate 700 DEG C and obtains the pillared V of carbon2C MXene material.With the obtained pillared V of carbon2C MXene material is by real
The method executing example 1 makes electrode, is assembled into mould lithium ion battery, circulates the electric discharge after 50 times and hold under 100mA/g electric current density
Amount is close to 520mAh/g, compared to the V of the most pillared process2Capacity (～105mAh/g) cycle performance of CMXene is good.
Claims (10)
1. a carbon pillared MXene composite, its preparation method comprises the steps:
(1) take MAX raw material, process in HF solution and obtain MXene material；
(2) the MXene material that step (1) obtains being immersed in cationic carbon matrix precursor content is the solution of 0.005-20g/mL
In, at 30-100 DEG C, stir 0.5～72h, be then centrifuged for, wash, be dried to obtain pre-pillared MXene material；
(3) by pre-pillared MXene material under protective atmosphere with the ramp of 2～10 DEG C/min to 300-800 DEG C, insulation is forged
Burning processes 0.5～4h, obtains carbon pillared MXene material.
2. carbon pillared MXene composite as claimed in claim 1, it is characterised in that: in step (1), MXene material is
Ti3C2、Ti2C、Ti2N、Nb2C、Nb4C3、Ta2C、Ta4C3、V2C、V3C2、Cr2C、Cr3C2、(Ti0.5Nb0.5)2C or Ti3
(C0.5N0.5)2。
3. carbon pillared MXene composite as claimed in claim 1 or 2, it is characterised in that: in step (2), cationic carbon
Presoma is cationic natural polymer or cationic polyelectrolyte.
4. carbon pillared MXene composite as claimed in claim 3, it is characterised in that: described cationic carbon matrix precursor
Selected from one of following: gelatin, chitosan, chitin, diallyl dimethyl ammoniumchloride, polydiallyldimethyl ammonium chloride, poly-
Aziridine, polyvinylamine.
5. carbon pillared MXene composite as claimed in claim 1 or 2, it is characterised in that: in step (2), described solution
Solvent is water, ethanol, methanol or acetone.
6. carbon pillared MXene composite as claimed in claim 1 or 2, it is characterised in that: in step (2), solution middle-jiao yang, function of the spleen and stomach from
Subtype carbon matrix precursor content is 0.05-15g/mL, and the inventory of the solution containing cationic carbon matrix precursor is with MXene material
Quality is calculated as 5～1000mL/g.
7. carbon pillared MXene composite as claimed in claim 1 or 2, it is characterised in that: in step (3), protect during calcining
Atmosphere is the combination of one or both arbitrary proportions in argon, nitrogen.
8. carbon pillared MXene composite as claimed in claim 1 or 2, it is characterised in that: in step (3), calcining heat is
400-700 DEG C, calcination time is 1～4 hour.
9. carbon pillared MXene composite as claimed in claim 1 or 2, it is characterised in that: described preparation method is by step
(1)～(3) composition.
10. carbon pillared MXene composite as claimed in claim 1 or 2 is as lithium ion battery or electrode of super capacitor
The application of material.
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