CN104733712A - Preparation method of transition metal oxide/carbon-based laminated composite material - Google Patents
Preparation method of transition metal oxide/carbon-based laminated composite material Download PDFInfo
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- CN104733712A CN104733712A CN201510125481.3A CN201510125481A CN104733712A CN 104733712 A CN104733712 A CN 104733712A CN 201510125481 A CN201510125481 A CN 201510125481A CN 104733712 A CN104733712 A CN 104733712A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method of a transition metal oxide/carbon-based laminated composite material. According to the preparation method, a conducting material such as metal carbide, metal nitride or metal carbonitride with a two-dimensional laminated structure is taken as a precursor, a gas containing oxygen elements is taken as an oxidant, and the two-dimensional conducting material is converted into the transition metal oxide/carbon-based laminated composite material by in-situ oxidation under the condition of controlling the oxidation temperature at 300-1000 DEG C and controlling the oxidation time at 1-300 min. The method disclosed by the invention has the advantages of simplicity and easiness in operation, controllable structure and morphology, controllable crystal form and electrochemical properties of metal oxides, and the like; the preparation method is environment-friendly, and nuisanceless, has no by-product, can be used for reducing the economic costs of traditional preparation methods, and can be popularized; and the transition metal oxide/carbon-based laminated composite material not only can be used as a key electrode material of a new energy storage device, but also can be used as a denitration catalyst, so that the material can be applied to the fields of environmental remediation, and the like.
Description
Technical field
The present invention relates to material with carbon element field, especially relate to the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material.
Background technology
Chemical power source, if rechargeable battery (also known as secondary cell) is a kind of device directly stored with the form of chemical energy by electric energy.Because the conversion ratio of convenient, fast, energy and utilance high, chemical power source obtains fast development in nearest decades.The working mechanism of lithium ion battery is that its chemical energy stored is very large, and energy density is very high by lithium ion to the lithiumation of intercalation compound with go lithiumation to carry out reversible chemical reaction.But because carried out chemical reaction is limited to lithium ion diffusion and electronics transmission (conductivity of intercalation compound is generally on the low side, and electronics transmits slow) process, therefore the charge-discharge velocity of lithium ion battery is very slow, and power density is very low.Ultracapacitor then has the advantages such as discharge and recharge time short (<30s), power density high (10kW/kg), energy density high (1 ~ 10Wh/kg), good cycle (500,000 times), coulombic efficiency high (98%), but the cost of ultracapacitor is generally higher.Therefore with regard to the manufacturing cost of more effective reduction ultracapacitor, especially material manufacturing cost, becomes the bottleneck place of technological break-through.
The electrode material of super capacitor can be divided into three major types substantially: porous carbon material, metal oxide, conducting polymer.For porous carbon material, duct reaches all the more, and corresponding theoretical ratio capacitance is higher, but because be subject to can close to the restriction of active sites number, the specific area increasing Carbon Materials can not make ratio capacitance linearly increase, the usual <200F/g of ratio capacitance.This is because specific area is larger, hole wall is thinner, the electric double layer adjoined is easily overlapping, the three-dimensional effect in hole causes under certain electric field strength, and hole wall can not hold the electric charge of same quantity, causes ratio capacitance that " saturated " (O.Barbieri etc. occur, Carbon, 2005, the 43rd volume, 1303rd ~ 1310 pages).Therefore the concept of fake capacitance is introduced by numerous researchers, to by there is redox reaction fast at material surface or nearly surface, providing the fake capacitance because Charger transfer causes, thus promoting the overall chemical property of material.By in Carbon Materials skeleton or nitrating (H.Chen etc., J.Phys.Chem.C, 2013 years on the surface, 117th volume, 8318th ~ 8328 pages), boron-doping (D.Wang etc., Chem.Mater., 2008,20th volume, 7195th ~ 7200 pages), oxygen-doped (G.Lota, J.Power Sources, 2010,195th volume, 7535th ~ 7539 pages), all can provide fake capacitance.Combined with conducting polymer by porous carbon material, the composite material formed also can provide very high ratio capacitance (E.Frackowiak etc., Journal of Power Sources, the 153rd volume, 413rd ~ 418 pages in 2006).But, because polymer capacity attenuation in repeated charge process is too fast, the use of such composite material is restricted (J.Zhang etc., the 116th volume, 5420th ~ 5426 pages in 2012).In addition, because the metallic atom in transition metal oxide has multiple valence state, thus have very high theoretical specific capacity, porous carbon material then has good conductivity and flourishing pore passage structure.Therefore, transition metal oxide and porous carbon material are combined, while raising material monolithic ratio capacitance, utilize the spacial framework of Carbon Materials porous, promote the quick transmission of electronics on material back bone network, while material energy densities and power density can be realized, promote (C.Zhang etc., J.Power Sources, 2015, the 274th volume, 121st ~ 129 pages).
The network configuration of porous carbon material prosperity substantially prolongs the evolving path and the diffusion time of lithium ion.When being greater than discharge time, can cause the uneven lithiumation of material/go lithiumation, the non-homogeneous stress of generation can the efflorescence of accelerated material, and metal oxide nanoparticles is reunited, and finally causes adverse effect to the high rate performance of composite material diffusion time.Therefore, construct the transition metal oxide/based composite material of carbon with convenient lithium ion the evolving path, be expected in lithium ion battery, ultracapacitor, play excellent chemical property.
As the typical two-dimensional material of one, the discovery of Graphene causes great sensation.Graphene be a kind of by carbon atom with sp
2hybridized orbit composition hexangle type is the flat film of honeycomb lattice, has many excellent properties, as the conductivity (0.3 × 10 of superelevation
6and thermal conductivity coefficient (~ 3000W/m K) S/m), electron transfer fast and semimetal band structure etc. (A.K.Geim etc., Nat.Mater., 2007,6th volume, 183rd ~ 191 pages), obtain at numerous areas such as transistor, touch-screen, solar panels rapidly and explore and application.Adopt Graphene as carbon carrier, the conductivity of composite material can be significantly improved.By changing synthetic method, can prepare the sandwich style laminar composite of metal oxide/Graphene, its layer structure is conducive to rapid diffusion and the migration of ion, for the high-rate characteristics of lithium ion battery provides theory support.But due to the effect of Van der Waals force, Graphene is easy to reunite, and offsets the advantage that its layer structure is beneficial to ion diffuse.There is again a large amount of defect and functional group in the multi-layer graphene that chemical stripping method obtains, causes specific area and conductivity all significantly to reduce, finally have a negative impact to the chemical property of metal oxide/Graphene.In addition, preparation technology is tediously long, cost is high, also makes conventional method construct the Commercial Prospect of transition metal oxide/Graphene laminar composite uncertain.
Summary of the invention
Object of the present invention is exactly provide the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material to overcome defect that above-mentioned prior art exists, and provide the chemical property of gained laminar composite in ultracapacitor and lithium ion battery, thus achieve high power capacity, high magnification, the low cost of high life electrode material, the non-harmful preparation of environmental protection.The method also can prepare the V of stratiform
2o
5/ C, TiO
2/ C, thus be applied in the environment remediation fields such as denitration.
Object of the present invention can be achieved through the following technical solutions:
The preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material, two-dimentional electric conducting material is adopted to be presoma, the gas containing oxygen element is utilized to be oxidant, controlled oxidization temperature is 300 ~ 1000 DEG C, oxidization time is 1 ~ 300min, be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen
Described two-dimentional electric conducting material is the metal carbides of two-dimensional layered structure, metal nitride or carbonitride.
Described two-dimentional electric conducting material is MXene, and wherein M is metallic element, and X is carbon and/or nitrogen, and lamellar spacing is 1nm, and interlayer has a large amount of containing oxygen and fluorine-containing functional group, makes MXene be water wetted material.Theoretical MXene (Bu Dai functional group) has with the similar conductivity of Graphene, and the MXene containing functional group is semi-conducting material, and energy level difference is 2.0eV.
Described two-dimentional electric conducting material is Ti
2c, Ti
2n, Ti
3c
2, Ti
4n
3, Ta
2c, Ta
4c
3, Cr
2c, Cr
3c
2, V
2c, V
3c
2, Nb
2c or Nb
4c
3, (Ti
0.5nb
0.5)
2c or Ti
3(C
0.5n
0.5)
2.
Described two-dimentional electric conducting material is preferably Ti
3c
2, Nb
2c, Nb
4c
3or Ti
3(C
0.5n
0.5)
2.
Described two-dimentional electric conducting material and the ratio of oxidant are 0.05-5g/1-250sccm.
Described oxidant is carbon dioxide, air, nitrogen dioxide etc.
Before carrying out in-situ oxidation; inert gas is adopted to carry out slow rinse 10-120min to reaction system; then two-dimentional electric conducting material controls heating rate under the protection of inert gas is 2-60 DEG C/min, is warming up to 300 ~ 1000 DEG C, then passes into oxidant and carry out in-situ oxidation.
When carrying out in-situ oxidation, when the amount of two-dimensional material is 0.1-1g, the flow of oxidant is 10-200sccm, and oxidizing temperature is 600-900 DEG C, oxidization time is 10 ~ 120min, can be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen.
The transition metal oxide prepared/charcoal base layer-shaped composite material particle size is 1 ~ 30 μm, and the metal oxide contained is 10 ~ 100nm, and composite material retains the layer structure of two-dimentional electric conducting material.
The transition metal oxide prepared/charcoal base layer-shaped composite material is applied on ultracapacitor and/or lithium ion battery, all show high discharge capacity, lithium ion the behavior of fake capacitance intercalation, possess the excellent specific property such as fast charging and discharging ability and good useful life.
Compared with prior art, the present invention utilizes the layer structure of MXene can provide passage easily for the rapid diffusion of ion; The charcoal formed and the MXene of non-complete oxidation all can improve the inferior position of metal oxide conductivity deficiency, and the metal oxide nanoparticles formed is exposed to sheet surfaces, thus increase the contact area with electrolyte, improve the utilance of active sites.
The present invention adopt first in-situ oxidation two dimension MXene thinking, one-step method has prepared transition metal oxide/charcoal base layer-shaped composite material, the method environmental protection, simple to operation, can promote.The composite material of gained has good electrochemistry capacitance, multiplying power, extend the useful life of electrode material, thus the laminar composite solving traditional transition metal oxide/charcoal high cost, high pollution, the complex process prepared and the problems such as capacity attenuation is obvious, specifically have the following advantages:
(1) to prepare the process route of transition metal oxide/based composite material of carbon tediously long for tradition, and accessory substance is many, and particle size is large and disperse uneven.And present invention process route is short, preparation method is simply controlled, with low cost, environmental protection.
(2) traditional rhombic system Nb
2o
5(T-Nb
2o
5the preparation of)/C composite adopts two step method usually, namely first prepares Nb
2o
5, then heat treatment forms T-Nb at 600 DEG C in atmosphere
2o
5, then at T-Nb
2o
5coated one deck charcoal outside particle, forms T-Nb
2o
5/ C composite.Step is numerous, method is tediously long, variable is many, not easy to operate.And the present invention adopts the thinking of in-situ oxidation MXene, one-step method has prepared T-Nb from two-dimentional MXene
2o
5/ C laminar composite, no coupling product.By the condition of regulation and control oxidation, can implement to control to the crystal formation, particle size, chemical property etc. of oxide in gained composite material.
(3) traditional preparation T-Nb
2o
5in/C technique, have employed a lot of organic solvent, as phenmethylol etc., these organic solvents easily volatilize when solvent-thermal process, and after synthetic product, organic solvent becomes waste liquid, bring not little pressure to environment.And the oxygen-containing gas that the present invention adopts is as oxidant, process cleans, tail gas environmental protection, can not bring environmental pollution.
(4) with the T-Nb reported
2o
5the chemical property of/C composite is compared, and the present invention adopts the T-Nb of preparation method's gained
2o
5/ C laminar composite, not only in ultracapacitor, there is high specific capacitance, charging and discharging capabilities and good cycle life fast, and as the negative material of lithium ion battery, also there is high discharge capacity, coulombic efficiency and cycle performance, absolutely prove that the dual-use occasion of ultracapacitor and lithium ion battery is competent at by the composite material prepared by this simple and easy method.In addition, the method is adopted to prepare the V of stratiform
2o
5/ C, TiO
2/ C composite, then can be applied in the environment remediation fields such as denitration.
(5) traditional method is confined to a certain specific metal oxide system, and the preparation method that the present invention adopts, not only can the superior T-Nb of processability
2o
5/ C laminar composite, can also change presoma, prepares Detitanium-ore-type TiO
2/ C laminar composite, makes preparation method become universal method, solves the problems such as synthetic method practicality is wideless, achieves the amplification of technique.This technique drastically increases efficiency prepared by composite material, significantly shortens the manufacturing cycle of material.
Accompanying drawing explanation
Fig. 1 is for obtaining ESEM and the transmission electron microscope photo of sample prepared by course of reaction each in embodiment 1.
Embodiment
The preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material, two-dimentional electric conducting material is adopted to be presoma, the gas containing oxygen element is utilized to be oxidant, the ratio of two dimension electric conducting material and oxidant is 0.05-5g/1-250sccm, controlled oxidization temperature is 300 ~ 1000 DEG C, oxidization time is 1 ~ 300min, is transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen
Metal carbides, metal nitride or carbonitride that the two-dimentional electric conducting material used is two-dimensional layered structure.Specifically, two-dimentional electric conducting material is MXene, and wherein M is metallic element, and X is carbon and/or nitrogen, and lamellar spacing is 1nm, and interlayer has a large amount of containing oxygen and fluorine-containing functional group, makes MXene be water wetted material.Theoretical MXene (Bu Dai functional group) has with the similar conductivity of Graphene, and the MXene containing functional group is semi-conducting material, and energy level difference is 2.0eV.Such as, two-dimentional electric conducting material can be Ti
2c, Ti
2n, Ti
3c
2, Ti
4n
3, Ta
2c, Ta
4c
3, Cr
2c, Cr
3c
2, V
2c, V
3c
2, Nb
2c or Nb
4c
3, (Ti
0.5nb
0.5)
2c or Ti
3(C
0.5n
0.5)
2.
Oxidant is carbon dioxide, air, nitrogen dioxide etc.
In addition; before carrying out in-situ oxidation, adopt inert gas to carry out slow rinse 10-120min to reaction system, then two-dimentional electric conducting material controls heating rate under the protection of inert gas is 2-60 DEG C/min; be warming up to 300 ~ 1000 DEG C, then pass into oxidant and carry out in-situ oxidation.When carrying out in-situ oxidation, when the amount of two-dimensional material is 0.1-1g, the flow of oxidant is 10-200sccm, and oxidizing temperature is 600-900 DEG C, oxidization time is 10 ~ 120min, can be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen.
The transition metal oxide prepared/charcoal base layer-shaped composite material particle size is 1 ~ 30 μm, and the metal oxide contained is 10 ~ 100nm, and composite material retains the layer structure of two-dimentional electric conducting material.Can be applied on ultracapacitor and/or lithium ion battery, all show high discharge capacity, lithium ion the behavior of fake capacitance intercalation, possess the excellent specific property such as fast charging and discharging ability and good useful life.
Be described below in detail embodiments of the invention, the example of described embodiment, all with reference to shown in accompanying drawing, forms the device schematic diagram preparing transition metal oxide/charcoal base layer-shaped composite material.In order to more easily understand the present invention, with reference to following concrete exemplifying embodiment, these concrete exemplifying embodiments for describing the present invention, and can not be interpreted as limitation of the present invention.
Embodiment 1
Take the Nb that particle diameter is 30 μm
2cT
x(T
xrepresent wherein containing functional group, lower same) 100mg, put into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connect pipeline, guarantee air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 850 DEG C, and retain 30min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compression CO
2, flow is 75sccm, and inlet period is 30min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after oxidation.
Fig. 1 is Nb
2cT
xobtain ESEM and the transmission electron microscope photo of sample prepared by each course of reaction, wherein (a) is Nb
2cT
xscanning electron microscope (SEM) photograph before oxidation, (b), (c) are the scanning electron microscope (SEM) photographs after oxidation, and (d) is Nb
2cT
xtransmission electron microscope picture after oxidation.Find out from scanning electron microscope (SEM) photograph, the Nb before oxidation
2cT
xthere is smooth surface texture.After oxidation, layer creates the nano particle of a large amount of size uniform, material is still left layer structure.As can be seen from transmission electron microscope picture, between newly-generated nano particle, there is unformed charcoal, and nano particle intercrystalline is apart from being 0.36nm, with orthogonal type Nb
2o
5(001) crystal face coincide, illustrate that, after oxidizing thermal treatment, MXene is converted into Nb
2o
5/ C laminar composite.
Using the electrode material of above-mentioned electrode as ultracapacitor and lithium ion battery, three-electrode method evaluates its chemical property.In vacuum glove box, assemble the super capacitor of three way type, collector is stainless steel, and the composite material prepared by employing is as work electrode, and commercial active carbon is to electrode, and filamentary silver is reference electrode, 1M LiClO
4/ EC/DMC is electrolyte, and means of testing comprises cyclic voltammetric, constant current charge-discharge, AC impedance etc.Adopt integration method to obtain ratio capacitance from cyclic voltammetric charging curve, and obtain life-span and high rate performance.During assembling lithium ion battery, the composite material prepared by employing as work electrode, lithium sheet as to electrode and reference electrode, 1M LiClO
4/ EC/DEC is electrolyte, and stainless steel is collector.Means of testing comprises constant current charge-discharge, AC impedance, cyclic voltammetric etc.Adopt discharge capacity as the actual capacity of material, and under different current density, have rated the high rate performance of material.Result of the test is: resulting materials is with rhombic system Nb
2o
5be main, define T-Nb
2o
5/ C laminar composite, the highest in ultracapacitor reaches 462C/g (0.5mV/s) than electricity, and the lithium ion intercalation behavior in fake capacitance type, has fast charging and discharging characteristic.In lithium ion battery, peak capacity reaches 187mAh/g (50mA/g), and capacity still has 120mAh/g under 1000mA/g, and coulombic efficiency is close to 100%, and after 300 circulations, capacity retention rate is 97%.
Embodiment 2
Take the Nb that particle diameter is 30 μm
2cT
x100mg, puts into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connects pipeline, guarantees air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 800 DEG C, and retain 30min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compression CO
2, flow is 150sccm, and inlet period is 60min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after being oxidized.
After after above-mentioned oxidation, gained composite material is prepared into electrode, be assembled into three electric pole type ultracapacitors, example one is shown in method of testing and data analysis.Resulting materials is with rhombic system Nb
2o
5be main, define T-Nb
2o
5/ C laminar composite, the highest in ultracapacitor reaches 320C/g (0.5mV/s) than electricity, and after 2000 circulations, capacity retention rate is 96%, and the lithium ion intercalation behavior in fake capacitance type, has fast charging and discharging characteristic.
Embodiment 3
Take the Nb that particle diameter is 30 μm
2cT
x100mg, puts into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connects pipeline, guarantees air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 850 DEG C, and retain 30min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compression CO
2, flow is 150sccm, and inlet period is 60min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after being oxidized.
After after above-mentioned oxidation, gained composite material is prepared into electrode, be assembled into three electric pole type ultracapacitors, example one is shown in method of testing and data analysis.Result of the test is: resulting materials is with rhombic system Nb
2o
5be main, define T-Nb
2o
5/ C laminar composite, the highest in ultracapacitor reaches 402C/g (0.5mV/s) than electricity, and the lithium ion intercalation behavior in fake capacitance type, has fast charging and discharging characteristic.
Embodiment 4
Take the Nb that particle diameter is 30 μm
2cT
x100mg, puts into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connects pipeline, guarantees air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 850 DEG C, and retain 30min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compression CO
2, flow is 75sccm, and inlet period is 60min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after being oxidized.
After after above-mentioned oxidation, gained composite material is prepared into electrode, be assembled into three electric pole type ultracapacitors, example one is shown in method of testing and data analysis.Result of the test is: resulting materials is with rhombic system Nb
2o
5be main, define T-Nb
2o
5/ C laminar composite, the highest in ultracapacitor reaches 531C/g (0.5mV/s) than electricity, and the lithium ion intercalation behavior in fake capacitance type, has fast charging and discharging characteristic.
Embodiment 5
Take the Nb that particle diameter is 30 μm
2cT
x100mg, puts into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connects pipeline, guarantees air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 400 DEG C, and retain 30min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compressed air, and flow is 150sccm, and inlet period is 60min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after being oxidized.
After after above-mentioned oxidation, gained composite material is prepared into electrode, be assembled into three electric pole type ultracapacitors, example one is shown in method of testing and data analysis.Result of the test is: resulting materials is with rhombic system Nb
2o
5be main, particle size is comparatively large, forms T-Nb
2o
5/ C laminar composite, the highest in ultracapacitor reaches 427C/g (0.5mV/s) than electricity, and the lithium ion intercalation behavior in fake capacitance type, has fast charging and discharging characteristic.
Embodiment 6
Take the Nb that particle diameter is 30 μm
4c
3t
x100mg, puts into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connects pipeline, guarantees air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 850 DEG C, and retain 30min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compression CO
2, flow is 75sccm, and inlet period is 30min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after being oxidized.
After after above-mentioned oxidation, gained composite material is prepared into electrode, be assembled into three electric pole type ultracapacitor and fastening lithium ionic cells, example one is shown in method of testing and data analysis.Result of the test is: resulting materials is with rhombic system Nb
2o
5be main, define T-Nb
2o
5/ C laminar composite, the highest in ultracapacitor reaches 502C/g (0.5mV/s) than electricity, and the lithium ion intercalation behavior in fake capacitance type, has fast charging and discharging characteristic, and after 2000 circulations, capacity retention rate is 88%.In lithium ion battery, peak capacity reaches 210mAh/g (50mA/g), and capacity still has 152mAh/g under 1000mA/g, and coulombic efficiency is close to 100%, and after 300 circulations, capacity retention rate is 98%.
Embodiment 7
Take the Ti that particle diameter is 30 μm
3c
2t
x100mg, puts into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connects pipeline, guarantees air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 500 DEG C, and retain 30min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compression CO
2, flow is 150sccm, and inlet period is 60min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after being oxidized.
After after above-mentioned oxidation, gained composite material is prepared into electrode, be assembled into three electric pole type ultracapacitor and fastening lithium ionic cells, example one is shown in method of testing and data analysis.Result of the test is: resulting materials is with Detitanium-ore-type TiO
2be main, define A-TiO
2/ C laminar composite, the highest in ultracapacitor reaches 368C/g (0.5mV/s) than electricity, and the lithium ion intercalation behavior in fake capacitance type, has fast charging and discharging characteristic, and after 2000 circulations, capacity retention rate is 85%.In lithium ion battery, peak capacity reaches 120mAh/g (50mA/g), and capacity still has 70mAh/g under 2000mA/g, and coulombic efficiency is close to 100%, and after 300 circulations, capacity retention rate is 100%.
Embodiment 8
Take the Nb that particle diameter is 30 μm
4c
3t
x100mg, puts into quartz boat, and quartz boat is placed on the centre of quartz ampoule, connects pipeline, guarantees air tight.Then open inert gas steel cylinder, adopt high-purity argon to purge airtight quartz ampoule 45min with flow velocity 75sccm, then start heating, and with the heating rate of 30 DEG C/min, cavity temperature in tube furnace is risen to 850 DEG C, and retain 60min.Close inert gas pressure-reducing valve afterwards, open oxidizing gas steel cylinder pressure-reducing valve, the air inlet of tube furnace is switched to compression CO
2, flow is 75sccm, and inlet period is 30min.Close oxidizing gas steel cylinder pressure-reducing valve afterwards, open inert gas pressure-reducing valve, flow is 75sccm, and closes heat button, after tube furnace is naturally cooled to room temperature under the protection of inert atmosphere, obtains the composite material after being oxidized.
After above-mentioned oxidation the composite material of gained after tested (method of testing is shown in example one) known, this composite material is with rhombic system Nb
2o
5be main, define T-Nb
2o
5/ C layered composite structure.Above-mentioned composite material being filled in internal diameter is in the fixed bed reactors of 10mm, and controlling reaction temperature is 200 DEG C, and air speed is 3000h
-1, simulated flue gas consists of: 500ppmv NO, 500ppmv NH
3, 5.4vol%O
2, 2.5vol%H
2o, N
2as Balance Air, atmospheric operation.Result of the test is: under the operating conditions described above, and NO removal efficiency is 88%.
Embodiment 9
The preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material, two-dimentional electric conducting material is adopted to be presoma, the gas containing oxygen element is utilized to be oxidant, controlled oxidization temperature is 300 DEG C, oxidization time is 300min, be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen
In the present embodiment, the two-dimentional electric conducting material of use is MXene, and wherein M is metallic element, and X is carbon and/or nitrogen, and lamellar spacing is that 1nm, MXene have with the similar conductivity of Graphene, can be (Ti in the present embodiment
0.5nb
0.5)
2c, the oxidant of use is air, and the ratio of two-dimentional electric conducting material and oxidant is 0.05g/1sccm.
Before carrying out in-situ oxidation, inert gas can also be adopted to carry out slow rinse 10min to reaction system, then two-dimentional electric conducting material controls heating rate under the protection of inert gas is 2 DEG C/min, is warming up to 300 DEG C, then passes into oxidant and carry out in-situ oxidation.
The transition metal oxide prepared/charcoal base layer-shaped composite material particle size is 1 μm, the metal oxide contained is 10nm, composite material retains the layer structure of two-dimentional electric conducting material, can be applied on ultracapacitor and/or lithium ion battery, all show high discharge capacity, lithium ion the behavior of fake capacitance intercalation, possess the excellent specific property such as fast charging and discharging ability and good useful life.
Embodiment 10
The preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material, two-dimentional electric conducting material is adopted to be presoma, the gas containing oxygen element is utilized to be oxidant, controlled oxidization temperature is 600 DEG C, oxidization time is 120min, be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen
In the present embodiment, the two-dimentional electric conducting material of use is MXene, and wherein M is metallic element, and X is carbon and/or nitrogen, and lamellar spacing is that 1nm, MXene have with the similar conductivity of Graphene, can be Ti in the present embodiment
3(C
0.5n
0.5)
2, the oxidant of use is air, and the ratio of two-dimentional electric conducting material and oxidant is 0.1g/10sccm.
The transition metal oxide prepared/charcoal base layer-shaped composite material particle size is 10 μm, the metal oxide contained is 20nm, composite material retains the layer structure of two-dimentional electric conducting material, can be applied on ultracapacitor and/or lithium ion battery, all show high discharge capacity, lithium ion the behavior of fake capacitance intercalation, possess the excellent specific property such as fast charging and discharging ability and good useful life.
Embodiment 11
The preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material, two-dimentional electric conducting material is adopted to be presoma, the gas containing oxygen element is utilized to be oxidant, controlled oxidization temperature is 900 DEG C, oxidization time is 10min, be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen
In the present embodiment, the two-dimentional electric conducting material of use is MXene, and wherein M is metallic element, and X is carbon and/or nitrogen, and lamellar spacing is that 1nm, MXene have with the similar conductivity of Graphene, can be Ta in the present embodiment
2c, the oxidant of use is carbon dioxide, and the ratio of two-dimentional electric conducting material and oxidant is 1g/200sccm.
The transition metal oxide prepared/charcoal base layer-shaped composite material particle size is 30 μm, the metal oxide contained is 80nm, composite material retains the layer structure of two-dimentional electric conducting material, can be applied on ultracapacitor and/or lithium ion battery, all show high discharge capacity, lithium ion the behavior of fake capacitance intercalation, possess the excellent specific property such as fast charging and discharging ability and good useful life.
Embodiment 12
The preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material, two-dimentional electric conducting material is adopted to be presoma, the gas containing oxygen element is utilized to be oxidant, controlled oxidization temperature is 1000 DEG C, oxidization time is 1min, be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen
In the present embodiment, the two-dimentional electric conducting material of use is MXene, and wherein M is metallic element, and X is carbon and/or nitrogen, and lamellar spacing is 1nm, and interlayer has a large amount of containing oxygen and fluorine-containing functional group, makes MXene be water wetted material.MXene containing functional group is semi-conducting material, and energy level difference is 2.0eV.Can be Cr in the present embodiment
3c
2, the oxidant of use is nitrogen dioxide, and the ratio of two-dimentional electric conducting material and oxidant is 5g/250sccm.
Before carrying out in-situ oxidation; inert gas can also be adopted to carry out slow rinse 120min to reaction system; then two-dimentional electric conducting material controls heating rate under the protection of inert gas is 60 DEG C/min, is warming up to 1000 DEG C, then passes into oxidant and carry out in-situ oxidation.
The transition metal oxide prepared/charcoal base layer-shaped composite material particle size is 30 μm, the metal oxide contained is 100nm, composite material retains the layer structure of two-dimentional electric conducting material, can be applied on ultracapacitor and/or lithium ion battery, all show high discharge capacity, lithium ion the behavior of fake capacitance intercalation, possess the excellent specific property such as fast charging and discharging ability and good useful life.
Claims (10)
1. the preparation method of transition metal oxide/charcoal base layer-shaped composite material, it is characterized in that, the method adopts two-dimentional electric conducting material to be presoma, the gas containing oxygen element is utilized to be oxidant, the ratio of two dimension electric conducting material and oxidant is 0.05-5g/1-250sccm, and controlled oxidization temperature is 300 ~ 1000 DEG C, and oxidization time is 1 ~ 300min, be transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material in-situ oxidation
Described two-dimentional electric conducting material is the metal carbides of two-dimensional layered structure, metal nitride or carbonitride.
2. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to claim 1, is characterized in that, described two-dimentional electric conducting material is MXene, wherein M is metallic element, X is carbon and/or nitrogen, and lamellar spacing is 1nm, has with the similar conductivity of Graphene.
3. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to claim 1, it is characterized in that, the interlayer of described two-dimentional electric conducting material MXene has a large amount of containing oxygen and fluorine-containing functional group, and make MXene be hydrophilic semi-conducting material, energy level difference is 2.0eV.
4. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to any one of claim 1-3, is characterized in that, described two-dimentional electric conducting material is Ti
2c, Ti
2n, Ti
3c
2, Ti
4n
3, Ta
2c, Ta
4c
3, Cr
2c, Cr
3c
2, V
2c, V
3c
2, Nb
2c, Nb
4c
3, (Ti
0.5nb
0.5)
2c or Ti
3(C
0.5n
0.5)
2.
5. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to claim 4, is characterized in that, described two-dimentional electric conducting material is preferably Nb
2c, Nb
4c
3, Ti
3c
2or Ti
3(C
0.5n
0.5)
2.
6. want the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to any one of 1 according to right, it is characterized in that, described oxidant is carbon dioxide, air or nitrogen dioxide.
7. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to any one of 1 is wanted according to right; it is characterized in that; before carrying out in-situ oxidation; inert gas is adopted to carry out slow rinse 10-120min to reaction system; then two-dimentional electric conducting material controls heating rate under the protection of inert gas is 2-60 DEG C/min; be warming up to 300 ~ 1000 DEG C, then pass into oxidant and carry out in-situ oxidation.
8. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to claim 1, it is characterized in that, the ratio of two dimension electric conducting material and oxidant is preferably 0.1-1g/10-200sccm, oxidizing temperature is 600-900 DEG C, oxidization time is 10 ~ 120min, is transition metal oxide/charcoal base layer-shaped composite material by two-dimentional electric conducting material original position oxygen.
9. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to claim 1, it is characterized in that, the transition metal oxide prepared/charcoal base layer-shaped composite material particle size is 1 ~ 30 μm, the metal oxide contained is 10 ~ 100nm, and composite material retains the layer structure of two-dimentional electric conducting material.
10. the preparation method of a kind of transition metal oxide/charcoal base layer-shaped composite material according to claim 1 or 9, is characterized in that, the transition metal oxide prepared/charcoal base layer-shaped composite material is applied on ultracapacitor and/or lithium ion battery.Also can be applied in the environment remediation fields such as denitration.
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Application publication date: 20150624 |