CN104860294A - Three-dimensional graphene nanoribbon/carbon nanoribbon bridged structural material, and preparation method and application thereof - Google Patents
Three-dimensional graphene nanoribbon/carbon nanoribbon bridged structural material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nanometer materials, and specifically relates to a three-dimensional graphene nanoribbon/carbon nanoribbon bridged aerogel material, a preparation method and application thereof. According to the invention, aerogel is prepared by assembling basic structural units formed by bridging the graphene nanoribbon stripped from the carbon nanoribbon with unstripped carbon nanoribbon and doping the basic structural units with heteroatom as needed. The preparation of the aerogel comprises the following steps: preparing a carboxylic carbon nanotube solution, wherein a proper amount of a soluble dopant is added or not added into the solution; then carrying out hydrothermal treatment so as to obtain uniform hydrogel, placing the hydrogel in an ionic impregnation agent for complete replacement, then carrying out secondary hydrothermal treatment so as to finish a stripping process; and finally, carrying out drying and carbonizing so as to obtain the graphene nanoribbon/carbon nanoribbon bridged structural aerogel. The aerogel can be used as an anode material of lithium ion battery, shows high specific capacity and excellent stability and rate performance, and has important research significance and good application prospects.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the aerogel material of a kind of three-dimensional grapheme nano belt/carbon nanotube bridge crosslinking structure, preparation method and application thereof.
Background technology
Along with various electromobile, the widespread use of cell phone and portable power source, the rechargeable cell with height ratio capacity and cyclical stability receives global extensive concern.In order to meet the day by day demand of people to the energy, height ratio capacity is all developed in effort in countries in the world, the high performance lithium ion battery of outstanding high rate performance and long-range stability.The negative material of traditional business-like lithium ion battery is commercial graphite, but due to its lower theoretical specific capacity (372 mAh g
-1) and limited high rate performance greatly limit its practical application.Therefore, find a kind of efficient, cheap, environmental friendliness, specific storage lithium cell cathode material that is high and good stability is extremely urgent.What current research maximum met these conditions is exactly nano level carbon material, such as soccerballene, carbon nanotube, Graphene and porous carbon etc.Although these nano-carbon materials have good electroconductibility and stability, the characteristic of easily assembling due to it and limited storage lithium site make the performance based on the lithium cell of these carbon materials not reach the requirement of expection far away.Therefore find a kind of novel carbon material that there is abundant storage lithium site and be not easy to assemble and the high performance lithium ion battery of development is seemed particularly important.
Graphene nanobelt (GNRs) is a kind of Graphene of accurate one dimension form, can by obtaining in enormous quantities easily Single Walled Carbon Nanotube or multi-walled carbon nano-tubes solution slide fastener.Due to its special fringing effect, enjoy the extensive concern of lithium cell expert.Theoretical experiment has proved that graphene nanobelt is due to its special fringing effect, and its storage lithium ability will improve 2 orders of magnitude compared to random graphene nanometer sheet, is the one very promising lithium cell cathode material of tool.Although so far more existing be in the news about graphene nanobelt base battery material, still there are some most basic problems and do not solve in the electrode materials of these lithium celies: one is that specific storage is not high, and another is exactly cyclical stability difference.Such as, although the GNRs stability obtained by Na/K alloy solution slide fastener of the Jamous M T teaching inventive of rice university of the U.S. is better, its reversible specific capacity only has 250 mAh g
-1, no more than commercial graphite.Cause the not high major cause of specific storage to be cause its effective ratio area greatly to reduce because quasi-one-dimensional GNRs easily occurs to assemble, thus largely reducing its storage lithium ability.Another kind of by chemical oxidization method (KMnO
4/ H
2sO
4) GNRs that obtains, although after circulation 15 circle, its specific storage can also keep 500 mAh g
-1, but significantly can observe its specific storage along with cycle index increase and decaying always, that is non-constant of stability.This is because when peeling off carbon pipe by chemical oxidization method, not only can destroy the regularity of the GNRs obtained, and in oxidising process, a large amount of defects and hole (because creating a large amount of oxygen-containing functional groups) also can be produced on the GNRs obtained, the existence of these defects and hole greatly reduces the mechanical property of GNRs.Therefore in circulation removal lithium embedded process, GNRs structure is easily caved in, and causes the storage lithium space of battery to reduce, thus shows as the poor stability of lithium cell.Therefore these two difficult problems of GNRs electrode materials will be overcome, first be to locate an effective synthetic method and obtain GNRs under the prerequisite not destroying its structural regularity, another is just to locate the gathering of a kind of strategy restriction GNRs, thus the active material obtained compared with bigger serface, to improve storage lithium site and the storage lithium space of material.
Aerogel, the cellular solid that a kind of three-dimensional is ultralight, because it has high porosity (80 % ~ 98 %), specific surface area (20 ~ 2000 m of superelevation
2/ g), performance that continuous print porousness etc. is excellent, become an important branch of porous material research at present.Aerogel not only can use as high temperature insulating material, imitative electrostatic coating, and due to its abundant pore structure, it also becomes a kind of desirable electrode materials day by day, be widely used in various energy device, such as lithium ion battery, ultracapacitor, dye cell and solar cell etc.
Summary of the invention
The object of this invention is to provide the aerogel structure material of a kind of graphene nanobelt/carbon nanotube (GNRs@CNT) bridging, preparation method and application, described aerogel material has ultralow density, large specific surface area and the electroconductibility of excellence, therefore the electron transmission of this material and mass transport are extremely rapid, fully.And compared with the known GNRs obtained by chemical oxidization method or Na/K alloyage solution slide fastener at present, it is more regular that we insert by ion the GNRs structure that embedding method obtains, and the GNRs CNT bridge crosslinking structure obtained not easily is assembled, and makes it have larger specific surface area.Compared with traditional nano-carbon material, it has more avtive spot and storage lithium space, and Stability Analysis of Structures, is a kind of negative material of ideal lithium cell.Through lithium electrical testing, its reversible specific capacity, high rate performance and stability have exceeded nano-carbon material known so far.
For achieving the above object, technical scheme of the present invention is as follows:
An aerogel material for graphene nanobelt/carbon nanotube bridging, the bridge crosslinking structure that described aerogel is made up of graphene nanobelt and carbon nanotube assembles as basic construction unit.Heteroatomic doping can be carried out to material when preparing this material simultaneously, thus improve its electrochemical activity further, improve its storage lithium ability.
Described graphene nanobelt/carbon nanotube bridge crosslinking structure inserts the concentration of embedding dose by controlling ion, controlledly at suitable temperature successively peels off lower graphene nanobelt from carbon nanotube, forms the bridge crosslinking structure of graphene nanobelt/carbon nanotube.Therefore it is different from traditional hybrid material that graphene nanobelt and carbon nanotube are mechanically mixed, but the seamless hydridization bridge crosslinking structure of a kind of graphene nanobelt and carbon nanotube.
The aperture of preferred described graphene nanobelt/carbon nanotube bridge crosslinking structure aerogel is 1 nm ~ 50 μm, porosity 90 % ~ 98 %, and density is 0.03 ~ 0.80 g/cm
3, specific surface area is 20 ~ 2000 m
2/ g, electric conductivity is 10
-5~ 10
4s/m.
A preparation method for three-dimensional grapheme nano belt/carbon nanotube bridge crosslinking structure material, described method steps is as follows:
(1) the carboxylic carbon nano-tube aqueous solution is prepared:
Wherein the carboxylic carbon nano-tube aqueous solution is prepared in water system environment by slight chemical oxidation style, change carbon nanotube is water miscible while, introduces a small amount of defect in carbon nano tube surface.Its preparation method is as follows: 1) be dispersed in the 250 mL vitriol oils by ultrasonic for carbon nanotube (5g) or stirring 1-12 h; 2) in ice bath, adding the potassium permanganate of SODIUMNITRATE (1.53g) and three times of equivalents successively, (15 g), and continues to stir energetically; 3) in reaction solution, add the distilled water of 500 mL after stirring at normal temperature 1-12h, then continue to react 1-24h under room temperature; 4) question response adds the hydrogen peroxide of 500mL distilled water and 25 mL after completing; 5) reaction solution is carried out centrifugal, get lower sediment and dialyse; 6) dialyse and to take out the reactant ultrasonic 1-24h that adds water after 10-15 days and become black even dispersion liquid to be the carboxylic carbon nano-tube aqueous solution; 7) the carboxylic carbon nano-tube aqueous solution preparing 0.1-50 mg/mL is for subsequent use.
Described carbon nanotube is selected from: multi-walled carbon nano-tubes, double-walled carbon nano-tube, three wall carbon nano tubes, many walls array carbon nano tube etc.Carbon nanotube production process is not limit, and can be chemical vapour deposition also can be, and arc discharge method is produced.
(2) carbon nanotube hydrogel is prepared:
Get the carboxylic carbon nano-tube aqueous solution (0.1 ~ 100 mg/mL) 15 mL of different concns, (note: as adulterated, solubility 1 vol%-50 vol% doping agent can be added), after ultrasonic disperse, be placed in 20 mL hydrothermal reaction kettles, 80 DEG C of-200 DEG C of hydro-thermal 1-48h, obtain the carbon nanotube hydrogel that uniform mechanical property is good.
This synthesis can be selected do not add or add doping agent, and as added doping agent, preferential described doping agent is selected from pyrroles, aniline, urea, ammoniacal liquor, Cys, the solubility nitrogenous source of the band such as Dyhard RU 100 nitrogen-atoms; Phosphenylic acid can be selected, triphenyl phosphorus, the soluble sources of the band such as phosphoric acid phosphorus atom, can select boric acid, boronation amine, the solubility boron source of the band such as boric acid ester boron atom, can select thiophene, methionine(Met), sulphur powder, n-dodecyl mereaptan, thiosemicarbazide, the solubility sulphur source of the band such as three acidifying Sulfurs sulphur atom.
In step (1) and step (2), dispersing mode is ultrasonic disperse or emulsion dispersion, and described emulsification carries out on high speed shear dispersion machine.
(3) original position solution slide fastener is carried out to carbon nanotube hydrogel:
The ion carbon nanotube hydrogel obtained in advance being placed in 0.1 ~ 10 M inserts embedding dose of (KNO
3or K
2sO
4) in carry out solvent exchange 12-48h, until ion insert embedding dose the water in hydrogel space is all cemented out after, again hydrogel is placed in 20 mL hydrothermal reaction kettles, 120 DEG C of-250 DEG C of hydro-thermal 12-48h, obtains the columnar water gel that uniform mechanical property is good.Ion inserts embedding dose acting as: during rising along with temperature, potassium ion can embed in the lattice of C-C key of carbon nanotube, makes a breach on the surface of carbon nanotube.The negatively charged ion of solvation at high temperature can strengthen this embeddeding action, and collaborative potassium ion causes in carbon pipe indentation, there separates slide fastener, thus carbon pipe is opened into the graphene nanobelt of rule.
(4) hydrogel is carried out drying, obtain corresponding aerogel.
Dry is lyophilize or the drying of supercutical fluid mode.
In step (4), cryodesiccated concrete grammar is: in hydrogel, add the trimethyl carbinol, after soaking 5 ~ 10 h, the trimethyl carbinol is poured out, after repeating 4 ~ 8 times, by freezing at-5 DEG C ~-50 DEG C for alcogel >=30 min, then at-50 DEG C ~ 100 DEG C drying 30 min ~ 48 h, the aerogel of structural integrity is obtained; Freezing and drying process is all carried out under the vacuum tightness of 1 ~ 1000 Pa.
Described freeze drying process, by the restriction of freeze drying equipment, can complete in the freeze drying equipment of any business or non-commercial.Alcogel also first can adopt liquid nitrogen freezing, then proceeds to vacuum-drying in lyophilizer; Also can direct lyophilize in lyophilizer.Freezing mode can adopt directed freezing (controlling freezing direction), and non-directional also can be adopted freezing.
In step (4), the concrete grammar of supercutical fluid mode drying is: in hydrogel, add ethanol or acetone, pour out after soaking 5 ~ 10 h, repeat 4 ~ 8 times, obtain alcogel or ketone gel, then with Supercritical Ethanol or supercritical co drying >=2h, the aerogel of structural integrity is obtained.
Described supercritical drying process by the restriction of supercritical drying equipment, can any business or non-commercial supercritical drying equipment in complete the supercritical drying of hydridization alcohol (or ketone) gel, to obtain corresponding aerogel.
(5) dried aerogel is carried out Pintsch process under an inert atmosphere, obtain graphene nanobelt of the present invention/carbon nanotube bridging aerogel material.
Described carbonization temperature is 200 ~ 1500 DEG C, and rare gas element is argon gas or nitrogen, and temperature rise rate is 1 ~ 50 DEG C/min, and carbonization time is 1 ~ 48 h, and rate of temperature fall is 1 ~ 50 DEG C/min.Described charing can be carried out in high temperature carbonization furnace.
An application for three-dimensional grapheme nano belt overseas Chinese federation carbon nanotube porous material, described application makes button cell after being ground by the aerogel material obtained in advance, tests its charging and discharging lithium battery, circulation and high rate performance.As an example, we select the GNRs@CNT aerogel material of nitrogen sulphur codoped as typical case.After this material is made button cell, it is under 2A/g current density, and first loading capacity is 3500 mAh/g, and reversible specific capacity is 1500 mAh/g.And at 0.5A/g, 1A/g, 2A/g, 5A/g, have extraordinary high rate performance under 10 A/g current densities, even if under the condition of 10A/g, its specific storage can also keep close to 500 mAh/g.And cycle performance test is carried out under 2A/g current density, after finding its circulation 300 circle, the specific storage of about 1050 mAh/g can also be kept, and any obvious decay does not occur, show that the stability of this electrode materials is very good.
Useful invention effect:
The invention provides the aerogel material of a kind of three-dimensional grapheme nano belt/carbon nanotube bridging, described bridge crosslinking structure shows as a large amount of graphene nanobelt peels off formation graphene nanobelt and carbon nanotube seamless hydridization bridge crosslinking structure from carbon nano tube surface.This material combines the characteristic of graphene nanobelt, the many excellences of carbon nanotube, also uses aerogel material porous and the advantage such as specific surface area is large.
The invention provides the preparation method of a kind of three-dimensional grapheme nano belt/carbon nanotube bridge crosslinking structure material, the nano level graphene nanobelt that wherein many regularities are intact gets off from the sur-face peeling of carbon nanotube, and a small amount of carbon pipe of internal layer maintains its original structure, do not destroy, the conductive contact keeping it good and mechanical stability.
Three-dimensional grapheme nano belt provided by the invention and carbon nanotube bridge crosslinking structure can carry out electric transmission and mass transfer effectively.In this material, the complete graphene nanobelt stripped down provides large specific surface area and good mechanical property, internal layer unbroken carbon pipe maintains its good electroconductibility and mechanical property, after it can be used as structural unit to be assembled into aerogel, because aerogel can provide a good three-dimensional transmission path, because of the electric transmission in the aerogel material of graphene nanobelt/carbon nanotube bridging for this reason and mass transfer very rapidly and fully.
Three-dimensional grapheme nano belt provided by the invention/carbon nanotube bridge crosslinking structure material effectively can suppress a gathering difficult problem for graphene nanobelt and carbon nanotube.Be embodied in, when adjacent graphene nanobelt is close to each other, the carbon nanotube of bridging effectively can suppress it to assemble further as barrier agent.Similarly, when adjacent carbon nanotube near time, the graphene nanobelt of stripping also can hinder the further gathering of carbon nanotube as barrier agent, because of be designed with for this reason effect solve conventional graphite alkene nano belt, carbon nano-tube material assemble a difficult problem.
Three-dimensional grapheme nano belt overseas Chinese federation provided by the invention carbon nanotube structure material, after the doping of nitrogen sulphur atom, effectively improves its electrochemical activity, and its storage lithium ability is strengthened.When the negative material as lithium cell uses, show as higher reversible specific capacity, excellent high rate performance and cyclical stability, its lithium electrical property has even exceeded the Conventional nano level carbon material reported so far.
Three-dimensional grapheme nano belt provided by the invention/carbon nanotube bridging material is also expected to and is applied in biosensor, fuel cell, ultracapacitor, support of the catalyst, adsorb be separated, the field such as molecular device and life science.
Accompanying drawing explanation
Fig. 1 is the SEM image of the GNRs@CNT aerogel of the N doping that embodiment 1 obtains.
Fig. 2 is the TEM image of the GNRs@CNT aerogel of the sulfur doping that embodiment 2 obtains.
Fig. 3 is the nitrogen adsorption/desorption curve of the GNRs@CNT aerogel that embodiment 1 ~ 3 obtains.
Fig. 4 is the GNRs@CNT aerogel that obtains of embodiment 1 ~ 3
i-Vcurve.
Fig. 5 is the cyclic voltammetry curve of GNRs@CNT aerogel material as lithium cell cathode material of the nitrogen sulphur codoped that embodiment 3 obtains.
Fig. 6 is that the GNRs@CNT aerogel material of the nitrogen sulphur codoped that embodiment 3 obtains is as the charging and discharging curve of lithium cell cathode material under 2A/g current density.
Fig. 7 is that the GNRs CNT aerogel material of the nitrogen sulphur codoped that embodiment 3 obtains is as the stable circulation performance curve of lithium cell cathode material under 2A/g current density.
Fig. 8 is that the GNRs@CNT aerogel material of the nitrogen sulphur codoped that embodiment 3 obtains is as the high rate performance curve of lithium cell cathode material under different current density.
Fig. 9 is the charge-discharge test curve of battery under 2A/g current density.
Figure 10 is the cycle performance test result of battery under 2A/g.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
(1) get the carboxylic carbon nano-tube solution of 10 mL 0.5 mg/mL, add 100 uL pyrroles as N source, ultrasonic disperse is until form uniform suspension 1.
(2) be sealed in by suspension 1 in the hydrothermal reaction kettle of 15 mL, the baking oven being placed in 180 DEG C reacts 12 h, can obtain block carbon nanotube hydrogel.
(3) the carbon nanotube hydrogel obtained in advance is placed in 2 M KNO
3carry out solvent exchange 24h in solution, to be replaced completely after, taken out by hydrogel and be sealed in the hydrothermal reaction kettle of 15 mL, the baking oven being then placed in 180 DEG C reacts 48 h, can obtain GNRs@CNT hydrogel.
(4) hydrogel obtained is placed in 1L water to replace, washes away residual impurity (KNO
3and its byproduct of reaction), after displacement 10h, distilled water is poured out, repeat 6-8 time.Then the trimethyl carbinol hydrogel of wash clean being placed in 500 mL is replaced, and is poured out by the trimethyl carbinol, repeat 3-4 time, by freezing at-70 DEG C for hydrogel >=30 min, then at 70 DEG C of drying 30 min, obtain GNRs CNT aerogel after displacement 10h; Freezing and drying process is all carried out under the vacuum tightness of 10 Pa.
(5) the GNRs CNT aerogel charing 3h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 1050 DEG C, and temperature rise rate is 10 DEG C/min, and rate of temperature fall is 10 DEG C of min.Obtain the GNRs@CNT aerogel of N doping.
Embodiment 2
(1) get the carboxylic carbon nano-tube solution of 15 mL 10 mg/mL, add 1 mL thiophene as S source, ultrasonic disperse is until form uniform suspension 2.
(2) be sealed in by suspension 2 in the hydrothermal reaction kettle of 20 mL, the baking oven being placed in 200 DEG C reacts 6 h, can obtain block carbon nanotube hydrogel.
(3) the carbon nanotube hydrogel obtained in advance is placed in 1 M K
2sO
4carry out solvent exchange 48 h in solution, to be replaced completely after, taken out by hydrogel and be sealed in the hydrothermal reaction kettle of 20 mL, the baking oven being then placed in 180 DEG C reacts 36 h, can obtain GNRs@CNT hydrogel.
(4) hydrogel obtained is placed in 1 L distilled water to replace, washes away residual impurity (K
2sO
4and its byproduct of reaction), after replacing 10 h, distilled water is poured out, repeat 6-8 time.In hydrogel, add acetone, after soaking 10 h, acetone is poured out, after repeating 4 times, obtain ketone gel, the supercritical CO produced with SFT company of the U.S.
2dry 24 h of drying instrument, supercritical CO
2dry critical temperature is 40 DEG C, and emergent pressure is 7.5 Pa, obtains GNRs@CNT aerogel.
(5) GNRs CNT aerogel charing 6 h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 900 DEG C, and temperature rise rate is 20 DEG C/min, and rate of temperature fall is 20 DEG C/min.Obtain the GNRs@CNT aerogel of sulfur doping.
Embodiment 3
(1) get the carboxylic carbon nano-tube solution of 30 mL 15 mg/mL, add the thiophene of 3 mL pyrroles and 3 mL respectively as N, S source, ultrasonic disperse is until form uniform suspension 3.
(2) be sealed in by suspension 3 in the hydrothermal reaction kettle of 50 mL, the baking oven being placed in 140 DEG C reacts 24 h, can obtain block carbon nanotube hydrogel.
(3) the carbon nanotube hydrogel obtained in advance is placed in 1 M KNO
3solvent exchange 48 h is carried out in solution.To be replaced completely after, taken out by hydrogel and be sealed in the hydrothermal reaction kettle of 50 mL, the baking oven being then placed in 180 DEG C reacts 60 h, can obtain GNRs@CNT hydrogel.
(4) hydrogel obtained is placed in 1L water to replace, washes away residual impurity (KNO
3and its byproduct of reaction), after displacement 10h, distilled water is poured out, repeat 6-8 time.Then in hydrogel, add ethanol, after soaking 5 h, ethanol is poured out, after repeating 4 times, in hydrogel, add water, after soaking 5 h, water is poured out, after repeating 6 times, by freezing at-80 DEG C for hydrogel >=60 min, then at 40 DEG C of drying 48 h, obtain GNRs@CNT aerogel; Freezing and drying process is all carried out under the vacuum tightness of 1 Pa.
(5) GNRs CNT aerogel charing 3 h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 800 DEG C, and temperature rise rate is 10 DEG C/min, and rate of temperature fall is 20 DEG C/min.Obtain nitrogen sulphur codoped GNRs@CNT aerogel.
Embodiment 4
(1) get the carboxylic carbon nano-tube aqueous solution of 25 mL 20 mg/mL, add 2.5 mL phosphoric acid as phosphorus source, ultrasonic disperse is until form uniform suspension 4.
(2) be sealed in by suspension 4 in the hydrothermal reaction kettle of 50 mL, the baking oven being placed in 160 DEG C reacts 10 h, can obtain block carbon nanotube hydrogel.
(3) hydrogel obtained is placed in 1 M K
2sO
4carry out displacement 48 h in solvent, after displacement completely, gel is taken out the hydrothermal reaction kettle again putting into 50 mL, the baking oven being then placed in 200 DEG C reacts 36 h, can obtain GNRs CNT hydrogel.
(4) hydrogel obtained is placed in 1 L distilled water to replace, washes away residual impurity (K
2sO
4and its byproduct of reaction), after replacing 10 h, distilled water is poured out, repeat 6-8 time.In hydrogel, add the trimethyl carbinol, after soaking 12 h, the trimethyl carbinol is poured out, after repeating 6 times, obtain alcogel, the supercritical CO produced with SFT company of the U.S.
2dry 48 h of drying instrument, supercritical CO
2dry critical temperature is 40 DEG C, and emergent pressure is 7.38 Pa, obtains GNRs@CNT aerogel.
(5) GNRs CNT aerogel charing 2 h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 1100 DEG C, and temperature rise rate is 5 DEG C/min, and rate of temperature fall is 5 DEG C/min.Obtain the GNRs@CNT aerogel of phosphorus doping.
Embodiment 5
(1) get the carboxylic carbon nano-tube aqueous solution of 25 mL 8 mg/mL, add 5 mL boric acid as boron source, ultrasonic disperse is until form uniform suspension 5.
(2) be sealed in by suspension 5 in the hydrothermal reaction kettle of 50 mL, the baking oven being placed in 180 DEG C reacts 12 h, can obtain block carbon nanotube hydrogel.
(3) the carbon nanotube hydrogel obtained is placed in 0.5 M K
2sO
4in carry out solvent exchange 48h, to be replaced completely after, gel is taken out the hydrothermal reaction kettle again putting into 50 mL, the baking oven being then placed in 200 DEG C reacts 24 h, can obtain GNRs@CNT hydrogel.
(4) distilled water first the carbon nanotube hydrogel obtained being placed in 2 L carries out solvent exchange, washes away residual impurity (K
2sO
4and its byproduct of reaction), after replacing 8 h, distilled water is poured out, repeat 8-10 time.Then hydrogel is immersed in the trimethyl carbinol of 500 mL, pours out after displacement 6h, repeat 1-2 time, obtain alcogel, then alcoholic solution is placed in liquid nitrogen and carries out freezing, be then placed in freeze drier and carry out dry 48h, the cold-trap of freeze drier is-80 DEG C, and vacuum tightness is 0.8 Pa.Finally obtain GNRs@CNT aerogel.
(5) aerogel obtained is placed in high temperature carbonization furnace (production of Tianjin Zhong Huan company) and carries out charing process, carbonization temperature is 1100 DEG C, the charing hold-time is 3 h, and intensification and rate of temperature fall are all 10 DEG C/min, obtain boron doped GNRs@CNT aerogel.
Embodiment 6
(1) get the carboxylic carbon nano-tube aqueous solution of 15 mL 10 mg/mL, ultrasonic disperse is until form uniform suspension 6.
(2) be sealed in by suspension 6 in the hydrothermal reaction kettle of 20 mL, the baking oven being placed in 180 DEG C reacts 12 h, can obtain block carbon nanotube hydrogel.
(3) carbon nanotube hydrogel is first washed once, be then placed in 5 M K
2sO
4carry out solvent exchange in solution, take out after displacement 48h, put into the hydrothermal reaction kettle of 20 mL, the baking oven being placed in 200 DEG C reacts 48 h, obtains GNRs@CNT hydrogel.
(4) distilled water GNRs@CNT hydrogel being placed in 2L carries out solvent exchange, after 10h, distilled water is poured out, repetition like this 8-10 time, then the gel washed is placed in the trimethyl carbinol and carries out solvent exchange, after 10h, the trimethyl carbinol is poured out, repetition like this 6-8 time, is finally placed on refrigerator and cooled by the alcogel obtained and freezes 24h.To be frozen completely after gel taken out to be positioned in freeze drier carry out lyophilize 48 h, the condenser temperature of freeze drier is-40 DEG C, and vacuum tightness is 5 Pa.Finally obtain GNRs@CNT aerogel.
(5) aerogel obtained is placed in high temperature carbonization furnace and carries out anneal, annealing temperature is 1200 DEG C, and annealing time is 5 h, and temperature rise rate is 10 DEG C/min, and rate of temperature fall is 20 DEG C/min.Obtain final unadulterated GNRs@CNT aerogel.
Embodiment 7
(1) the stannic oxide/graphene nano band solution (license number: 201410653970.1) partially opened of 30 mL 15 mg/mL is got, add the thiophene of 3 mL pyrroles and 3 mL respectively as N, S source, ultrasonic disperse is until form uniform suspension 7.
(2) be sealed in by suspension 7 in the hydrothermal reaction kettle of 50 mL, the baking oven being placed in 140 DEG C reacts 24 h, can obtain block carbon nanometer leaf hydrogel.
(3) in hydrogel, ethanol is added, after soaking 5 h, ethanol is poured out, after repeating 4 times, water is added in hydrogel, after soaking 5 h, water is poured out, after repeating 6 times, by freezing at-80 DEG C for hydrogel >=60 min, then at 40 DEG C of drying 48 h, carbon nanometer leaf aerogel is obtained; Freezing and drying process is all carried out under the vacuum tightness of 1 Pa.
(4) carbon nanometer leaf aerogel charing 3 h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 800 DEG C, and temperature rise rate is 10 DEG C/min, and rate of temperature fall is 20 DEG C/min.Obtain nitrogen sulphur codoped carbon nanometer leaf aerogel.
Test the GNRs@CNT aerogel that embodiment 1 ~ 7 obtains, result is as follows:
Fig. 1 is scanning electron microscope (SEM) image of the GNRs@CNT aerogel of the N doping obtained in embodiment 1, and Fig. 2 is transmission electron microscope (TEM) image of the GNRs@CNT aerogel of the sulfur doping obtained in embodiment 2.As can be seen from Figure 1, described GNRs@CNT aerogel is the knot of the hierarchical porous of a kind of three-dimensional, and its essentially consist unit is the carbon nanotube structure of graphene nanobelt bridging.Because obtained nano belt width is smaller, so in order to reduce its surface energy, the nano belt that major part is peeled off is all curling shape, but significantly can observe the opening of carbon nanotube.As can be seen from Figure 2, the bridge crosslinking structure of the slitless connection that described GNRs@CNT aerogel is made up of graphene nanobelt and carbon nanotube, wherein not destroyed carbon nanotube is connected to the graphene nanobelt stripped down from carbon pipe.And form the three-dimensional net structure piled up each other.
Fig. 3 is the nitrogen adsorption/desorption curve of the GNRs@CNT aerogel that embodiment 1 ~ 3 obtains, curve a, b, c be corresponding embodiment 1 respectively, 2,3, wherein transverse axis is test pressure, the longitudinal axis is adsorptive capacity, and the GNRs@CNT aerogel described in explanation is meso-hole structure, and the specific surface area of embodiment 1,2,3 is respectively 599 m
2/ g, 529 m
2/ g, 621 m
2/ g, aperture is respectively 2 nm, 5 nm, 9 nm.The aerogel aperture that embodiment 4 ~ 6 obtains is 1 nm ~ 20 μm, and density is 0.03 ~ 0.8 g cm
-3, specific surface area is 20 ~ 2000 m
2g
-1.
Fig. 4 is the GNRs@CNT aerogel that obtains of embodiment 1 ~ 3
i-Vcurve, curve a, b, c be corresponding embodiment 1,2,3 respectively, and wherein X-coordinate is voltage, and ordinate zou is electric current, GNRs@CNT aerogel described in explanation is three-dimensional conductive hybrid aerogel, and the electric conductivity of embodiment 1 ~ 3 correspondence is respectively 98.1,101.3,104.7 S m
-1.The hybrid aerogel specific conductivity that embodiment 4 ~ 6 obtains is 10
-5~ 10
4s m
-1.
Carry out lithium cell performance test to the GNRs@CNT aerogel that embodiment 1 ~ 6 obtains, method is as follows:
The GNRs@CNT aerogel mortar of the nitrogen sulphur codoped in embodiment 3 is ground, after grinding, takes a certain amount of aerogel as active material, add conductive agent carbon black, and binding agent PTFE.The ratio control of active material, conductive agent and binding agent is at 80:10:10.Mixture is placed in mortar and repeatedly grinds 2h, when thing to be mixed becomes the liquid of thickness, be poured on lithium paper tinsel, after doctor blade, be positioned in the baking oven of 180 DEG C and toast 12h, the electrode materials after drying is cut out conglobate electrode slice, after calculating the quality of active substance on electrode slice, electrode slice is placed in glove box, is assembled into button cell.The electrolytic solution of battery is 1 M LiPO
6(be dissolved in (1:1 Vol:Vol) in EC/DEC, pure lithium paper tinsel is as to electrode for solution.After compressing tablet, electrode slice is left standstill 12h, then electrode slice is placed in blue electric system to test, test voltage is 0.005 V-3V, and all electro-chemical tests (test such as cyclic voltammetric and discharge and recharge) are all produced in CHI760D(Shanghai Chen Hua company) carry out in electrochemical workstation.Fig. 5 is the cyclic voltammetry curve of battery, and as can be seen from the figure, material has a peak to occur between 0.5V ~ 1.0V when first lap, this peak is the formation of SEI.When continuing to sweep, material the 2nd enclose and the 3rd circle repetition fairly good, namely now electrode materials close to steady state.Fig. 6 is the charge-discharge test of battery under 2A/g current density, and as can be seen from the figure, the primary just loading capacity of material is very large, and can reach 3400 mAh/g, primary reversible specific capacity is 1500 mAh/g.Show excellent storage lithium performance.The reason of the loss of reversible capacity is exactly Li defines one deck SEI film cause in electrode material surface for the first time.Along with the carrying out of discharge and recharge, the loading capacity that electrode materials is the 2nd time very close to (1450 mAh/g), shows that material is in follow-up discharge and recharge in the loading capacity of the 3rd time, does not continue to form SEI film.So the loss of loading capacity is smaller.Fig. 7 is the corresponding coulombic efficiency of stability that the circulation 300 of battery under 2A/g current density is enclosed.As can be seen from the figure, electrode materials, under high current density, still keeps extraordinary stability, and its coulombic efficiency is almost close to 100%.And after circulation 100 circle, the specific storage of material has slight rising, and the rising of specific storage is mainly because electrode materials there occurs partial activation phenomenon.Fig. 8 is the high rate performance test of battery under different current density.As can be seen from the figure, battery still keeps good stability and high rate performance under different current density.Even if under the current density of 10A/g, battery still maintains the specific storage close to 500 mAh/g.There is some evidence, this material is the extremely promising cell negative electrode material of one, has very important Research Significance.
Lithium cell performance test is carried out to the carbon nanometer leaf aerogel of the nitrogen sulphur codoped in embodiment 7.
Fig. 9 is the charge-discharge test of battery under 2A/g current density, as can be seen from the figure, this material also there is higher first loading capacity (2892 mAh/g), primary reversible specific capacity is 1364 mAh/g.But along with the carrying out of charge and discharge cycles, the performance of electrode materials declines gradually, is embodied in specific storage and decays gradually, the specific storage after 100 circles only has 175 mAh/g.Figure 10 is the cycle performance of battery under 2A/g, and same is the same with Fig. 9 conclusion, and along with the carrying out of circulation, the specific storage of material reduces gradually, and after 140 circles, battery specific storage is only 130 mAh/g, and battery almost breaks down.Although the material structure of carbon nanometer leaf and carbon nanotube bridging graphene nanobelt structural similitude, but because carbon nanometer leaf is obtained by Strong oxdiative method, a lot of defects and oxygen-containing functional group can be produced at carbon material surface in preparation process, cause the mechanical properties decrease of material, therefore easy structural collapse thus cause stability test to decline in working cycle.By the improvement of this patent method, successfully solve the problem that stability of material is bad, make this material can have better application prospect at lithium electrical domain.
In sum, these are only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the aerogel GNRs CNT material of three-dimensional grapheme nano belt/carbon nanotube bridge crosslinking structure, it is characterized in that the graphene nanobelt that a large amount of defect is few, regularity is good gets off from the sur-face peeling of carbon nanotube, form the bridging hybrid structure of graphene nanobelt/carbon nanotube, described aerogel to be assembled as basic structural unit by graphene nanobelt/carbon nanotube bridge crosslinking structure and carries out heteroatomic doping to it on demand simultaneously.
2. a kind of three-dimensional grapheme nano belt/carbon nanotube bridge crosslinking structure aerogel according to claim 1, is characterized in that: the aperture of described GNRs@CNT aerogel is 1 nm ~ 50 μm, and porosity is 90 % ~ 99 %, and density is 0.03 ~ 0.80 g/cm
3, specific surface area is 20 ~ 2000 m
2/ g, electric conductivity is 10
-5~ 10
4s/m.
3. a preparation method for three-dimensional grapheme nano belt as claimed in claim 1/carbon nanotube bridge crosslinking structure aerogel, is characterized in that described method steps is as follows:
(1) utilize oxidation style first to prepare carboxylated carbon nano-tube aqueous solutions, change carbon nanotube is water miscible while, introduce a small amount of defect in carbon nano tube surface;
(2) do not add in the carboxylic carbon nano-tube aqueous solution or add appropriate different types of soluble dopant, and at 80 DEG C ~ 200 DEG C hydro-thermal 1 ~ 48 h, obtain uniform carbon nanotube hydrogel;
(3) hydrogel obtained is placed in ion to insert embedding dose and carry out solvent exchange, to be replaced completely after, carry out secondary hydro-thermal and complete original position stripping process, the GNRs CNT hydrogel after peeling off can be obtained, described ion insert embedding dose for concentration be the KNO of 0.1 ~ 10 M
3or K
2sO
4the aqueous solution;
(4) the GNRs@CNT hydrogel obtained is carried out drying, obtain corresponding aerogel;
(5) GNRs@CNT aerogel is carried out pyroprocessing under protection of inert gas, if now have doping agent, Pintsch process occurs, doping agent original position mixes the lattice into GNRs@CNT, obtains the GNRs@CNT aerogel material of described Heteroatom doping; As do not added doping agent, then the object of high temperature annealing is deoxygenation, and improve the electroconductibility of material, what finally obtain is described unadulterated GNRs@CNT aerogel material.
4. the preparation method of the aerogel material of a kind of three-dimensional grapheme nano belt/carbon nanotube bridge crosslinking structure as claimed in claim 3, it is characterized in that: in step (1), when preparing the carboxylic carbon nano-tube aqueous solution, described carbon nanotube is multi-walled carbon nano-tubes, double-walled carbon nano-tube, three wall carbon nano tubes or many walls array carbon nano tube.
5. the preparation method of the aerogel material of a kind of three-dimensional grapheme nano belt carbon nanotube bridge crosslinking structure as claimed in claim 3, it is characterized in that: in step (2), do not add any doping agent or add doping agent, doping agent is selected from pyrroles, aniline, urea, ammoniacal liquor, Cys or the Dyhard RU 100 nitrogenous source as the solubility of band nitrogen-atoms; Or be selected from phosphenylic acid, triphenyl phosphorus or the phosphoric acid soluble sources as band phosphorus atom, or be selected from boric acid, boronation amine or the boric acid ester solubility boron source as band boron atom, or be selected from the solubility sulphur source of the band sulphur atoms such as thiophene, methionine(Met), sulphur powder, n-dodecyl mereaptan, thiosemicarbazide or three acidifying Sulfurs.
6. the preparation method of the aerogel material of a kind of three-dimensional grapheme nano belt/carbon nanotube bridge crosslinking structure as claimed in claim 3, is characterized in that: in step (4), and described drying process is that lyophilize or supercutical fluid mode are dry;
Wherein lyophilize, be specially: in the hydrogel obtained in advance, add distilled water, after soaking 5 ~ 12 h, distilled water is poured out, after repeating 4 ~ 10 times, then add the trimethyl carbinol in hydrogel, after soaking 5 ~ 12 h, the trimethyl carbinol is poured out, after repeating 2 ~ 4 times, by freezing at-5 DEG C ~-50 DEG C for alcogel >=30 min, then at 10 DEG C ~ 100 DEG C drying 30 min ~ 48 h, obtain the aerogel of structural integrity; Freezing and drying process is all carried out under the vacuum tightness of 1 ~ 1000 Pa;
Supercutical fluid mode is dry, is specially: in the hydrogel obtained in advance, add ethanol or acetone, pours out after soaking 5 ~ 10 h, repeat 4 ~ 8 times, obtain alcogel or ketone gel, then with Supercritical Ethanol or supercritical co drying >=2h, obtain the aerogel of structural integrity.
7. a kind of three-dimensional grapheme nano belt carbon nanotube bridge crosslinking structure aerogel preparation method as claimed in claim 3, it is characterized in that: in step (5), described carbonization temperature is 200 ~ 1100 DEG C, rare gas element is argon gas or nitrogen, temperature rise rate is 1 ~ 50 DEG C/min, carbonization time is 1 ~ 48 h, and rate of temperature fall is 1 ~ 50 DEG C/min.
8. a three-dimensional grapheme nano belt carbon nanotube bridge crosslinking structure aerogel material as the negative material of lithium cell, biosensor, fuel cell, ultracapacitor, support of the catalyst, adsorb be separated, the application in molecular device field.
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