CN105271205B - A kind of method that the controllable high-quality graphene of the number of plies is prepared using electrochemical process - Google Patents
A kind of method that the controllable high-quality graphene of the number of plies is prepared using electrochemical process Download PDFInfo
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Abstract
The invention belongs to technical field of graphene preparation, specially a kind of method that the controllable high-quality graphene of the number of plies is prepared using electrochemical process.The present invention is reactive material using graphite, and lithium ion can be stored in the controllable insertion of graphite layers（Chemical combination, insertion etc.）Intercalated object（Such as metal salt, metal oxide, polymer or simple substance etc.）, form the controllable graphite intercalation compound of exponent number（GICs）；Electrode is made in graphite intercalation compound, as negative electrode of lithium ion battery, by the irreversible electrochemical process in part, the Van der Waals force of graphite intercalation compound interlayer disappears, and is converted to graphene, by processing such as scattered, washings, obtains the controllable graphene of the number of plies.The present invention is destroyed the intermolecular force of graphite by electrochemical process, need not move through the vigorous reaction process such as ultrasound or expansion, course of reaction is gentle, and it can accurately control the graphene number of plies, obtained graphene film has defect few, the advantages that electrical conductivity is high, it is easy to large-scale industrialized production.
Description
Technical field
The invention belongs to technical field of graphene preparation, and in particular to a kind of controllable using the electrochemical process preparation number of plies
The method of high-quality graphene.
Background technology
Graphene（graphene）It is by a kind of tightly packed carbonaceous into bi-dimensional cellular shape lattice structure of single layer of carbon atom
New material.Before graphene is found, most of physicists think, thermodynamics fluctuation does not allow any two dimensional crystal limited
At a temperature of exist.2004, Univ Manchester UK physicist An Deliehaimu and Constantine's Nuo Woxiao loves
A kind of carbon film of monoatomic thickness, this bidimensional carbon materials are prepared for using " micromechanical forces disintegrating method " (microfolitation)
Material is demonstrated by very high crystallinity and unusually stablized, and it can be with individualism.Undoubtedly, graphene is received after carbon
Another great discovery after mitron, fullerene ball, the people of Hai Mu and Nuo Woxiao loves two is also because of starting in two-dimensional graphene material
Journal of Sex Research, Nobel Prize in physics in 2010 is obtained jointly.Due to the unique two-dimensional structure of graphene and excellent crystallography knot
Structure, graphene have contained abundant and novel physical phenomenon, have had important theoretical research and application value.
Because the performance of graphene has substantial connection with its number of plies, in order to realize the business application of graphene, low cost height
It is a very important research direction that yield, which prepares the controllable high-quality graphene of the number of plies,.At present, the method for preparing graphene
Including following several：（1）Micromechanics stripping method, graphene crystal structure is complete made from this method, but yield is too low, is not suitable for
Large-scale production；（2）Chemical vapour deposition technique（CVD）, graphene crystal structure prepared by this method is more complete, passes through control condition
It is controllable that the number of plies can be achieved, but cost is higher, preparation technology requires higher, it is difficult to realizes large-scale production；（3）Epitaxial growth method,
This method can obtain the graphene of large area, but graphene platelet is not easy to substrate separation, and cost is higher；（4）Solvent is shelled
From method, this method is peeled off, this method can obtain better quality by the way that graphite is mixed with part intercalator in appropriate solvent
Graphene, but this method needs the processing procedures such as prolonged ultrasound or ball milling, and often yield is not high；（5）Oxygen
Change reducing process, the method is a large amount of methods for preparing graphene the most frequently used at this stage, but graphene defect is more made from this method,
The electric conductivity of graphene is poor.And the method is difficult to realize number of plies control, Chinese patent《A kind of controllable high quality of number of plies
The preparation method of graphene》（CN101993061A）By regulating and controlling the degree of oxidation of graphite, number of plies control is realized.But this method makes
With hydrogen-argon-mixed in 300-1000oReduction-oxidation graphite at a high temperature of C, recovery time length be present, reaction high to equipment requirement
Cost is high, the problems such as high energy consumption.Therefore, exploitation is a kind of simple, prepared by the extensive controllable high-quality graphene of the number of plies for preparing
Method is extremely important.To solve the problems, such as that report method is present, the present invention is reactive material using graphite, by graphite linings
Between controllable insertion can store lithium ion（Chemical combination, insertion etc.）Intercalated object（Such as metal salt, metal oxide, polymer or list
Matter etc.）, form the controllable graphite intercalation compound of exponent number（GICs）；Electrode is made in graphite intercalation compound, as lithium ion
GND, by the irreversible electrochemical process in part, the Van der Waals force of graphite intercalation compound interlayer disappears, and is converted to stone
Black alkene, by a series of processing such as scattered, washings, obtain the controllable graphene of the number of plies.The present invention makes stone by electrochemical process
The intermolecular force of ink is destroyed, it is not necessary to which, by the vigorous reaction process such as ultrasound or expansion, course of reaction is gentle, and energy
The accurate control graphene number of plies, obtained graphene film have the advantages that defect is few, and electrical conductivity is high, are easy to extensive industry metaplasia
Production.
The content of the invention
It is a kind of simple it is an object of the invention to develop, it is extensive to prepare the controllable high-quality graphene preparation side of the number of plies
Method.
The present invention proposes a kind of method that the controllable high-quality graphene of the number of plies is prepared using electrochemical process, specific steps
It is as follows：
（1）Graphite is mixed with that can store up the intercalator of lithium, the graphite intercalation compound of different rank is made（GICs）；
（2）By step（1）Obtained graphite intercalation compound is used as GND in the electrolyte of lithium ion battery,
By charge and discharge process, the intermolecular force of graphene film interlayer is set to disappear（Process is as shown in Figure 1）, it is compound to obtain graphene
Thing；
（3）By step（2）Obtained graphene complex disperses in a solvent, is handled by ultrasonic method, then filter,
Washing, obtains the high-quality graphene of the different numbers of plies.Wherein：
Watt level, the particle size of graphite when described ultrasonic time depends on ultrasonication, due to intermolecular
Active force has been destroyed, and ultrasonic time was controlled within 30 minutes（General ultrasonic 5-25 minutes）, ultrasonic power 200-
2000W, frequency 15-100kHz.
In the present invention, step（1）Described graphite intercalation compound, its exponent number general control be 1 to 10 between it is single
Rank or the compound containing not same order, as desired by the ratio and reaction condition of regulation graphite and intercalator, regulation generation
Different rank.
In the present invention, step（1）The preparation method of described graphite intercalation compound includes solid phase insertion, liquid phase is inserted,
One kind in gas phase insertion method, or the wherein mixing of several method.According to the difference of insert state during reaction, GICs system
Preparation Method can be divided into：Dual chamber method, chemical method, electrochemical process, mixing method, pressurization and molten-salt growth method etc..To now the normal of GICs be prepared
It is specifically described as follows with method：
1. dual chamber method synthesizes GICs：Dual chamber method is to prepare GICs classical way, particularly suitable for alkali metal-GICs and
Metal chloride-GICs preparation.In the reative cell at heat resistant glass reactor both ends, placing graphite and insert, take out respectively
After vacuum sealing, control the temperature of glass reactor both ends reative cell respectively with two groups of electric furnaces, make Tg>Ti (the temperature of graphite sample
Spend Tg>The temperature Ti of insert), to ensure that insert can be smoothly inserted into graphite layers, while prevent the intercalation chemical combination of generation
Thing is decomposed reaction when temperature is too high；
2. chemical method synthesizes GICs：With natural flake graphite and H2SO4For raw material, Cl2, bichromate, H2O2、HNO3Deng
For oxidant, aoxidize graphite carbon-coating by oxidant, with dense H2SO4Intercalation is carried out as main intercalator.Crystalline flake graphite is through oxygen
After change processing, pi-electron is lost, anion enters graphite layers, forms compound between graphite layers；
3. electrochemical process synthesizes GICs：Electrochemical process synthesis GICs is by natural flake graphite and impressed current anode together structure
Into anode chamber, intercalant solution makees electrolyte, leads to direct current or pulse current, carries out anodic oxidation, depickling, washes, dehydrates
Obtain.This is a kind of insert is inserted into graphite layers in the form of ion using electrochemical reaction and prepares GICs side
Method；
4. mixing method synthesizes GICs：This is that one kind directly mixes graphite with insert, then in mobility protective atmosphere
Method that is lower or being heat-treated in closed system and prepare GICs；
5. pressurization synthesizes GICs：In pressurization bar after alkaline-earth metal and rare earth metal powder etc. are mixed with graphite matrix
Reaction generation M-GICs under part；
6. molten-salt growth method (also referred to as blended liquid phase method) synthesis GICs：Molten-salt growth method is can to melt system based on each component eutectic
Point reduces the property of (fusing point for being less than each component) and put forward, and is that one kind can while (must by two or more material
Must can be formed melts salt system) insert graphite layers preparation ternary or polynary GICs method.This method make original needs compared with
The reactive material that high reaction temperature could insert graphite layers just can be inserted into graphite layers under relatively low reaction temperature, thus
With important practical value.
In addition synthesis GICs methods also have photochemical method, catalyst method, explosion method etc., these synthetic methods, respectively have its excellent
Point and weak point, synthetic object are also not quite similar, and because of less use, are not elaborated here.
In the present invention, step（1）Described intercalation main body is, graphite includes but are not limited to native graphite, modified graphite,
Delanium（Such as HOPG, pitch based carbon fiber, vapor-grown carbon fibers, PAN-based carbon fiber）, graphited carbon materials
At least one of the graphite of material with layer structure.These material parts or all with graphite-structure, carbon atom in aspect
With SP2Hybridized orbit electronically forms covalent bond, while each carbon atom forms metallic bond with 2pZ orbital electron again, and shape is firm
Hexagonal net plane layer of charcoal.
In the present invention, step（1）Described intercalator is one kind in metal salt, metal oxide, polymer, simple substance,
Or wherein several mixture.Specific material is shown in Table 1, and specific material includes but are not limited to material described in table 1.
In the present invention, step（2）Described charge and discharge process can stop in the discharged condition, can also be in charged state
Lower stopping.
In the present invention, step（3）Described dispersion process, it is conventional organic that solvent for use includes water and ethanol, benzene, toluene etc.
Solvent.
The graphene that preparation method of the present invention is made, its graphene number of plies are 1-10 layers, and graphite lattice defect is few, are presented
Go out than more complete hexagon, graphenic surface is without oxy radicals such as epoxy radicals, carboxyl, hydroxyls；Electron mobility exceedes
3000cm2/ Vs, graphene conductive are good.
Brief description of the drawings
Fig. 1 is that the present invention makes the destroyed procedure chart of intermolecular force by discharge and recharge.
Fig. 2 is the XRD of the second order iron chloride copper chloride graphite intercalation compound prepared by the present invention.
Fig. 3 is the transmission electron microscope of 2 layer graphenes prepared by the present invention（TEM）Picture.
Fig. 4 is the Raman of 2 layer graphenes prepared by the present invention（Raman）Spectrum.
Fig. 5 is the electron transport test result of 2 layer graphenes prepared by the present invention.
Embodiment
The present invention may be better understood from following examples, but the present invention is not limited solely to following examples
Embodiment 1：
6g graphite is weighed, 3.24g anhydrous ferric chlorides, after 2.69g anhydrous cupric chlorides are sufficiently mixed, is done in 80 DEG C of vacuum drying ovens
Dry 8 hours, dried sample sealed in a kettle, 400 DEG C of 6 hours of processing.Products obtained therefrom is washed with deionized water to washing
Wash in liquid without Fe3+、 Cu2+.Sample after washing 120 DEG C of dryings 10 hours in vacuum drying oven, are made second order iron chloride chlorination
Copper graphite intercalation compound.（Refer to Fig. 1）
Above-mentioned made second order iron chloride copper chloride graphite intercalation compound is directly born against into nickel foam electrode is made on the net, it
After be placed in 80 DEG C of vacuum drying ovens dry 12 hours, in this, as the working electrode of lithium ion battery.In glove box according to
The order assembling of positive pole/barrier film/negative pole carries out single electrode test.Single electrode is tested using lithium piece as negative pole, 1M LiPF6 •EC/
DEC/DMC（Volume ratio is 1:1:1）For electrolyte, barrier film uses commercial li-ion battery diaphragm, is assembled into battery.Battery works
Section is 0 ~ 3.0V, charging and discharging currents 100mA/g, and first circle discharges into 0V, filled after returning to 3V, battery is taken apart, graphite is inserted
Layer compound electrode is distributed in water, ultrasonic disperse 10 minutes, and washing, watery hydrochloric acid filter after washing, you can 2 layers of graphite is made
Alkene（Refer to Fig. 2）, so obtained graphene defect is seldom（Refer to Fig. 3）, electric conductivity is very excellent（Refer to Fig. 4）.
Embodiment 2：
6g graphite is weighed, 3.24g anhydrous ferric chlorides, after 2.69g anhydrous cupric chlorides are sufficiently mixed, is done in 80 DEG C of vacuum drying ovens
Dry 8 hours, dried sample sealed in a kettle, 400 DEG C of 6 hours of processing.Products obtained therefrom is washed with deionized water to washing
Wash in liquid without Fe3+、 Cu2+.Sample after washing 120 DEG C of dryings 10 hours in vacuum drying oven, are made second order iron chloride chlorination
Copper graphite intercalation compound.（Refer to Fig. 1）
Above-mentioned made second order iron chloride copper chloride graphite intercalation compound is directly born against into nickel foam electrode is made on the net, it
After be placed in 80 DEG C of vacuum drying ovens dry 12 hours, in this, as the working electrode of lithium ion battery.In glove box according to
The order assembling of positive pole/barrier film/negative pole carries out single electrode test.Single electrode is tested using lithium piece as negative pole, 1M LiPF6 •EC/
DEC/DMC（Volume ratio is 1:1:1）For electrolyte, barrier film uses commercial li-ion battery diaphragm, is assembled into battery.Battery works
Section is 0 ~ 3.0V, charging and discharging currents 100mA/g, and first circle discharges into 0V, fills and return to 1.5V, battery is taken apart, graphite is inserted
Layer compound electrode is distributed in water, ultrasonic disperse 10 minutes, and washing, watery hydrochloric acid filter after washing, you can 2 layers of graphite is made
Alkene.
Embodiment 3：
6g graphite is weighed, 3.24g anhydrous ferric chlorides, after 2.69g anhydrous cupric chlorides are sufficiently mixed, is done in 80 DEG C of vacuum drying ovens
Dry 8 hours, dried sample sealed in a kettle, 400 DEG C of 6 hours of processing.Products obtained therefrom is washed with deionized water to washing
Wash in liquid without Fe3+、 Cu2+.Sample after washing 120 DEG C of dryings 10 hours in vacuum drying oven, are made second order iron chloride chlorination
Copper graphite intercalation compound.（Refer to Fig. 1）
Above-mentioned made second order iron chloride copper chloride graphite intercalation compound is directly born against into nickel foam electrode is made on the net, it
After be placed in 80 DEG C of vacuum drying ovens dry 12 hours, in this, as the working electrode of lithium ion battery.In glove box according to
The order assembling of positive pole/barrier film/negative pole carries out single electrode test.Single electrode is tested using lithium piece as negative pole, 1M LiPF6 •EC/
DEC/DMC（Volume ratio is 1:1:1）For electrolyte, barrier film uses commercial li-ion battery diaphragm, is assembled into battery.Battery works
Section is 0 ~ 3.0V, charging and discharging currents 100mA/g, after the circle of 0-3V sections circulation 5, battery is taken apart, by graphite intercalation
Compound electrode is distributed in water, ultrasonic disperse 25 minutes, and washing, watery hydrochloric acid filter after washing, you can 2 layers of graphene is made.
Embodiment 4：
8g graphite is weighed, 5.36g anhydrous ferric chlorides, after being sufficiently mixed, is dried 8 hours in 80 DEG C of vacuum drying ovens, after drying
Sample seal in a kettle, 550 DEG C processing 12 hours.Products obtained therefrom is washed with deionized water into cleaning solution without Fe3+、
Cu2+.Sample after washing 120 DEG C of dryings 10 hours in vacuum drying oven, are made quadravalence iron chloride graphite intercalation compound.
Above-mentioned made quadravalence iron chloride graphite intercalation compound is directly born against into nickel foam electrode is made on the net, placed afterwards
Dried 12 hours in 80 DEG C of vacuum drying ovens, in this, as the working electrode of lithium ion battery.In glove box according to positive pole/every
The order assembling of film/negative pole carries out single electrode test.Single electrode is tested using lithium piece as negative pole, 1M LiPF6 •EC/DEC/DMC
（Volume ratio is 1:1:1）For electrolyte, barrier film uses commercial li-ion battery diaphragm, is assembled into battery.Battery operation interval is 0
~ 3.0V, charging and discharging currents 100mA/g, first circle discharge into 0V, filled after returning to 3V, battery is taken apart, by graphite intercalation compound
Electrode is distributed in water, ultrasonic disperse 20 minutes, and washing, watery hydrochloric acid filter after washing, you can four layers of graphene is made.
Embodiment 5：
12g graphite is weighed, 5.36g anhydrous ferric chlorides, after being sufficiently mixed, is dried 8 hours in 80 DEG C of vacuum drying ovens, after drying
Sample seal in a kettle, 600 DEG C processing 12 hours.Products obtained therefrom is washed with deionized water into cleaning solution without Fe3+、
Cu2+.Sample after washing 120 DEG C of dryings 10 hours in vacuum drying oven, are made six rank iron chloride graphite intercalation compounds.
Above-mentioned made quadravalence iron chloride graphite intercalation compound is directly born against into nickel foam electrode is made on the net, placed afterwards
Dried 12 hours in 80 DEG C of vacuum drying ovens, in this, as the working electrode of lithium ion battery.In glove box according to positive pole/every
The order assembling of film/negative pole carries out single electrode test.Single electrode is tested using lithium piece as negative pole, 1M LiPF6 •EC/DEC/DMC
（Volume ratio is 1:1:1）For electrolyte, barrier film uses commercial li-ion battery diaphragm, is assembled into battery.Battery operation interval is 0
~ 3.0V, charging and discharging currents 100mA/g, first circle discharge into 0V, filled after returning to 3V, battery is taken apart, by graphite intercalation compound
Electrode is distributed in water, ultrasonic disperse 10 minutes, and washing, watery hydrochloric acid filter after washing, you can six layers of graphene is made.
Embodiment 6：
6g graphite is weighed, 4.33g waterless cobaltous chlorides, after being sufficiently mixed, is dried 8 hours in 80 DEG C of vacuum drying ovens, after drying
Sample seal in a kettle, 700 DEG C processing 3 hours.Products obtained therefrom is washed with deionized water into cleaning solution without Fe3+、
Cu2+.Sample after washing 120 DEG C of dryings 10 hours in vacuum drying oven, are made the cobalt chloride graphite intercalation that three rank quadravalences mix rank
Compound.
The cobalt chloride graphite intercalation compound of above-mentioned made mixed rank is directly born against into nickel foam electrode, Zhi Houfang are made on the net
Put and dried 12 hours in 80 DEG C of vacuum drying ovens, in this, as the working electrode of lithium ion battery.In glove box according to positive pole/
The order assembling of barrier film/negative pole carries out single electrode test.Single electrode is tested using lithium piece as negative pole, 1M LiPF6 •EC/DEC/DMC
（Volume ratio is 1:1:1）For electrolyte, barrier film uses commercial li-ion battery diaphragm, is assembled into battery.Battery operation interval is 0
~ 3.0V, charging and discharging currents 100mA/g, first circle discharge into 0V, filled after returning to 3V, battery is taken apart, by graphite intercalation compound
Electrode is distributed in water, ultrasonic disperse 10 minutes, and washing, watery hydrochloric acid filter after washing, you can the stone based on three layers, four layers is made
Black alkene.
The graphite intercalation compound guest materials list of table 1
。
Claims (7)
- A kind of 1. method that the controllable high-quality graphene of the number of plies is prepared using electrochemical process, it is characterised in that specific steps are such as Under：（1）Graphite is mixed with that can store up the intercalator of lithium, the graphite intercalation compound of different rank is made；（2）By step（1）Obtained graphite intercalation compound is used as GND in the electrolyte of lithium ion battery, passes through Charge and discharge process, the intermolecular force of graphene film interlayer is disappeared, obtain graphene complex；（3）By step（2）Obtained graphene complex disperses in a solvent, is handled by ultrasonic method, then filters, washes Wash, obtain the high-quality graphene of the different numbers of plies；The intercalation main body of the graphite intercalation compound is graphite；Intercalated object is that intercalator is reversible or part reversible storage lithium The material of ion, intercalator include one kind in metal salt, metal oxide, polymer, simple substance, or wherein several mixing Body；The graphite is native graphite, Delanium or modified graphite.
- 2. according to the method for claim 1, it is characterised in that described graphite intercalation compound, exponent number are 1 to 10 list Single order or the compound containing not same order.
- 3. according to the method for claim 1, it is characterised in that the preparation method of graphite intercalation compound include solid phase insertion, One kind in liquid phase insertion, gas phase insertion method, or the wherein mixing of several method.
- 4. according to the method for claim 1, it is characterised in that charge and discharge process stops in the discharged condition, or is charging Stop under state.
- 5. according to the method for claim 1, it is characterised in that scattered solvent for use is water and ethanol, benzene or toluene.
- 6. according to the method for claim 1, it is characterised in that the prepared graphene number of plies is 1-10 layers, and graphite lattice lacks Fall into few.
- 7. according to the method for claim 1, it is characterised in that described ultrasonic time is that ultrasonic power is within 30 minutes 200-2000W, frequency 15-100kHz.
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| PCT/CN2016/106625 WO2017084632A1 (en) | 2015-11-20 | 2016-11-21 | Method for preparing high-quality graphene having controllable layer number by utilizing electrochemical process |
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| CN105271205B (en) * | 2015-11-20 | 2017-12-29 | 复旦大学 | A kind of method that the controllable high-quality graphene of the number of plies is prepared using electrochemical process |
| CN107215867B (en) * | 2016-03-22 | 2019-05-10 | 中国科学院金属研究所 | A kind of method that serialization prepares graphene oxide microplate |
| CN106006613A (en) * | 2016-05-24 | 2016-10-12 | 广州市霆宇能源科技有限责任公司 | Method for preparing graphene |
| CN107032339B (en) * | 2017-06-20 | 2018-03-20 | 成都新柯力化工科技有限公司 | It is a kind of based on the electrostatic repulsion method that continuously stripping prepares graphene |
| CN109216044A (en) * | 2018-09-12 | 2019-01-15 | 中南民族大学 | Graphene/metal oxide combination electrode material is prepared in situ in mechanochemical reaction |
| CN112978721A (en) * | 2019-12-02 | 2021-06-18 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene by double-pulse electrochemical technology |
| CN113307261B (en) * | 2021-04-21 | 2022-07-12 | 浙江大学 | Preparation method of graphite intercalation compound cathode material suitable for quick-charging lithium ion battery, product and application thereof |
| CN114572973B (en) * | 2022-05-03 | 2024-04-09 | 营口理工学院 | Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method |
| CN115417401A (en) * | 2022-05-12 | 2022-12-02 | 太原理工大学 | Method for preparing graphene by recoverable low-temperature molten salt |
| CN116873912A (en) * | 2023-05-24 | 2023-10-13 | 国电投重庆能源研究院有限公司 | Water-soluble conductive graphene and preparation method thereof |
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| WO2017084632A1 (en) | 2017-05-26 |
| CN105271205A (en) | 2016-01-27 |
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