CN108172838A - A kind of preparation method and application of graphene coating copper foil current collector - Google Patents
A kind of preparation method and application of graphene coating copper foil current collector Download PDFInfo
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- CN108172838A CN108172838A CN201810005423.0A CN201810005423A CN108172838A CN 108172838 A CN108172838 A CN 108172838A CN 201810005423 A CN201810005423 A CN 201810005423A CN 108172838 A CN108172838 A CN 108172838A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/66—Selection of materials
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to a kind of preparation method and applications of graphene coating copper foil current collector；Preparation method includes the following steps：Improved Hummers methods is used to prepare the preparation that degree of oxidation coats copper foil for the preparation of 7%~28% graphene, dry graphene oxide, the preparation of the graphene colloidal solution of Monodispersed, graphene；With the internal resistance of cell can be reduced, the adhesion strength of active material is improved, reduce Li dendrite and formed, battery high rate performance is improved so as to reach, the advantages of cycle life and safety.
Description
Technical field
The invention belongs to affluxion body in lithium ion batteries field of material technology, and in particular to a kind of graphene coats copper foil afflux
The preparation method and application of body.
Background technology
New-energy automobile is as strategic emerging industries, and positive fast-developing in the world, many countries all formulate
Prohibit fuel vehicle timetable, Chinese Ministry of Industry and Information is also formulating the fuel vehicle timetable that prohibits selling, and on October 19th, 2017, ChangAn Automobile was sent out
The newest new energy strategy of cloth, suspends sale of fuel vehicle in 2025 comprehensively.It is contemplated that within following more than ten years, new-energy automobile
It will put into operation on a large scale.Power battery development as its core component is swift and violent, and demand will increase sharply.Lithium ion battery by
In with quickly-chargeable ability, energy density is big, have extended cycle life, average output voltage is high, self discharge is small outstanding advantages of,
Be widely used in the portable electronics such as mobile communication, laptop and electric tool, unmanned plane, electric vehicle, military affairs and
The fields such as aerospace.As the vehicle power supply of new-energy automobile, other than above-mentioned performance, power battery is also needed to Gao Rong
Amount, high power, long-life, wide thermal adaptability and high security etc..Collector will not only support positive and negative anodes active material, also
It is responsible for collecting the electronics of electrochemical reaction, other than having chemistry and electrochemical stability, the electric conductivity of itself also will be direct
The performance of electrode active material performance is influenced, then influences the comprehensive performances such as multiplying power, the cycle life of entire battery.Cathode easily goes out
The existing deposition (due to the influence of internal electrochemistry) of lithium metal and coming off (effect of external mechanical stress etc.) for active material, institute
Splendid and high comprehensive performance the metal using copper foil as a kind of electric conductivity, although expensive, is usually still chosen as cathode collection
Fluid；Anode usually select it is cheap, be easily worked and aluminium foil that density is light is as collector.
In general, negative electrode active material is coated in the surfaces such as copper foil in a certain way, it is anti-that electrochemistry occurs in battery charging and discharging
At once, generated electronics is collected by the conductive path in electrode active material on collector.Due in active material and
Contact resistance is generated between collector two-phase interface, increases the internal resistance of cell, generates polarization, battery operating voltage declines and leads to electricity
Pond performance deterioration.In addition, the potential of cathode phase after cycling, embedding lithium potential and lithium metal is very close, therefore extreme at some
In the case of, for example, big multiplying power and low temperature charging may be such that graphite cathode potential become negative potential, so as to cause lithium metal
It is precipitated in negative terminal surface, the lithium metal of precipitation can cause electrolyte decomposition and SEI films to thicken so that the porosity of cathode is further
It reducing, seriously affects the performance of lithium ion battery, part metals lithium can lose the connection with conductive network, so as to form dead lithium,
In severe cases, these lithium metals can even form metal Li dendrite, puncture diaphragm, the peace of serious threat lithium ion battery
Entirely.In addition, in order to which active material is made to be firmly bonded in smooth metal collection copper flow surface, many adhesives are usually added in,
This greatly reduces the electric conductivity and energy density of electrode.Chinese patent (publication number CN102832392A) discloses a kind of utilization
Carbon material (conductive black Super P and carbon fiber VGCF) coated collector forms conductive node and conductive network, can be effective
Interface impedance is reduced, reduces internal resistance, improves battery cycle life and high rate performance；Chinese patent (publication number CN106868536A)
A kind of preparation method of Carbon dioxide electrochemical reduction with porous copper electrode is disclosed, porous copper electrode prepared by this method has
Pore-size and the characteristics of quantity is adjustable, good permeability, high specific surface area；And Chinese patent (publication number CN106784853A) is public
A kind of preparation method of graphene coating aluminum foil current collector is opened, graphene coating aluminum foil current collector is simultaneously applied to lithium ion battery
In, the internal resistance of cell is reduced, improves the adhesion strength of active material, battery cycle life and high rate performance are improved so as to reach, these
Not only show that it in lithium ion battery, has vast application prospect in the medium electrochemical device of ultracapacitor.
Graphene (Graphene) be it is a kind of can with two dimension (2D) atomic crystal of self-existent single carbon atom layer thickness,
It is current most thin material, and has the peculiar property of tough and tensile densification, outstanding feature, that is, electron conduction, at room temperature
Carrier mobility may be up to 100,000cm2V-1s-1(Geim,A.K.；Novoselov,K.S.NatureMaterials
2007,6,183).Meanwhile graphene also has higher mechanical performance and huge specific surface area, these good characteristics make it
Different graphene dispersing solutions, graphene conductive liquid, graphene conductive slurry and graphene conductive cream etc. are prepared to, is added to
The performance of material is further played in different materials.
At present, carbon material is prepared mainly using stirring simple for process or ultrasonic power dispersion solution, but due to stirring
A large amount of predecessor reaction sources are needed in the process, and dispersion effect is limited；And large power supersonic use will also result in heat moment and gather
Knot, volatilized solvent, so additional cooling system, particularly ultrasound is needed to also result in, carbon material is excessively broken, and there are many formation lacks
It falls into, affects material electrochemical performance；In addition graphene is prepared using direct method, since graphene dispersion is poor, easily rolled into a ball
It is poly- so that graphene coated conductive can not make full use of, and increase and interelectrode contact resistance；In addition, in preparation process,
Due to graphene dispersion unevenness, graphene dispersing solution is caused to settle so that graphene coating copper foil is difficult to control, and is greatly influenced
The effect of coating.
Invention content
The purpose of the present invention is to overcome the defects in the prior art, and the internal resistance of cell can be reduced by providing one kind, improves
Adhesion strength, the formation of reduction Li dendrite, the high rate performance so as to reach raising battery of active material, cycle life and safety
The preparation method and application of black alkene coating copper foil current collector.
The object of the present invention is achieved like this：The preparation method includes the following steps：
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：It is cooled down in ice bath
Agitating device is equipped in device, the concentrated sulfuric acid that 20ml~25ml mass fractions are 98% is placed in agitating device, takes 1g original stones
Ink powder is added in the above-mentioned concentrated sulfuric acid, and is added in the sodium nitrate of 0.3g~0.5g and be stirred with rotating speed 500-1000r/min, is stirred
The potassium permanganate of 2g~6g is slowly added to while mixing into solution, ice bath cooling device is removed after addition, stops stirring,
It stands and keeps 30min, obtain paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：The water of 50ml is slowly added and stirs evenly institute in step 1
It stands and is kept for 15 minutes in the paste stated, after addition, suspension is made；Then with the warm water that temperature is 30 DEG C~40 DEG C
Suspension is further diluted to 140ml~160ml, and adds in the hydrogen peroxide that 1.5ml~3ml mass fractions are 30% and carries out
After oxidation, glassy yellow suspension is uniformly mixing to obtain, glassy yellow suspension is filtered while hot in time, obtains yellowish-brown filter cake, and
It is washed 3 times with the HCl solution and deionized water that volume fraction is 5% respectively, often washed once centrifugation once, obtain filter cake；Most
Filter cake is placed in 60 DEG C of drying box afterwards and is fully dried, obtains graphene oxide；The rate of the centrifugation for 10000~
12000 revs/min；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to disperse
In 100mlN, dinethylformamide solution, by the graphite oxide that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；It is measured with liquid getting device
The hydrazine hydrate of 60 μ l is positioned in the graphene oxide colloidal solution of high dispersive by after ultrasonic wave separating apparatus ultrasonic disperse 5min,
It is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, take out simultaneously cooled to room temperature after keeping the temperature 2h, obtain
The graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, is formed and porous big compares table
The graphene colloidal solution of Monodispersed described in step 3 is coated in the table of pretreated copper foil material by the structure of area
Then face is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room
The graphene coating copper foil current collector of high reduction degree is made in temperature.
Preferably, the temperature of glassy yellow suspension is 30 DEG C when glassy yellow suspension filters while hot in time in the step 2
~60 DEG C.
Preferably, in the step 4 to copper foil carry out surface roughening pretreatment mode be by oxalic acid to copper foil into
Row surface roughening pre-processes, and after copper foil is immersed in mass fraction for 10min in 10%~30% oxalic acid solution, quickly spends
Ionized water is rinsed well, after vacuum drying.
Preferably, the graphene coating layer thickness in the step 4 in graphene coating copper foil current collector is micro- for 1~100
Rice.
The present invention also provides application of the graphene coating copper foil current collector in lithium ion battery is prepared.
The present invention has the following advantages：
1st, graphene coated collector prepared in the present invention is leading in copper foil surface one layer of favorable dispersibility of coating
Graphene；By the graphene laminated structure of high dispersive itself, interparticle contact is increased so that graphite ene coatings are with afflux
Body is in close contact, but also active material has good caking property with collector；The use of binding agent, fully profit are reduced simultaneously
With the high electric conductivity of graphene, the conductive network to collector is formed in the electrodes, greatly reduces active material with collector
Between contact resistance so that prepared graphene coating copper foil can effectively be promoted the cycle life of battery, high rate performance and
Energy density.
2nd, the DMF that the present invention uses has graphene oxide dispersibility well, it is ensured that the graphene dispersion after reduction
Uniformly, using coating machine coated copper foil etc., the simple controllable, economical and efficient of preparation process is suitable for industrialized production.
3rd, the present invention has good dissolubility in N,N-dimethylformamide (DMF) solution according to graphene oxide and divides
Property is dissipated, the high graphene of oxidizability, the method then restored, to solve graphene point are prepared using improved Hummers methods
The problem of difficult is dissipated, is suitable for industrialization production；And the graphene coating copper foil electrode prepared not only has satisfactory electrical conductivity, machinery
Intensity is high, also has certain characteristic that Li dendrite is inhibited to be formed, can be applied to lithium ion battery particularly power battery to again
The particular/special requirement of rate performance can be also used for the exploitation of the electrochemical devices such as electrolytic capacitor, ultracapacitor, application prospect
It is wide.
In summary, high conductivity and huge specific surface area, particularly its sheet of the present invention by using graphene
Structure makes to prepare graphene dispersing solution coated in this hair on porous copper foil, prepared applied in lithium ion battery, has energy
The internal resistance of cell is enough reduced, improves the adhesion strength of active material, Li dendrite is reduced and is formed, battery high rate performance is improved so as to reach,
The advantages of cycle life and safety.
Specific embodiment
The present invention coats the preparation method and application of copper foil current collector for a kind of graphene, and specific preparation method includes
Following steps：
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：It is cooled down in ice bath
Agitating device is equipped in device, the concentrated sulfuric acid that 20ml~25ml mass fractions are 98% is placed in agitating device, takes 1g original stones
Ink powder is added in the above-mentioned concentrated sulfuric acid, and is added in the sodium nitrate of 0.3g~0.5g and be stirred with rotating speed 500-1000r/min, is stirred
The potassium permanganate of 2g~6g is slowly added to while mixing into solution, ice bath cooling device is removed after addition, stops stirring,
It stands and keeps 30min, obtain paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：The water of 50ml is slowly added and stirs evenly institute in step 1
It stands and is kept for 15 minutes in the paste stated, after addition, suspension is made；Then with the warm water that temperature is 30 DEG C~40 DEG C
Suspension is further diluted to 140ml~160ml, and adds in the hydrogen peroxide that 1.5ml~3ml mass fractions are 30% and carries out
After oxidation, glassy yellow suspension is uniformly mixing to obtain, glassy yellow suspension is filtered while hot in time, obtains yellowish-brown filter cake, and
It is washed 3 times with the HCl solution and deionized water that volume fraction is 5% respectively, often washed once centrifugation once, obtain filter cake；Most
Filter cake is placed in 60 DEG C of drying box afterwards and is fully dried, obtains graphene oxide；The rate of the centrifugation for 10000~
12000 revs/min；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to disperse
In 100mlN, dinethylformamide solution, by the graphite oxide that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；It is measured with liquid getting device
The hydrazine hydrate of 60 μ l is positioned in the graphene oxide colloidal solution of high dispersive by after ultrasonic wave separating apparatus ultrasonic disperse 5min,
It is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, take out simultaneously cooled to room temperature after keeping the temperature 2h, obtain
The graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, is formed and porous big compares table
The graphene colloidal solution of Monodispersed described in step 3 is coated in the table of pretreated copper foil material by the structure of area
Then face is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room
The graphene coating copper foil current collector of high reduction degree is made in temperature.When glassy yellow suspension filters while hot in time in the step 2
The temperature of glassy yellow suspension is 30 DEG C~60 DEG C.It is to the mode of copper foil progress surface roughening pretreatment in the step 4
Surface roughening pretreatment is carried out to copper foil by oxalic acid, copper foil is immersed in mass fraction as in 10%~30% oxalic acid solution
It after 10min, is quickly rinsed well with deionized water, after vacuum drying.Graphene coats copper foil afflux in the step 4
Graphene coating layer thickness in body is 1~100 micron.
The present invention also provides application of the graphene coating copper foil current collector in lithium ion battery is prepared.
Heretofore described graphene oxide obtains oxidizability assay method：Pass through infrared spectroscopic determination graphite oxide
Alkene oxidizability；There is the principle of similar graphene oxide structure based on benzoic acid, using benzoic acid as standard substance, benzoic acid
FTIR spectrum is respectively 1591,1504,1423cm-1Locate as phenyl ring skeleton stretching vibration characteristic absorption peak, in 1692cm-1Locate the stretching vibration characteristic absorption peak for C=O in carboxyl, and the FTIR spectrum of graphene oxide is in 1630cm-1For
The stretching vibration of class phenyl ring framework C=C, in 1730cm-1For the stretching vibration characteristic absorption peak of C=O in carboxyl, in this way, can profit
With the peak area of C=O in C=C on the peak area ratio and graphene oxide of C=O in phenyl ring on benzoic acid and carboxyl and carboxyl
Ratio is calculated by structural analysis and formula, obtains the value of oxidizability.
For the more detailed explanation present invention, the present invention is further elaborated in conjunction with embodiment.Specific embodiment
It is as follows：
Embodiment one
A kind of preparation method of graphene coating copper foil current collector, the preparation method include the following steps：
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：It is cooled down in ice bath
Agitating device is equipped in device, the concentrated sulfuric acid that 20ml mass fractions are 98% is placed in agitating device, 1g original graphite powders is taken to add
Enter into the above-mentioned concentrated sulfuric acid, and add in the sodium nitrate of 0.3g and be stirred with rotating speed 500-1000r/min, to molten while stirring
The potassium permanganate of 2g is slowly added in liquid, ice bath cooling device is removed after addition, stops stirring, stands and keeps 30min, obtain
To paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：The water of 50ml is slowly added and stirs evenly institute in step 1
It stands and is kept for 15 minutes in the paste stated, after addition, suspension is made；Then it will be suspended with the warm water that temperature is 30 DEG C
Liquid is further diluted to 140ml, and add in 1.5ml mass fractions be 30% hydrogen peroxide aoxidized after, stir evenly
To glassy yellow suspension, glassy yellow suspension is filtered while hot in time, obtains yellowish-brown filter cake, and be with volume fraction respectively
5% HCl solution and deionized water washs 3 times, often washed once centrifugation once, obtains filter cake；Filter cake is finally placed in 60 DEG C
Drying box in it is fully dry, obtain graphene oxide；The rate of the centrifugation is 10000 revs/min；The graphene oxide
Oxidizability is 7%；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to disperse
In the n,N-Dimethylformamide solution of 100ml, by the oxidation stone that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Black alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；With liquid getting device amount
The hydrazine hydrate of 60 μ l is taken to be positioned in the graphene oxide colloidal solution of high dispersive through ultrasonic wave separating apparatus ultrasonic disperse 5min
Afterwards, it is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, simultaneously cooled to room temperature is taken out after keeping the temperature 2h,
Obtain the graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, is formed and porous big compares table
The graphene colloidal solution of Monodispersed described in step 3 is coated in the table of pretreated copper foil material by the structure of area
Then face is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room
The graphene coating copper foil current collector of high reduction degree is made in temperature.When glassy yellow suspension filters while hot in time in the step 2
The temperature of glassy yellow suspension is 30 DEG C.The mode of surface roughening pretreatment is carried out in the step 4 to copper foil to pass through grass
Acid carries out surface roughening pretreatment to copper foil, after copper foil is immersed in mass fraction for 10min in 10% oxalic acid solution, quickly
It is rinsed well with deionized water, after vacuum drying.Graphene in the step 4 in graphene coating copper foil current collector
Coating layer thickness is 1 micron.
Embodiment two
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：It is cooled down in ice bath
Agitating device is equipped in device, the concentrated sulfuric acid that 20ml mass fractions are 98% is placed in agitating device, 1g original graphite powders is taken to add
Enter into the above-mentioned concentrated sulfuric acid, and add in the sodium nitrate of 0.4g and be stirred with rotating speed 500-1000r/min, to molten while stirring
The potassium permanganate of 3g is slowly added in liquid, ice bath cooling device is removed after addition, stops stirring, stands and keeps 30min, obtain
To paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：The water of 50ml is slowly added and stirs evenly institute in step 1
It stands and is kept for 15 minutes in the paste stated, after addition, suspension is made；Then it will be suspended with the warm water that temperature is 30 DEG C
Liquid is further diluted to 140ml, and add in 1.5ml mass fractions be 30% hydrogen peroxide aoxidized after, stir evenly
To glassy yellow suspension, glassy yellow suspension is filtered while hot in time, obtains yellowish-brown filter cake, and be with volume fraction respectively
5% HCl solution and deionized water washs 3 times, often washed once centrifugation once, obtains filter cake；Filter cake is finally placed in 60 DEG C
Drying box in it is fully dry, obtain graphene oxide；The rate of the centrifugation is 10000 revs/min；The graphene oxide
Oxidizability is 10%；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to disperse
In the n,N-Dimethylformamide solution of 100ml, by the oxidation stone that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Black alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；With liquid getting device amount
The hydrazine hydrate of 60 μ l is taken to be positioned in the graphene oxide colloidal solution of high dispersive through ultrasonic wave separating apparatus ultrasonic disperse 5min
Afterwards, it is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, simultaneously cooled to room temperature is taken out after keeping the temperature 2h,
Obtain the graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, is formed and porous big compares table
The graphene colloidal solution of Monodispersed described in step 3 is coated in the table of pretreated copper foil material by the structure of area
Then face is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room
The graphene coating copper foil current collector of high reduction degree is made in temperature.When glassy yellow suspension filters while hot in time in the step 2
The temperature of glassy yellow suspension is 30 DEG C.The mode of surface roughening pretreatment is carried out in the step 4 to copper foil to pass through grass
Acid carries out surface roughening pretreatment to copper foil, after copper foil is immersed in mass fraction for 10min in 10% oxalic acid solution, quickly
It is rinsed well with deionized water, after vacuum drying.Graphene in the step 4 in graphene coating copper foil current collector
Coating layer thickness is 20 microns.
Embodiment three
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：It is cooled down in ice bath
Agitating device is equipped in device, the concentrated sulfuric acid that 20ml mass fractions are 98% is placed in agitating device, 1g original graphite powders is taken to add
Enter into the above-mentioned concentrated sulfuric acid, and add in the sodium nitrate of 0.4g and be stirred with rotating speed 500-1000r/min, to molten while stirring
The potassium permanganate of 5g is slowly added in liquid, ice bath cooling device is removed after addition, stops stirring, stands and keeps 30min, obtain
To paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：The water of 50ml is slowly added and stirs evenly institute in step 1
It stands and is kept for 15 minutes in the paste stated, after addition, suspension is made；Then it will be suspended with the warm water that temperature is 30 DEG C
Liquid is further diluted to 140ml, and add in 1.5ml mass fractions be 30% hydrogen peroxide aoxidized after, stir evenly
To glassy yellow suspension, glassy yellow suspension is filtered while hot in time, obtains yellowish-brown filter cake, and be with volume fraction respectively
5% HCl solution and deionized water washs 3 times, often washed once centrifugation once, obtains filter cake；Filter cake is finally placed in 60 DEG C
Drying box in it is fully dry, obtain graphene oxide；The rate of the centrifugation is 11000 revs/min；The graphene oxide
Oxidizability is 17%；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to disperse
In the n,N-Dimethylformamide solution of 100ml, by the oxidation stone that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Black alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；With liquid getting device amount
The hydrazine hydrate of 60 μ l is taken to be positioned in the graphene oxide colloidal solution of high dispersive through ultrasonic wave separating apparatus ultrasonic disperse 5min
Afterwards, it is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, simultaneously cooled to room temperature is taken out after keeping the temperature 2h,
Obtain the graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, is formed and porous big compares table
The graphene colloidal solution of Monodispersed described in step 3 is coated in the table of pretreated copper foil material by the structure of area
Then face is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room
The graphene coating copper foil current collector of high reduction degree is made in temperature.When glassy yellow suspension filters while hot in time in the step 2
The temperature of glassy yellow suspension is 30 DEG C.The mode of surface roughening pretreatment is carried out in the step 4 to copper foil to pass through grass
Acid carries out surface roughening pretreatment to copper foil, after copper foil is immersed in mass fraction for 10min in 10% oxalic acid solution, quickly
It is rinsed well with deionized water, after vacuum drying.Graphene in the step 4 in graphene coating copper foil current collector
Coating layer thickness is 50 microns.
Example IV
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：It is cooled down in ice bath
Agitating device is equipped in device, the concentrated sulfuric acid that 25ml mass fractions are 98% is placed in agitating device, 1g original graphite powders is taken to add
Enter into the above-mentioned concentrated sulfuric acid, and add in the sodium nitrate of 0.5g and be stirred with rotating speed 500-1000r/min, to molten while stirring
The potassium permanganate of 5g is slowly added in liquid, ice bath cooling device is removed after addition, stops stirring, stands and keeps 30min, obtain
To paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：The water of 50ml is slowly added and stirs evenly institute in step 1
It stands and is kept for 15 minutes in the paste stated, after addition, suspension is made；Then it will be suspended with the warm water that temperature is 40 DEG C
Liquid is further diluted to 160ml, and add in 3ml mass fractions be 30% hydrogen peroxide aoxidized after, be uniformly mixing to obtain
Glassy yellow suspension filters glassy yellow suspension while hot in time, obtains yellowish-brown filter cake, and be respectively 5% with volume fraction
HCl solution and deionized water wash 3 times, it is primary often to washed once centrifugation, obtains filter cake；Filter cake is finally placed in 60 DEG C dry
It is fully dry in dry case, obtain graphene oxide；The rate of the centrifugation is 11000 revs/min；The oxidation of the graphene oxide
Spend is 28%；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to disperse
In the n,N-Dimethylformamide solution of 100ml, by the oxidation stone that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Black alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；With liquid getting device amount
60 μ l hydrazine hydrates is taken to be positioned in the graphene oxide colloidal solution of high dispersive by after ultrasonic wave separating apparatus ultrasonic disperse 5min,
It is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, take out simultaneously cooled to room temperature after keeping the temperature 2h, obtain
The graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, is formed and porous big compares table
The graphene colloidal solution of Monodispersed described in step 3 is coated in the table of pretreated copper foil material by the structure of area
Then face is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room
The graphene coating copper foil current collector of high reduction degree is made in temperature.When glassy yellow suspension filters while hot in time in the step 2
The temperature of glassy yellow suspension is 60 DEG C.The mode of surface roughening pretreatment is carried out in the step 4 to copper foil to pass through grass
Acid carries out surface roughening pretreatment to copper foil, after copper foil is immersed in mass fraction for 10min in 30% oxalic acid solution, quickly
It is rinsed well with deionized water, after vacuum drying.Graphene in the step 4 in graphene coating copper foil current collector
Coating layer thickness is 100 microns.
Embodiment five
A kind of preparation method of graphene coating copper foil current collector, the preparation method include the following steps：
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：It is cooled down in ice bath
Agitating device is equipped in device, the concentrated sulfuric acid that 22.5ml mass fractions are 98% is placed in agitating device, takes 1g original graphite powders
Be added in the above-mentioned concentrated sulfuric acid, and add in the sodium nitrate of 0.5g and be stirred with rotating speed 500-1000r/min, while stirring to
The potassium permanganate of 6g is slowly added in solution, ice bath cooling device is removed after addition, stops stirring, stands and keeps 30min,
Obtain paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：The water of 50ml is slowly added and stirs evenly institute in step 1
It stands and is kept for 15 minutes in the paste stated, after addition, suspension is made；Then it will be suspended with the warm water that temperature is 35 DEG C
Liquid is further diluted to 150ml, and add in 2.25ml mass fractions be 30% hydrogen peroxide aoxidized after, stir evenly
To glassy yellow suspension, glassy yellow suspension is filtered while hot in time, obtains yellowish-brown filter cake, and be with volume fraction respectively
5% HCl solution and deionized water washs 3 times, often washed once centrifugation once, obtains filter cake；Filter cake is finally placed in 60 DEG C
Drying box in it is fully dry, obtain graphene oxide；The rate of the centrifugation is 12000 revs/min；The graphene oxide
Oxidizability is 20%；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to disperse
In the n,N-Dimethylformamide solution of 100ml, by the oxidation stone that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Black alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；With liquid getting device amount
The hydrazine hydrate of 60 μ l is taken to be positioned in the graphene oxide colloidal solution of high dispersive through ultrasonic wave separating apparatus ultrasonic disperse 5min
Afterwards, it is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, simultaneously cooled to room temperature is taken out after keeping the temperature 2h,
Obtain the graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, is formed and porous big compares table
The graphene colloidal solution of Monodispersed described in step 3 is coated in the table of pretreated copper foil material by the structure of area
Then face is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room
The graphene coating copper foil current collector of high reduction degree is made in temperature.When glassy yellow suspension filters while hot in time in the step 2
The temperature of glassy yellow suspension is 45 DEG C.The mode of surface roughening pretreatment is carried out in the step 4 to copper foil to pass through grass
Acid carries out surface roughening pretreatment to copper foil, after copper foil is immersed in mass fraction for 10min in 20% oxalic acid solution, quickly
It is rinsed well with deionized water, after vacuum drying.Graphene in the step 4 in graphene coating copper foil current collector
Coating layer thickness is 80 microns.
Experimental example
Copper foil current collector is coated as cathode using the graphene that is prepared in the embodiment of the present invention three, and is combined with conventional cathode etc.
Ternary power soft bag lithium ionic cell is made, and using the ternary power soft bag lithium ionic cell as experimental group, while with common
Graphite is cathode, and is combined with conventional cathode etc. and ternary power soft bag lithium ionic cell is made, and with the ternary power Soft Roll lithium
Ion battery carries out cycle life, high rate performance and safety as a control group, by above-mentioned experimental group and control group and tests,
Its result such as following table：
As seen from the above table, the present invention be embodiment three prepare graphene coating copper foil current collector cycle life, times
Rate performance and safety are far superior to control group.
Foregoing detailed description is illustrated only for the feasibility embodiment of the present invention, they not to
It limits the scope of the invention, all equivalent implementations made without departing from skill spirit of the present invention, change and transformation should all
It is included within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of graphene coating copper foil current collector, it is characterised in that：The preparation method includes the following steps：
Step 1：Improved Hummers methods is used to prepare degree of oxidation as 7%~28% graphene：In ice bath cooling device
It is interior to be equipped with agitating device, the concentrated sulfuric acid that 20ml~25ml mass fractions are 98% is placed in agitating device, takes 1g original graphite powders
Be added in the above-mentioned concentrated sulfuric acid, and add in 0.3g~0.5g sodium nitrate and be stirred with rotating speed 500-1000r/min, stirring it is same
When 2g~6g potassium permanganate is slowly added into solution, remove ice bath cooling device after addition, stop stirring, stand and keep
30 minutes, obtain paste；The temperature of solution is controlled to be no more than 20 DEG C during being slowly added potassium permanganate；
Step 2：The preparation of dry graphene oxide：50ml water is slowly added and stirs evenly the paste described in step 1
It stands and is kept for 15 minutes in shape object, after addition, suspension is made；Then it will be suspended with the warm water that temperature is 30 DEG C~40 DEG C
Liquid is further diluted to 140ml~160ml, and adds in the hydrogen peroxide that 1.5ml~3ml mass fractions are 30% and aoxidized
Afterwards, glassy yellow suspension is uniformly mixing to obtain, glassy yellow suspension is filtered while hot in time, obtains yellowish-brown filter cake, and respectively
It is washed 3 times with the HCl solution and deionized water that volume fraction is 5%, often washed once centrifugation once, obtain filter cake；Finally will
Filter cake, which is placed in 60 DEG C of drying box, fully to be dried, and obtains graphene oxide；The rate of the centrifugation for 10000~12000 turns/
Point；
Step 3：The preparation of the graphene colloidal solution of Monodispersed：Graphene oxide 14mg described in step 2 is taken to be scattered in
The n,N-Dimethylformamide solution of 100ml, by the graphite oxide that high dispersive is obtained after ultrasonic wave separating apparatus ultrasonic disperse 2h
Alkene colloidal solution, the power by ultrasonic wave separating apparatus ultrasonic disperse are 500W, frequency 20kHz；It is measured with liquid getting device
The hydrazine hydrate of 60 μ l is positioned in the graphene oxide colloidal solution of high dispersive by after ultrasonic wave separating apparatus ultrasonic disperse 5min,
It is placed in stainless steel cauldron, reaction kettle is placed in 90 DEG C of baking oven, take out simultaneously cooled to room temperature after keeping the temperature 2h, obtain
The graphene colloidal solution of Monodispersed；The power of ultrasonic disperse is 500W, frequency 20kHz after addition hydrazine hydrate；
Step 4：Graphene coats the preparation of copper foil：Surface roughening pretreatment is carried out to copper foil, forms porous bigger serface
Structure, by the graphene colloidal solution of the Monodispersed described in step 3 be coated in pretreated copper foil material surface,
Then it is heat-treated in hydrogen and argon gas mixed atmosphere, is slowly warming up to 500 DEG C, and keep 2h, then naturally cools to room temperature,
The graphene coating copper foil current collector of high reduction degree is made.
2. a kind of preparation method of graphene coating copper foil current collector according to claim 1, it is characterised in that：The step
The temperature of glassy yellow suspension is 30 DEG C~60 DEG C when glassy yellow suspension filters while hot in time in rapid two.
3. a kind of preparation method of graphene coating copper foil current collector according to claim 1, it is characterised in that：The step
The mode for carrying out surface roughening pretreatment in rapid four to copper foil is to carry out surface roughening pretreatment to copper foil by oxalic acid, will
After copper foil is immersed in mass fraction as 10min in 10%~30% oxalic acid solution, quickly rinsed well with deionized water, vacuum is done
After dry.
4. a kind of preparation method of graphene coating copper foil current collector according to claim 1, it is characterised in that：The step
Graphene coating layer thickness in rapid four in graphene coating copper foil current collector is 1~100 micron.
5. a kind of application of graphene coating copper foil current collector as described in claim 1 in lithium ion battery is prepared.
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| CN110808356A (en) * | 2019-11-14 | 2020-02-18 | 北京乐华锂能科技有限公司 | Preparation method of lithium ion battery pole piece and lithium ion battery pole piece |
| CN112063998A (en) * | 2020-08-28 | 2020-12-11 | 南昌大学 | Preparation method of ultrathin copper/graphene composite foil |
| CN112599780A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院过程工程研究所 | Method for modifying surface of current collector of lithium slurry battery |
| KR20210101448A (en) * | 2020-02-10 | 2021-08-19 | 서울과학기술대학교 산학협력단 | Method for manufacturing carbon material-coated current collector and carbon material-coated current collector thereby |
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