CN104241615B - A kind of method that Graphene complex ternary material is prepared using monoalcohol solvent full-boiled process - Google Patents
A kind of method that Graphene complex ternary material is prepared using monoalcohol solvent full-boiled process Download PDFInfo
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention belongs to field of lithium ion battery anode, a kind of method preparing Graphene complex ternary material particularly to monoalcohol solvent full-boiled process.The method that monoalcohol solvent full-boiled process prepares Graphene complex ternary material, described ternary material is LiNixCoyMnzO2, x+y+z=1,0.2≤x≤0.6,0.1≤y≤0.4,0.2≤z≤0.5；Graphene complex ternary materials chemistry formula is Graphene/ LiNixCoyMnzO2, it is an advantage of the current invention that：1）Due to ternary material LiNixCoyMnzO2More sensitive for water, it is a kind of selection well as solvent that monohydric alcohol replaces water, because temperature is less than 220 DEG C, when pressure is not more than 3 MPa, monohydric alcohol easily forms subcritical state, nonflammable, low price, and toxicity is weak；2）The Graphene complex ternary positive electrode excellent electrochemical performance prepared by the present invention, its high rate performance is better than traditional composite；3）Preparation process is relatively simple, with low cost, suitable large-scale industrial production.
Description
Technical field
The invention belongs to field of lithium ion battery anode, prepare Graphene particularly to a kind of monoalcohol solvent full-boiled process
The method of complex ternary material.
Background technology
Lithium ion battery is a kind of novel secondary battery of alternative lead-acid battery, has high-energy-density, can discharge and recharge
Often, have a safety feature, the advantages of environmentally friendly.Lithium ion battery mainly by positive electrode, negative material, electrolyte and
Barrier film is constituted, and wherein positive electrode largely constrains lithium ion battery overall performance and lifted further, therefore, for just
The developmental research of pole material is increasingly paid attention to.
In recent years, the anode material for lithium-ion batteries of layer structure（Cobalt acid lithium LiCoO2, LiMn2O4 LiMnO2, lithium nickelate
LiNiO2）Become study hotspot, LiCoO2Irreversible capacity loss in charge and discharge process is little, good cycling stability, but it is subject to
Limit to cobalt resource and overcharge restriction with spontaneous, be only used for high-end small-capacity cells；LiMnO2Lower cost, but its appearance
Amount is also low, easily causes structural collapse, bad stability after repeatedly circulating； LiNiO2Actual specific capacity is 170mAh g-1, than
LiCoO2Big 20～40mAh g-1, and its cost is relatively low, but synthesis condition is harsh, and overcharge safety is poor.In conjunction with above-mentioned three
Plant the respective pluses and minuses of material and each of which easily forms the feature of solid solution, synthesize ternary material LiNixCoyMnzO2
（X+y+z=1）, it is with low cost, have a safety feature, actual specific capacity is more than LiNiO2Deng advantage enjoy researcher to like.
But there is also some problems, such as first charge-discharge efficiency is low, structural stability is poor, high rate performance under poorly conductive, high-pressure solid
Can not play.
Graphene is a kind of material of monoatomic layer laminated structure, has electron transport ability by force, and high mechanical strength is pliable and tough
Property good and heat conductivity good, be considered to substitute other conductive agents（Acetylene black, flaky graphite alkene, hard carbon etc.）Preferred material,
Graphene can effectively improve electronics and ionic conductivity, usage amount compared to other conductive agents above-mentioned after being combined with positive electrode
Few, superior performance, therefore grapheme composite positive electrode material have become the another bright spot improving battery overall performance.
Content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of monoalcohol solvent full-boiled process is prepared Graphene and is combined three
The method of first material, the Graphene complex ternary material that the method is prepared has higher energy density, also has good simultaneously
High rate performance.
The present invention is achieved through the following technical solutions：
A kind of method that monoalcohol solvent full-boiled process prepares Graphene complex ternary material, described ternary material is
LiNixCoyMnzO2, x+y+z=1,0.2≤x≤0.6,0.1≤y≤0.4,0.2≤z≤0.5；Graphene complex ternary material
Chemical general formula is Graphene/ LiNixCoyMnzO2It is characterised in that：Including following preparation process：
（1）Early stage is processed：By ternary material LiNixCoyMnzO2, Graphene be placed in baking oven, dry at 120～200 DEG C
Dry 1～3 h；It is ground respectively after cooling, put into standby in exsiccator；
（2）Under room temperature, weigh step（1）Gained graphene powder, is well-dispersed in equipped with anhydrous monoalcohol solvent
Reactor in, prepare graphene dispersing solution；
（3）Determine LiNixCoyMnzO2The mass percent being combined with Graphene, weighs step（1）Gained
LiNixCoyMnzO2Powder, is divided into 2-6 addition step（2）Reactor in, sealing is stirred, and makes LiNixCoyMnzO2With
Graphene is sufficiently mixed；
（4）Reactor is put in heater, sets reaction temperature and response time, natural cooling after the completion of reaction,
Sucking filtration, washing, drying, obtain the complex of Graphene and ternary material；
（5）By step（4）Gained complex sinters in an inert atmosphere, and after natural cooling, excessively ground 200 mesh sieves obtain
Final Graphene complex ternary material Graphene/ LiNixCoyMnzO2.
Step（2）Described anhydrous monohydric alcohol is methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, sec-butyl alcohol and the tert-butyl alcohol
The mixed liquor of one or more.
Step（2）The mass concentration of gained graphene dispersing solution is 0.3～6mg/ml.
Step（3）The mass percent that described Graphene is combined with ternary material is 0.3～10：100, preferably 0.3～
3：100.
Step（4）Described in washing process use step（2）In monohydric alcohol used washed.
Step（4）Described heater is the heater that baking oven or oil bath pan or reactor carry.
Step（4）Described reaction temperature is 150～220 DEG C, and the response time is 3～24 h.
Step（5）Described inert atmosphere is one kind of nitrogen, helium or argon.
Step（5）Described sintering temperature is 200～600 DEG C, and sintering time is 2～6 h.
The method that the monoalcohol solvent full-boiled process of the present invention prepares Graphene complex ternary material, has an advantage in that：1）Due to
Ternary material LiNixCoyMnzO2More sensitive for water, it is a kind of selection well as solvent that monohydric alcohol replaces water, because
Temperature is less than 220 DEG C, and when pressure is not more than 3 MPa, monohydric alcohol easily forms subcritical state, nonflammable, low price, toxicity
Weak；2）The Graphene complex ternary positive electrode excellent electrochemical performance prepared by the present invention, its high rate performance is better than tradition
Composite；3）Preparation process is relatively simple, with low cost, suitable large-scale industrial production.
Brief description
The present invention is described in further detail below in conjunction with the accompanying drawings, and protection scope of the present invention is not to be embodied as
Example is for limiting, but is defined in the claims.
Accompanying drawing 1 is the wide-angle x-ray diffraction instrument of embodiment 1 and comparative example 1（XRD）Collection of illustrative plates；
Accompanying drawing 2 is the field emission scanning electron microscope under the different amplification of embodiment 3（SEM）Photo；
Accompanying drawing 3 is the transmission scanning electron microscope of embodiment 3（TEM）Photo；
Accompanying drawing 4 is embodiment 1 and the different multiplying discharge curve comparing 1；
Accompanying drawing 5 is the different multiplying discharge curve of embodiment 2 and embodiment 3；
Accompanying drawing 6 is the field emission scanning electron microscope of embodiment 4（SEM）Photo；
Accompanying drawing 7 is the field emission scanning electron microscope of embodiment 7（SEM）Photo.
Specific embodiment
The present invention is further illustrated with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
By commodity ternary material LiNi0.5Co0.3Mn0.2O2（523 types）, commercial graphite alkene carries out early stage process：Will
LiNi0.5Co0.3Mn0.2O2, Graphene in 120 DEG C of baking ovens, is dried 3 h, is ground respectively to not reuniting after cooling
Till phenomenon, then it is respectively put into standby in exsiccator；Using the above-mentioned Graphene of balance precise 0.1000 g, disperseed
In the reactor filling 50 ml anhydrous isopropyl alcohols, put into magneton, using ultrasonic assistant dispersion；Using balance precise
10.0021 g ternary materials, Graphene and LiNi0.5Co0.3Mn0.2O2Mass percent is 1:100, point 3 addition reactors
In liner, stir 30 min, magneton is taken out, closed reaction kettle, put it in 180 DEG C of baking oven, after reaction 12 h, from
So cool down, then take out inner liner of reaction kettle and carry out sucking filtration, wash with isopropanol three times, after drying, obtain Graphene and
LiNi0.5Co0.3Mn0.2O2Complex, gained complex is put into tube type resistance furnace in N2Heat-agglomerating in atmosphere, arranges program
Heat up as 5 DEG C/min, sintering temperature is 400 DEG C, sintering time is 4 h, after cooling, to obtain Graphene multiple for ground 200 mesh sieves
Close ternary material Graphene/ LiNi0.5Co0.3Mn0.2O2Sample.
Using wide-angle x-ray diffraction instrument (XRD, Bruker D8, German Bruker-axs company) analyzing crystal phase knot
Structure, crystal parameterses, the microstructure such as crystallite dimension, from accompanying drawing 1, Graphene compound for ternary material
LiNi0.5Co0.3Mn0.2O2Do not cause the change in structure, there is no the peak of other impurities, little to its Effects on Microstructure.
Chemical property is tested by button battery, for the button simulated battery positive pole of electrochemical property test
Material is the Graphene complex ternary material Graphene/ LiNi that embodiment 1 is obtained0.5Co0.3Mn0.2O2, mass ratio is according to just
Pole material：Conductive agent acetylene black（SP）：Binding agent PVDF：Solvent N-methyl pyrilidone（NMP）For 94.5：3：2.5：60, slurry
After material mix homogeneously, it is applied in current collector aluminum foil, 3 hs, electronic twin rollers at 120 DEG C, are dried（MR-100A, Shenzhen section crystalline substance intelligence
Reach）Tabletting, carries out cut-parts and weighs, and compacted depth is 65 um（Wherein aluminum foil thickness is 24 um）, compacted density is 3.59 g/
cm3, surface density is 150.33g/m2, simulated battery be assembled in argon protection glove box in carry out, negative pole be metal lithium sheet,
Celgard2300 capillary polypropylene is barrier film, the LiPF6/EC+DMC (volume ratio 1 of 1 mol/L:1, Beijing chemical reagent is studied
Institute) solution be electrolyte.Electro-chemical test condition：Activated 2 times with 0.2C rate charge-discharge, charging/discharging voltage is 2.75-4.3v.
Embodiment 2：
By commodity ternary material LiNi0.5Co0.3Mn0.2O2（523 types）, Graphene carries out early stage process：Will
LiNi0.5Co0.3Mn0.2O2, Graphene in 150 DEG C of baking ovens, 2h is dried, is ground existing to not occurring to reunite after cooling respectively
As till, be then respectively put into standby in exsiccator；Using balance precise 0.1001 g Graphene, it is scattered in and is filled
In reactor in 50 ml dehydrated alcohol, put into magneton, using ultrasonic assistant dispersion；Using balance precise 10.0002 g
LiNi0.5Co0.3Mn0.2O2, Graphene and LiNi0.5Co0.3Mn0.2O2Mass percent is 1:100, point 4 addition inner liner of reaction kettle
In, stir 30 min, magneton is taken out, closed reaction kettle, put it in the baking oven that temperature is 180 DEG C, after reaction 12 h,
Natural cooling, take out liner carry out sucking filtration, carry out washing three times with ethanol, then dry, obtain Graphene with
LiNi0.5Co0.3Mn0.2O2Complex；Gained complex is put into tube type resistance furnace in N2Heat in atmosphere, setting temperature programming is
5 DEG C/min, sintering temperature is 400 DEG C, and sintering time is 4 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary
Material Graphene/ LiNi0.5Co0.3Mn0.2O2Sample.
Chemical property is tested by button battery, for the button simulated battery positive pole of electrochemical property test
The Graphene complex ternary material Graphene/ LiNi that material is obtained by embodiment 20.5Co0.3Mn0.2O2Sample, mass ratio is pressed
According to positive electrode：Conductive agent acetylene black（SP）：Binding agent PVDF：Solvent N-methyl pyrilidone（NMP）For 94.5：3：2.5：
60, after its slurry mix homogeneously, it is applied in current collector aluminum foil, 120 DEG C of drying 3 h, electronic twin rollers（MR-100A, Shenzhen
Section's crystalline substance intelligence reaches）Tabletting, carries out cut-parts and weighs, and compacted depth is 65 um（Wherein aluminum foil thickness is 24 um）, compacted density is
3.52 g/cm3, surface density is 147.03g/m2.
Embodiment 3：
By commodity ternary material LiNi0.5Co0.3Mn0.2O2（523 types）, Graphene carries out early stage process：Will
LiNi0.5Co0.3Mn0.2O2, Graphene in 180 DEG C of baking ovens, 2h is dried, is ground existing to not occurring to reunite after cooling respectively
As till, be then respectively put into standby in exsiccator；Using balance precise 0.0999 g Graphene, it is scattered in and is filled
In 50 ml anhydrous isopropyl alcohol reactors, put into magneton, using ultrasonic assistant dispersion；Using balance precise 9.9992 g
LiNi0.5Co0.3Mn0.2O2, Graphene and LiNi0.5Co0.3Mn0.2O2Mass percent is 1:100, point 4 addition inner liner of reaction kettle
In, stir 30 min, magneton is taken out, closed reaction kettle, put it in the baking oven that temperature is 200 DEG C, after reaction 24 h,
Natural cooling, take out liner carry out sucking filtration, carry out washing three times with isopropanol, then dry, obtain Graphene with
LiNi0.5Co0.3Mn0.2O2Complex；Gained complex is put into tube type resistance furnace in N2Heat in atmosphere, setting temperature programming is
5 DEG C/min, sintering temperature is 600 DEG C, and sintering time is 4 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary
Material Graphene/ LiNi0.5Co0.3Mn0.2O2Sample.
From field emission scanning electron microscope（SEM,）And transmission scanning electron microscope（TEM）Analyze its sample and be combined feelings
Condition.From accompanying drawing 2, the method is prepared Graphene complex ternary material and is more uniformly dispersed, and more strip graphite
Alkene can closely be coated on ternary material surface, shows as cladding form.
Chemical property is tested by button battery, for the button simulated battery positive pole of electrochemical property test
Material has the material sample that embodiment is obtained, its positive electrode, conductive agent acetylene black（SP）, binding agent PVDF, Solvents N-methyl
Ketopyrrolidine（NMP）It is 94.5 according to mass ratio：3：2.5：60, after its slurry mix homogeneously, it is applied in current collector aluminum foil,
120 DEG C of drying 3 h, electronic twin rollers（MR-100A, Shenzhen section crystalline substance intelligence reaches）Tabletting, carries out cut-parts and weighs, and compacted depth is 65
um（Wherein aluminum foil thickness is 24 um）, compacted density is 3.59 g/cm3, and surface density is 144.11g/m2.
Embodiment 4：
By commodity ternary material LiNi0.5Co0.3Mn0.2O2（523 types）, Graphene carries out early stage process：Will
LiNi0.5Co0.3Mn0.2O2, Graphene in 150 DEG C of baking ovens, 2h is dried, is ground existing to not occurring to reunite after cooling respectively
As till, be then respectively put into standby in exsiccator；Using balance precise 0.3001g Graphene, it is scattered in and is filled
In reactor in 50 ml dehydrated alcohol, put into magneton, using ultrasonic assistant dispersion；Using balance precise 10.0012 g
LiNi0.5Co0.3Mn0.2O2, Graphene and LiNi0.5Co0.3Mn0.2O2Mass percent is 3:100, point 6 addition inner liner of reaction kettle
In, stir 30 min, magneton is taken out, closed reaction kettle, put it in the baking oven that temperature is 180 DEG C, after reaction 12 h,
Natural cooling, take out liner carry out sucking filtration, carry out washing three times with ethanol, then dry, obtain Graphene with
LiNi0.5Co0.3Mn0.2O2Complex；Gained complex is put into tube type resistance furnace heat in an ar atmosphere, temperature programming is set
For 5 DEG C/min, sintering temperature is 400 DEG C, and sintering time is 6 h, and after cooling, ground 200 mesh sieves obtain Graphene and are combined three
First material Graphene/ LiNi0.5Co0.3Mn0.2O2Sample.
From field emission scanning electron microscope（SEM,）Analyze its sample combining case.Fig. 6 is had to understand, the method prepares stone
Black alkene complex ternary material has obtained more strip Graphene and can closely be coated on ternary material surface；Its large stretch of Graphene
Around ternary material, it shows as cladding form.
Embodiment 5：
By commodity ternary material LiNi1/3Co1/3Mn1/3O2（111 types）, Graphene carries out early stage process：By LiNi1/3Co1/ 3Mn1/3O2, Graphene in 150 DEG C of baking ovens, 2h is dried, is ground respectively after cooling to there is not agglomeration, so
After be respectively put into standby in exsiccator；Using balance precise 0.0301g Graphene, it is scattered in that to fill 50 ml anhydrous
In reactor in ethanol, put into magneton, using ultrasonic assistant dispersion；Using balance precise 10.0012 g LiNi1/ 3Co1/3Mn1/3O2, Graphene and LiNi1/3Co1/3Mn1/3O2Mass percent is 0.3:100, in point 2 addition inner liner of reaction kettle,
Stir 30 min, magneton is taken out, closed reaction kettle, put it into and arranged in the oil bath pan that temperature is 150 DEG C, open
Stirring, the response time is 6 h, after reaction terminates natural cooling, takes out liner and carries out sucking filtration, with the tert-butyl alcohol, ethanol is washed
Three times, after drying, obtain Graphene and LiNi1/3Co1/3Mn1/3O2Complex；Gained complex is put into tube type resistance furnace in He
Heat in atmosphere, setting temperature programming is 5 DEG C/min, sintering temperature is 500 DEG C, sintering time is 4 h, ground after cooling
200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi1/3Co1/3Mn1/3O2Sample.
Embodiment 6：
By commodity ternary material LiNi00.4Co0.4Mn0.2O2（442 types）, Graphene carries out early stage process：Will
LiNi00.4Co0.4Mn0.2O2, Graphene in 150 DEG C of baking ovens, 2h is dried, is ground respectively after cooling to not reuniting
Till phenomenon, then it is respectively put into standby in exsiccator；Using balance precise 0.0300 g Graphene, it is scattered in Sheng
Have in reactor in 50 ml anhydrous isopropyl alcohols；Using balance precise 9.9989g LiNi00.4Co0.4Mn0.2O2, Graphene
With LiNi0.5Co0.3Mn0.2O2Mass percent is 0.3:100, point 4 addition reactors, stirring 30 min, closed reaction kettle,
Set 220 DEG C of reaction temperature, after reaction 12 h, natural cooling, take out liner and carry out sucking filtration, carry out washing three with isopropanol
Secondary, then dry, obtain Graphene and LiNi00.4Co0.4Mn0.2O2Complex；Gained complex is put into tube type resistance furnace in N2
Heat in atmosphere, setting temperature programming is 5 DEG C/min, sintering temperature is 200 DEG C, sintering time is 6 h, ground after cooling
200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi00.4Co0.4Mn0.2O2Sample.
Embodiment 7：
By commodity ternary material LiNi0.5Co0.3Mn0.2O2（523 types）, commercial graphite alkene carries out early stage process：Will
LiNi0.5Co0.3Mn0.2O2, Graphene in 120 DEG C of baking ovens, is dried 3 h, is ground respectively to not reuniting after cooling
Till phenomenon, then it is respectively put into standby in exsiccator；Using the above-mentioned Graphene of balance precise 0.3001 g, disperseed
In the reactor filling 25 ml anhydrous isopropyl alcohols and 25 ml dehydrated alcohol, put into magneton, using ultrasonic assistant dispersion；Profit
With balance precise 10.0021 g ternary material, Graphene and LiNi0.5Co0.3Mn0.2O2Mass percent is 3:100, divide 3
In the liner of secondary addition reactor, stir 30 min, magneton taken out, closed reaction kettle, put it in 180 DEG C of baking oven,
After reacting 24 h, natural cooling, then take out inner liner of reaction kettle and carry out sucking filtration, with isopropanol, ethanol washed once respectively, dries
Afterwards, Graphene and LiNi are obtained0.5Co0.3Mn0.2O2Complex, gained complex is put into tube type resistance furnace in N2Add in atmosphere
Thermal sintering, setting temperature programming is 5 DEG C/min, and sintering temperature is 400 DEG C, and sintering time is 4 h, ground 200 after cooling
Mesh sieve obtains Graphene complex ternary material Graphene/ LiNi0.5Co0.3Mn0.2O2Sample.
From field emission scanning electron microscope（SEM,）Analyze its sample combining case.From accompanying drawing 7, prepared by the method
Graphene complex ternary material Graphene/ LiNi0.5Co0.3Mn0.2O2Large stretch of Graphene also around ternary material, with anti-
Answer time lengthening, second particle occurs some and crushes, and can be seen that primary particle is attached to Graphene from the SEM in figure of accompanying drawing 7
On piece.
Comparative example 1
By commodity ternary material LiNi0.5Co0.3Mn0.2O2（523 types）, conductive agent acetylene black（SP）, binding agent PVDF, molten
Agent N-Methyl pyrrolidone（NMP）It is 94.5 according to mass ratio：3：2.5：60, after its slurry mix homogeneously, it is applied in collector
On aluminium foil, 120 DEG C of drying 3 h, electronic twin rollers（MR-100A, Shenzhen section crystalline substance intelligence reaches）Tabletting, carries out cut-parts and weighs, compacting
Thickness is 65 um（Wherein aluminum foil thickness is 24 um）, compacted density is 3.59 g/cm3, and surface density is 150.33g/m2.Simulation
Battery is assembled in the glove box of argon protection and carries out, and negative pole is metal lithium sheet, and Celgard2300 capillary polypropylene is barrier film,
LiPF6/EC+DMC (the volume ratio 1 of 1mol/L:1, Beijing Inst. of Chemical Reagent) solution is electrolyte.Electrochemical test bar
Part：Activated 2 times with 0.2C rate charge-discharge, charging/discharging voltage is 2.75-4.3V.
Claims (7)
1. a kind of method that monoalcohol solvent full-boiled process prepares Graphene complex ternary material, described ternary material is
LiNixCoyMnzO2, x+y+z=1,0.2≤x≤0.6,0.1≤y≤0.4,0.2≤z≤0.5；Graphene complex ternary material
Chemical general formula is Graphene/ LiNixCoyMnzO2It is characterised in that：Including following preparation process：
（1）Early stage is processed：By ternary material LiNixCoyMnzO2, Graphene be placed in baking oven, at 120～200 DEG C be dried 1～3
h；It is ground respectively after cooling, put into standby in exsiccator；
（2）Under room temperature, weigh step（1）Gained graphene powder, is well-dispersed in anti-equipped with anhydrous monoalcohol solvent
Answer in kettle, prepare graphene dispersing solution；
（3）Determine LiNixCoyMnzO2The mass percent being combined with Graphene, weighs step（1）Gained LiNixCoyMnzO2Powder
End, is divided into 2-6 addition step（2）Reactor in, sealing is stirred, and makes LiNixCoyMnzO2Fully mixed with Graphene
Close, the mass percent that described Graphene is combined with ternary material is 0.3～3：100；
（4）Reactor is put in heater, sets reaction temperature and response time, natural cooling after the completion of reaction, sucking filtration,
Washing, dry, obtain the complex of Graphene and ternary material, described reaction temperature is 150～220 DEG C, the response time for 3～
24 h；
（5）By step（4）Gained complex sinters in an inert atmosphere, and after natural cooling, ground 200 mesh sieves obtain final stone
Black alkene complex ternary material Graphene/ LiNixCoyMnzO2.
2. the method that a kind of monoalcohol solvent full-boiled process according to claim 1 prepares Graphene complex ternary material, it is special
Levy and be：Step（2）Described anhydrous monohydric alcohol is methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, sec-butyl alcohol and the tert-butyl alcohol
The mixed liquor of one or more.
3. the method that a kind of monoalcohol solvent full-boiled process according to claim 1 prepares Graphene complex ternary material, it is special
Levy and be：Step（2）The mass concentration of gained graphene dispersing solution is 0.3～6mg/ml.
4. the method that a kind of monoalcohol solvent full-boiled process according to claim 1 prepares Graphene complex ternary material, it is special
Levy and be：Step（4）Described in washing process use step（2）In monohydric alcohol washed.
5. the method that a kind of monoalcohol solvent full-boiled process according to claim 1 prepares Graphene complex ternary material, it is special
Levy and be：Step（4）Described heater is the heater that baking oven or oil bath pan or reactor carry.
6. the method that a kind of monoalcohol solvent full-boiled process according to claim 1 prepares Graphene complex ternary material, it is special
Levy and be：Step（5）Described inert atmosphere is one kind of nitrogen, helium or argon.
7. the method that a kind of monoalcohol solvent full-boiled process according to claim 1 prepares Graphene complex ternary material, it is special
Levy and be：Step（5）Described sintering temperature is 200～600 DEG C, and sintering time is 2～6 h.
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