A kind of boron atom doping vario-property grapheme material, preparation method and application
Technical field
Present invention relates particularly to a kind of boron atom doping vario-property grapheme material, and modified graphene material preparation side
Method and application, belong to electrode material production technical field.
Background technology
Double electric layers supercapacitor(It is also called super capacitor, Super Capacitor or Ultra Capacitor), it is
The novel energy-storing element occurred recently as the breakthrough of material science, the ratio that it has been filled up between ordinary capacitor and battery
Energy and specific power blank, with up to thousands of farads of capacitance, the electric current that sparks is up to kilo-ampere, while also having
It is safe and reliable, it is the breakthrough component for improving and solving electric power performance applications the characteristics of the scope of application is wide.Electric double layer surpasses
Level capacitor is in automobile(Particularly electric automobile, fuel combination automobile and exceptional load vehicle), wind energy, solar energy, national defence troops
The aspects such as work, electric power, railway, communication, consumption electronic products have huge application value and market potential, by countries in the world
Institute's extensive concern.Ultracapacitor is also referred to as double layer capacitor.Electrochemical capacitor be using electrode surface formed electric double layer or
There is two dimension or quasi- two dimension faraday's reaction storage electric energy in person.As a kind of new energy storage device, electrochemical capacitor with
Its high power and long-life cause the attention of numerous researchers.Carbon material as capacitor electrode material, research history compared with
It is long.Recent study is concentrated mainly on the sides such as the pore size and pore size distribution of the specific surface area and control carbon material for improving carbon material
Face.Although porous carbon materials can obtain comparing specific capacitance high, conductive capability is low, and its relatively low specific power is limited
Its as ultracapacitor application.Although its conduction of CNT and each side excellent ability, its contact electricity high
Resistance, and the colelctor electrode of costliness also limit its application.Grapheme material as Condensed Matter Physics a kind of brand-new two-dimentional material
Material, with larger specific surface area and excellent conductive capability, and cost price is low, and manufacture craft is simple, is as super electricity
The optimal selection of container electrode material.With the incorporation of hetero atom such as boron atom, nitrogen-atoms etc., grapheme material can be improved
Electric conductivity, and can provide a part fake capacitance, lifted ultracapacitor energy density.
The content of the invention
It is an object of the invention to provide a kind of boron atom doping vario-property grapheme material.
Meanwhile, the preparation method of the also same boron atom doping vario-property grapheme material of the present invention.
Finally, the present invention provides a kind of application of boron atom doping vario-property grapheme material in ultracapacitor is prepared.
In order to realize the above object the technical solution adopted in the present invention is:
A kind of boron atom doping vario-property grapheme material, boron atom proportion is 0.1~30wt%(Boron atom is modified
Mass percent in grapheme material).
The preparation method of the boron atom doping vario-property grapheme material is:Respectively by soluble oxidation Graphene and boracic
Atomic compound dissolves, and takes two kinds of solution mixing(Soluble oxidation Graphene chemically reacts with boracic atomic compound),
Solid precursor material is dried to obtain, then annealed treatment is obtained final product.
The preparation method of described soluble oxidation Graphene is:5g graphite, 3.75g sodium nitrate are weighed, both are mixed
Added after uniform in the there-necked flask of 2L, be further continued for, to the 332ml concentrated sulfuric acids are added in flask, stirring;Heating water bath, makes burning
System temperature maintains 35~45 DEG C in bottle, is then slowly added into potassium permanganate 22.5g, stirs 3 days;Add water 1L(It is added dropwise),
90~95 DEG C are maintained, 2 hours are incubated;Hydrogen peroxide is added dropwise, until solution is changed into light yellow completely, is stirred for 30 minutes, it is natural
Precipitation is centrifuged, and is drying to obtain.Or commercially available soluble oxidation Graphene is used, but need to ensure that metals content impurity is less than
20ppm, otherwise needs to carry out metal ion dialysis treatment, just can be used to prepare boron atom doping vario-property grapheme material.Dissolving
Soluble oxidation Graphene uses water, and concentration is 5mg/mL.
Described boracic atomic compound is boron oxide or boric acid.Dissolving boron oxide can use ethanol, and concentration is 1~10g
Boron oxide/50mL ethanol;Dissolving boric acid uses water, and concentration is 1~10g boric acid/50mL water.
Described drying can be dried using spray drying or low-temp low-pressure(Such as low-temperature vacuum drying)Method.Spray drying
Design parameter be:20~80 DEG C of feed temperature, 100~200 DEG C of outlet temperature, 60~1000 cubes ms/h of air mass flow.
Preferably:60 DEG C of feed temperature, 120 DEG C of outlet temperature, 100 cubes ms/h of air mass flow.Low-temp low-pressure is dried can be used-
20 DEG C of low pressure are dried(Solvent distils).
The step of described annealing is:In inert gas(Such as argon gas)Under protection, by persursor material with 1~15
DEG C/heating rate of min is warming up to 600~1500 DEG C, insulation is cooled down after 1~10 hour.Preferably:With 3 DEG C/min's
Heating rate is warming up to 1000 DEG C, is incubated 3 hours.
A kind of preparation method of boron atom doping vario-property grapheme material, comprises the following steps:
(1)Soluble oxidation graphene dispersion is obtained into the solution that concentration is 5mg/mL in water;
(2)Boracic atomic compound is scattered in solvent the solution for obtaining that concentration is 1~10g/50mL;
(3)By step(2)Solution be added to step(1)Solution in, dry persursor material after being sufficiently stirred for;
(4)Take step(3)Persursor material it is annealed treatment obtain final product boron atom doping vario-property grapheme material.
The step(1)The middle preferred ultrasonic disperse of dispersion, the frequency of ultrasonic disperse is 30~100kHz.
The step(2)Middle boracic atomic compound is boron oxide or boric acid.Dispersion boron oxide can use etoh solvent, point
Scattered boric acid uses aqueous solvent, concentration to be respectively 1~10g boron oxides/50mL ethanol, 1~10g boric acid/50mL water.
The step(3)Middle step(1)Solution and step(2)The volume ratio of solution is(10~90):(90~10).
The step(3)The time of middle stirring is 1~5 hour, and speed of agitator is 60~120r/min.
The step(3)Middle drying can use spray drying or the dry method of low-temp low-pressure, specifically ibid.
The step(4)The step of middle annealing is:In inert gas(Such as argon gas)Under protection, by persursor material with
The heating rate of 1~15 DEG C/min is warming up to 600~1500 DEG C, and insulation is cooled down after 3 hours.Preferably:With 3 DEG C/min's
Heating rate is warming up to 1000 DEG C, is incubated 3 hours.
A kind of application of boron atom doping vario-property grapheme material in ultracapacitor is prepared.Described boron atom doping
Modified graphene material is used as capacitor anode and/or the active material of negative pole.Concretely comprise the following steps:It is with mass ratio(80~
95):(20~5)Boron atom doping vario-property grapheme material is mixed with binding agent, mixing material is compressed in collector plate and is made
Standby positive/negative plate;Take positive/negative plate to place face-to-face, isolated with porous septum, add and obtained final product in electrolyte post package to battery case
Ultracapacitor.
Described boron atom doping vario-property grapheme material needs 120 DEG C of low temperature to dry 6 hours before mixing with binding agent.
Described binding agent is polytetrafluoroethylene (PTFE) or Kynoar.Active material is mixed with the preferred ultrasound of the mixing of binding agent
Close.
Described compacting uses 10~20MPa pressure, and collector plate is nickel foam collector plate.
Described positive/negative plate can be tailored into the circle of diameter 13mm, and wherein activity substance content is about 4mg.
Described porous septum can be using common diaphragm materials such as polypropylene films.
Described electrolyte is to use containing lithium salt electrolyte such as concentration as the tetraethyl boron fluoric acid ammonium salt of 1~2mol/L is electrolysed
Liquid, or tetraethyl boron fluoric acid ammonium salt/acetonitrile electrolyte that concentration is 1~2mol/L, it is 5~30wt% that can also use mass fraction
KOH electrolyte or H2SO4 electrolyte.
Beneficial effects of the present invention:
The monolithic size of boron atom doping vario-property grapheme material is in 10nm in the present invention2To 400 μm2Between, boron atom institute
Accounting example is 0.1~30wt%, and with two-dimensional structure, specific surface area is big, and electric conductivity is high.Wherein boron atom is entrained in carbon-to-carbon crystalline substance
In lattice, there is the performance for producing fake capacitance in extra electron hole, be produced using the unnecessary electronics of hetero atom itself and hole
Electrochemical reaction is given birth to improve the capacitive property of grapheme material.
Be sufficiently mixed for the two by preparing soluble oxidation graphene solution and boracic atomic compound solution by the present invention
The other dispersion of molecular level is realized, hydroxy functional group reacts with boracic atomic compound in being conducive to graphene oxide, makes boron
Atom is connected on graphene oxide in the way of chemical bond, and boron atom is entrained in carbon-to-carbon lattice.Preparation method letter
It is single, easy to operate, it is suitable to industrialization large-scale production and applies.
As electrode active material be used to boron atom doping vario-property grapheme material to prepare ultracapacitor by the present invention, has
Beneficial to the specific capacitance, specific power and the energy density that improve capacitor, can effectively be saved compared with conventional carbon type ultracapacitor
The energy is saved, the chemical property of capacitor can be effectively improved compared with carbon nano tube type ultracapacitor, its performance is remarkable, cost
It is cheap, it is suitable to large-scale industrial production and application.
Brief description of the drawings
Fig. 1 is the cyclic voltammetry curve of ultracapacitor in the embodiment of the present invention 1;
Fig. 2 is the ac impedance measurement curve of ultracapacitor in embodiment 1:
Fig. 3 is the x-ray photoelectron energy spectrum diagram of boron atom doping vario-property grapheme material in embodiment 1;
Fig. 4 is the cyclic voltammetry curve of ultracapacitor in embodiment 2.
Specific embodiment
Following embodiments are only described in further detail to the present invention, but do not constitute any limitation of the invention.
Embodiment 1
Boron atom doping vario-property grapheme material in the present embodiment, its preparation method is:
(1)The preparation of soluble oxidation Graphene
5g graphite, 3.75g sodium nitrate are weighed, by the there-necked flask of both addition 2L after well mixed, is further continued for burning
The 332ml concentrated sulfuric acids are added in bottle, is stirred;Heating water bath, makes system temperature in flask maintain 40 DEG C, is then slowly added into
Potassium permanganate 22.5g, stirs 3 days;Add water 1L(It is added dropwise), 90 DEG C are maintained, it is incubated 2 hours;Hydrogen peroxide is added dropwise, until solution
It is changed into light yellow completely, is stirred for 30 minutes, natural sedimentation or centrifugation is drying to obtain;
(2)200mg soluble oxidation Graphene ultrasonic disperses are obtained into the solution that concentration is 5mg/mL in water;
(3)By 1g boron oxides dispersed with stirring in 50mL ethanol solutions, then the ethanol solution of boron oxide is slowly added into
Step(2)Solution in, stirring at normal temperature 3 hours mixed liquor;
(4)Take step(3)Mixed liquor be spray-dried to obtain persursor material, the parameter of spray drying is:Feed temperature 60
DEG C, 120 DEG C of outlet temperature, 100 cubes ms/h of air mass flow;
(5)Under argon gas protection, persursor material is warming up to 1000 DEG C with the heating rate of 3 DEG C/min, insulation 3 is small
When, natural cooling obtains boron atom doping vario-property grapheme material.
The x-ray photoelectron energy spectrum diagram of the boron atom doping vario-property grapheme material of above-mentioned preparation is shown in Fig. 3.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, with quality is the polytetrafluoroethyl-ne of 5mg through after 120 DEG C of low temperature dryings 6 hours
Alkene ultrasonic wave mixes, and mixed electrode material is compressed in nickel foam collector plate under 16MPa pressure, is tailored into a diameter of
The circular electric pole piece of 13mm(The quality of active material boron atom doping vario-property grapheme material is about 4mg);Quality is close
Two panels electrode slice is placed face-to-face, middle to be isolated with polypropylene porous septum, and it is the tetraethyl boron fluorine of 1mol/L that 2mL concentration is added dropwise
Acid ammonium salt electrolyte, then encapsulates and obtains ultracapacitor to button cell shell, and its specific capacitance is 156F/g.
The cyclic voltammetry curve of the ultracapacitor of above-mentioned preparation, ac impedance measurement curve are shown in Fig. 1,2.
Embodiment 2
Boron atom doping vario-property grapheme material in the present embodiment is with embodiment 1.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, with quality is the polytetrafluoroethyl-ne of 10mg through after 120 DEG C of low temperature dryings 6 hours
Alkene ultrasonic wave mixes, and mixed electrode material is compressed in nickel foam collector plate under 16MPa pressure, is tailored into a diameter of
The circular electric pole piece of 13mm(The quality of active material boron atom doping vario-property grapheme material is about 4mg);Quality is close
Two panels electrode slice is placed face-to-face, middle to be isolated with polypropylene film, and it is the KOH electrolyte of 5wt% that 1mL mass fractions are added dropwise, so
Ultracapacitor is obtained in post package to button cell shell, its specific capacitance is 175F/g.
The cyclic voltammetry curve of ultracapacitor is shown in Fig. 4 in the present embodiment.
Embodiment 3
Boron atom doping vario-property grapheme material in the present embodiment is with embodiment 1.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, with quality is the polytetrafluoroethyl-ne of 15mg through after 120 DEG C of low temperature dryings 6 hours
Alkene ultrasonic wave mixes, and mixed electrode material is compressed in nickel foam collector plate under 16MPa pressure, is tailored into a diameter of
The circular electric pole piece of 13mm(The quality of active material boron atom doping vario-property grapheme material is about 4mg);Quality is close
Two panels electrode slice is placed face-to-face, middle to be isolated with polypropylene film, and 1mL mass fractions are added dropwise for the H2SO4 of 30wt% is electrolysed
Liquid, then encapsulates and obtains ultracapacitor to button cell shell, and its specific capacitance is 205F/g.
Embodiment 4
Boron atom doping vario-property grapheme material in the present embodiment is with embodiment 1.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, with quality is the polytetrafluoroethyl-ne of 5mg through after 120 DEG C of low temperature dryings 6 hours
The nodularization of alkene ultrasonic wave mixes, and mixed electrode material is compressed in nickel foam collector plate under 16MPa pressure, is tailored into straight
Footpath is the circular electric pole piece of 13mm(The quality of active material boron atom doping vario-property grapheme material is about 4mg);By quality phase
Near two panels electrode slice is placed face-to-face, middle to be isolated with polypropylene film, and 1mL mass fractions are added dropwise for the KOH of 30wt% is electrolysed
Liquid, then encapsulates and obtains ultracapacitor to button cell shell, and its specific capacitance is 230F/g.
Embodiment 5
Boron atom doping vario-property grapheme material in the present embodiment is with embodiment 1.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly:100mg boron atom doping vario-property Graphenes are taken, it is 8% to be added to 100g mass percents after 6 hours through 120 DEG C of low temperature dryings
Kynoar 1-METHYLPYRROLIDONE solution in, dispersion 3 hours obtain slurry, by slurry blade coating electricity is made on aluminium foil
Pole piece, then be vacuum dried 6 hours at 120 DEG C, it is tailored into the circular electric pole piece of a diameter of 13mm(Active material boron atom is adulterated
The quality of modified graphene material is about 14mg);The close two panels electrode slice of quality is placed face-to-face, it is middle thin with polypropylene
Film is isolated, and it is the tetraethyl boron fluoric acid ammonium salt/acetonitrile electrolyte of 1mol/L that 1.5mL concentration is added dropwise, and is then encapsulated to button cell
Ultracapacitor is obtained in shell, its specific capacitance is 173F/g.
Embodiment 6
Boron atom doping vario-property grapheme material in the present embodiment, its preparation method is:
(1)The preparation of soluble oxidation Graphene
5g graphite, 3.75g sodium nitrate are weighed, by the there-necked flask of both addition 2L after well mixed, is further continued for burning
The 332ml concentrated sulfuric acids are added in bottle, is stirred;Heating water bath, makes system temperature in flask maintain 45 DEG C, is then slowly added into
Potassium permanganate 22.5g, stirs 3 days;Add water 1L(It is added dropwise), 95 DEG C are maintained, it is incubated 2 hours;Hydrogen peroxide is added dropwise, until solution
It is changed into light yellow completely, is stirred for 30 minutes, natural sedimentation or centrifugation is drying to obtain;
(2)200mg soluble oxidation Graphene ultrasonic disperses are obtained into the solution that concentration is 5mg/mL in water;
(3)By 3g boric acid dispersed with stirring in 50mL water, then boron aqueous acid is slowly added into step(2)Solution
In, stirring at normal temperature obtains mixed liquor in 3 hours;
(4)Take step(3)Mixed liquor be spray-dried to obtain persursor material, the parameter of spray drying is:Feed temperature 60
DEG C, 120 DEG C of outlet temperature, 100 cubes ms/h of air mass flow;
(5)Under argon gas protection, persursor material is warming up to 800 DEG C with the heating rate of 3 DEG C/min, is incubated 3 hours,
Natural cooling obtains boron atom doping vario-property grapheme material.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, with quality is the polytetrafluoroethyl-ne of 5mg through after 120 DEG C of low temperature dryings 6 hours
Alkene ultrasonic wave mixes, and mixed electrode material is compressed in nickel foam collector plate under 16MPa pressure, is tailored into a diameter of
The circular electric pole piece of 13mm(The quality of active material boron atom doping vario-property grapheme material is about 4mg);Quality is close
Two panels electrode slice is placed face-to-face, middle to be isolated with polypropylene porous septum, and 1mL mass fractions are added dropwise for the KOH of 30wt% is electrolysed
Liquid, then encapsulates and obtains ultracapacitor to button cell shell, and its specific capacitance is 250F/g.
Embodiment 7
Boron atom doping vario-property grapheme material in the present embodiment is with embodiment 6.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, with quality is the polytetrafluoroethyl-ne of 5mg through after 120 DEG C of low temperature dryings 6 hours
The nodularization of alkene ultrasonic wave mixes, and mixed electrode material is compressed in nickel foam collector plate under 16MPa pressure, is tailored into straight
Footpath is the circular electric pole piece of 13mm(The quality of active material boron atom doping vario-property grapheme material is about 4mg);By quality phase
Near two panels electrode slice is placed face-to-face, middle to be isolated with polypropylene porous septum, and it is 30wt%'s that 2mL mass fractions are added dropwise
H2SO4Electrolyte, then encapsulates and obtains ultracapacitor to button cell shell, and its specific capacitance is 228F/g.
Embodiment 8
Boron atom doping vario-property grapheme material in the present embodiment is with embodiment 6.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, with quality is the polytetrafluoroethyl-ne of 5mg through after 120 DEG C of low temperature dryings 6 hours
The nodularization of alkene ultrasonic wave mixes, and mixed electrode material is compressed in nickel foam collector plate under 16MPa pressure, is tailored into straight
Footpath is the circular electric pole piece of 13mm(The quality of active material boron atom doping vario-property grapheme material is about 4mg);By quality phase
Near two panels electrode slice is placed face-to-face, middle to be isolated with polypropylene porous septum, and it is the tetraethyl of 1mol/L that 2mL concentration is added dropwise
Boron fluoric acid ammonium salt electrolyte, then encapsulates and obtains ultracapacitor to button cell shell, and its specific capacitance is 158F/g.
Embodiment 9
Boron atom doping vario-property grapheme material in the present embodiment is with embodiment 6.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared in the present embodiment, including following step
Suddenly it is:100mg boron atom doping vario-property Graphenes are taken, being added to 100g mass percents after 6 hours through 120 DEG C of low temperature dryings is
In the 1-METHYLPYRROLIDONE solution of 7% Kynoar, 3 hours of dispersion obtain slurry, and slurry blade coating is made on aluminium foil
Electrode slice, then be vacuum dried 6 hours at 120 DEG C, it is tailored into the circular electric pole piece of a diameter of 13mm(Active material boron atom is mixed
The quality of miscellaneous modified graphene material is about 14mg);The close two panels electrode slice of quality is placed face-to-face, centre is with polypropylene
Porous septum is isolated, and it is the tetraethyl boron fluoric acid ammonium salt/acetonitrile electrolyte of 1mol/L that 1mL concentration is added dropwise, and is then encapsulated to button
Ultracapacitor is obtained in battery case, its specific capacitance is 163F/g.
Embodiment 10
Boron atom doping vario-property grapheme material in the present embodiment, its preparation method is:
(1)Taking commercially available soluble oxidation Graphene carries out metal ion dialysis treatment, is less than metals content impurity
20ppm;
(2)Take step(1)Middle soluble oxidation Graphene 200mg, it is 5mg/mL's that ultrasonic disperse obtains concentration in water
Solution;
(3)By 10g boron oxides dispersed with stirring in 50mL ethanol solutions, then the ethanol solution of boron oxide is slowly added into
Step(2)Solution in, stirring at normal temperature 5 hours mixed liquor;
(4)Take step(3)Mixed liquor be spray-dried to obtain persursor material, the parameter of spray drying is:Feed temperature 20
DEG C, 100 DEG C of outlet temperature, 150 cubes ms/h of air mass flow;
(5)Under argon gas protection, persursor material is warming up to 600 DEG C with the heating rate of 1 DEG C/min, insulation 10 is small
When, natural cooling obtains boron atom doping vario-property grapheme material.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared is with embodiment 1 in the present embodiment.
Embodiment 11
Boron atom doping vario-property grapheme material in the present embodiment, its preparation method is:
(1)Taking commercially available soluble oxidation Graphene carries out metal ion dialysis treatment, is less than metals content impurity
20ppm;
(2)Take step(1)Middle soluble oxidation Graphene 200mg, it is 5mg/mL's that ultrasonic disperse obtains concentration in water
Solution;
(3)By 10g boric acid dispersed with stirring in 50mL water, then boron aqueous acid is slowly added into step(2)It is molten
In liquid, stirring at normal temperature obtains mixed liquor in 3 hours;
(4)Take step(3)Mixed liquor be spray-dried to obtain persursor material, the parameter of spray drying is:Feed temperature 81
DEG C, 200 DEG C of outlet temperature, 200 cubes ms/h of air mass flow;
(5)Under argon gas protection, persursor material is warming up to 1500 DEG C with the heating rate of 15 DEG C/min, insulation 1 is small
When, natural cooling obtains boron atom doping vario-property grapheme material.
Application of the boron atom doping vario-property grapheme material in ultracapacitor is prepared is with embodiment 6 in the present embodiment.