CN109860565A - A kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide - Google Patents
A kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide Download PDFInfo
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- CN109860565A CN109860565A CN201910135242.4A CN201910135242A CN109860565A CN 109860565 A CN109860565 A CN 109860565A CN 201910135242 A CN201910135242 A CN 201910135242A CN 109860565 A CN109860565 A CN 109860565A
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Abstract
The invention discloses a kind of preparation methods of Magnesium ion battery specific complex nanometer vanadium pentoxide, belong to battery material technical field.The present invention first disperses modified graphene oxide in alcohols solvent, sequentially adds fatty acid and Triisopropoxyvanadium(V) oxide, 4~6h of heating reflux reaction, and discharging obtains mixed dispersion liquid；Again by mixed dispersion liquid and tin chloride solution after ultrasonic disperse is uniform in proportion, under Yu Hengwen stirring, precipitating reagent is added dropwise and adjusts pH to alkalescent, continues after being stirred to react 2~4h, filters, wash, it is dry, obtain dry cake；By gained dry cake under inert gas shielding state, 480~500 DEG C, after pyroreaction are warming up to, anneal 10~15min in air atmosphere, and it is cooling, it discharges to get Magnesium ion battery specific complex vanadium pentoxide powder.Gained Magnesium ion battery specific complex nanometer vanadium pentoxide of the invention as it is positive when with excellent chemical property, battery has obtained effective extension.
Description
Technical field
The invention discloses a kind of preparation methods of Magnesium ion battery specific complex nanometer vanadium pentoxide, belong to battery material
Expect technical field.
Background technique
Currently, the research of Magnesium ion battery can be filled also in theoretical research stage, research emphasis is concentrated mainly on to battery
Two aspect of positive electrode and electrolyte system, also rarely has the research of battery other parts (such as cathode, diaphragm, collector)
It is related to.
As the positive electrode that can fill Magnesium ion battery, its requirement should be: (1) specific energy is high；(2) electrode potential is wanted
It is high；(3) discharge and recharge reaction good reversibility；(4) chemical stability in the electrolytic solution is good, and solubility is low (self discharge is low)；(5) have
There is higher electron conduction；(6) resourceful, it is cheap.
Transient metal sulfide is considered as the prototype of insert material, and people are to magnesium ion insertion double layered transition metal vulcanization
Object conducts extensive research, in this regard, Yuan Huatang etc. has carried out detailed summary.The sulfide of Mo is earliest for Mg2+It is " embedding
Enter " investigation of materials, and it is used for Li+" insert " there are also research work.Aurbach etc. has found Mo3S4Have
Chevrel phase structure is a kind of good positive electrode.In this configuration, magnesium ion can be reversibly embedded in and speed
Comparatively fast.In other Chevrel compounds, MgxMo3O4The crystal structure of anode may be considered Mo6X8The simple accumulation of block.
Channel of the embedded location of magnesium atom between heap block, these interatomic active forces are weaker, can be in the effect of no electric field
Under, or even migrated at room temperature.As it can be seen that Chevrel phase is comparatively ideal cathode material structure.Aurbach was ground in 2000
The rechargeable Mg/Mg of function is madexMo3S4Battery.Mg/MgxMo3S4System is to make electrolyte, Mg based on the organic halogen aluminium salt of magnesiumxMo3S4Make
Cathode, in MgxMo3S4Middle Mg2+Ion can be passed in and out with quickish kinetic rate.The organic halogen aluminium salt of magnesium such as Mg (AlCl3R)2With
Mg(AlCl2RR′)2Conductivity at room temperature in THF or polyether solutions is in 0.3~0.5molL of salinity-1When it is preferable, magnesium exists
Passivating film is not formed in the system, almost 100% ground is reversible for its deposition-dissolution；In addition, solution is (super in very wide voltage range
Cross 2.5V) in be all it is stable, this range will be wide than any electrolyte solution studied in the past.Aurbach etc.
A kind of positive electrode Cu of great potential is had studied recently2Mo6S8.The resulting material of initial preparation is extremely unstable, this makes electrode
Capacity sharply reduce.By XRD and XPS research its mechanical transient metal sulfide be found so far can be used for Mg
The preferred materials of the anode of secondary cell.But sulfide itself has some disadvantages: that oxidation stability is not so good and material
Preparation requires to carry out under anaerobic etc..
For the battery of high-energy density, oxide is a kind of electrode anode material being widely used.It is aoxidizing
Strong oxygen-metallic bond in object makes have high ion characteristic in transition metal oxide, so that compound be made to have high electricity
Position.In addition, oxide has higher chemical stability than sulfide.This is for the electrochmical power source it is hoped that there will be the long-life
A kind of highly advantageous factor.So transition metal oxide is most promising positive electrode.Just for rechargeable magnesium cell
Pole material mainly has Co3O4, V2O5, Mo3O4And the oxide of Mn, wherein V2O5Performance it is advantageous, be positive electrode in recent years
Research hotspot.When vanadium pentoxide used in Magnesium ion battery traditional at present is as positive electrode, reversible capacity is lower, and
As the number of charge and discharge cycles increases, reversible capacity decline is obvious, and battery is caused to reduce, thus also need to its into
Row research.
Summary of the invention
The present invention solves the technical problem of: for vanadium pentoxide used in traditional Magnesium ion battery as anode
When material, reversible capacity is lower, and as the number of charge and discharge cycles increases, and reversible capacity decline is obvious, and battery is caused to use
The drawbacks of service life reduction, provides a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
(1) according to parts by weight, 30~50 parts of Triisopropoxyvanadium(V) oxides are successively taken, 3~5 parts of titanate esters, 80~100 parts of alcohols are molten
Agent, 30~50 parts of fatty acid, 8~10 parts of modified graphene oxides first disperse modified graphene oxide in alcohols solvent, then
Fatty acid, titanate esters and Triisopropoxyvanadium(V) oxide, 4~6h of heating reflux reaction are sequentially added, discharging obtains mixed dispersion liquid；
(2) according to parts by weight, 80~100 parts of mixed dispersion liquids are successively taken, 60~80 parts of tin chloride solutions, ultrasonic disperse is uniform
Afterwards, under Yu Hengwen stirring, precipitating reagent is added dropwise and adjusts pH to alkalescent, continues after being stirred to react 2~4h, filters, wash, do
It is dry, obtain dry cake；
(3) by gained dry cake under inert gas shielding state, 500 DEG C, after pyroreaction are to slowly warm up to, in air gas
Anneal 10~15min in atmosphere, cooling, discharges to get Magnesium ion battery specific complex nanometer vanadium pentoxide.
Step (1) titanate esters are Butyl Phthalate, tetraisopropyl titanate, any one in metatitanic acid n-propyl.
Step (1) alcohols solvent is methanol, ethyl alcohol, normal propyl alcohol, any one in isopropanol.
Step (1) fatty acid is linoleic acid, linolenic acid, arachidonic acid, any one in ricinoleic acid.
Step (1) the modified graphene oxide modifying process are as follows: by graphene oxide and water be in mass ratio 1:8~1:
After 10 ultrasonic disperses, the kayexalate of graphene oxide quality 10~20% is added, after heating stirring reaction, filtering,
Washing, it is dry, pretreatment graphene oxide is obtained, then gained is pre-processed into graphene oxide and toluene di-isocyanate(TDI) in mass ratio
After 1:4~1:6 mixing, 2~4h of heating reflux reaction, using filter, washing and drying obtain modified graphene oxide.
Step (2) described precipitating reagent is the urea liquid that mass fraction is 8~10%, the ammonium hydroxide that mass fraction is 4~6%,
The sodium carbonate liquor that mass-dispersion is 4~8%, the sodium bicarbonate solution that mass-dispersion is 5~10%, mass-dispersion are 2~4%
Hydrogen-oxygen Warner solution, mass-dispersion are any one in 3~5% potassium hydroxide solution.
Step (2) described alkalescent are as follows: pH is 7.2~7.4.
Step (3) inert gas is nitrogen, helium, any one in argon gas.
It anneals in step (3) be set forth in air atmosphere are as follows: in air atmosphere, slowly dropped with 2~3 DEG C/min rate
Temperature annealing, until being cooled to room temperature.
Step (3) is described to be to slowly warm up to 500 DEG C are as follows: after being warming up to 300 DEG C with 4~6 DEG C/min rate program, continue with
0.2~0.4 DEG C/min rate program is warming up to 500 DEG C.
The beneficial effects of the present invention are:
(1) technical solution of the present invention adjusts the hydrolysis of Triisopropoxyvanadium(V) oxide using the esterification between fatty acid and alcohols solvent
Condition makes the nucleation rate of particle be greater than growth rate, and reaction system is in hypersaturated state, makes the vanadium pentoxide generated
Grain partial size is maintained at Nano grade, and once has vanadium pentoxide Crystallization that can be oxidized graphene absorption and fix, effectively
The reunion for avoiding vanadium pentoxide crystal makes it keep good dispersion performance, and since vanadium pentoxide crystal is lamella
Structure, graphene oxide is by modified, in monolithic layer structure disperses in system, therefore can be common with vanadium pentoxide crystal
Lamellar structure is constituted, the reinforcement effect to vanadium pentoxide crystal structure is played, effectively improves in battery charging and discharging cyclic process
In structural stability can, avoid cycle-index increases the decline for causing reversible capacity；Furthermore the oxygen after modification
Graphite alkene, lamellar structure edge is mutually exclusive with more negative electrical charges of the same race, so that interlayer spacing is widened, is conducive to magnesium
The diffusive migration of ion improves the chemical property of product；
(2) technical solution of the present invention is by using modified single-layer oxidized graphite alkene to the vanadium pentoxide crystal of lamellar structure
Intercalation modifying is carried out, the chemical stability of vanadium pentoxide is effectively increased, can effectively avoid acid-base medium to five oxidations two
The erosion of alum, and due to having hydrophobic region and hydrophilic area in graphene oxide structure, there is good surface-active, favorably
In the infiltration of electrolyte, be conducive to the diffusive migration of magnesium ion, so that the chemical property of product is further promoted, furthermore, lead to
Introducing titanium dioxide and tin oxide are crossed, the structural stability of product can be effectively improved, is primarily due to the two in system in single
Scattered porosity state exists, and reduces grain-to-grain stress and is become with structural volume caused in battery charging and discharging cyclic process
Change, further enhances the cyclical stability of battery, extend battery effectively.
Specific embodiment
It is in mass ratio that 1:8~1:10 is mixed and poured into beaker, and beaker is moved to super by nano graphene oxide and water
In sound separating apparatus, it is 45~55 DEG C in temperature, under the conditions of supersonic frequency is 55~60kHz, keeps the temperature 45~60min of ultrasonic disperse,
To the end of ultrasonic disperse, beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, and graphene oxide quality is added into beaker
10~20% kayexalate is 65~70 DEG C in temperature, and under the conditions of revolving speed is 400~600r/min, heating stirring is anti-
After answering 1~2h, filtering obtains filter residue, and be washed with deionized filter residue 3~5 times, then the filter residue vacuum refrigeration after washing is done
It is dry, obtain pretreatment graphene oxide；Again by gained pre-process graphene oxide and toluene di-isocyanate(TDI) be in mass ratio 1:4~
1:6 mixing is poured into the three-necked flask with reflux condensing tube, and after being heated to reflux, 2~4h of reaction is successively passed through to the end of reacting
It is filtered, washed and dried, obtains modified graphene oxide；According to parts by weight, 30~50 parts of Triisopropoxyvanadium(V) oxides are successively taken, 3~5
Part titanate esters, 80~100 parts of alcohols solvents, 30~50 parts of fatty acid, 8~10 parts of modified graphene oxides first will be modified oxidized
Graphene and alcohol solution mixing are poured into three-necked flask, under the conditions of supersonic frequency is 55~60kHz, ultrasonic disperse 45~
After 50min, then fatty acid, titanate esters and Triisopropoxyvanadium(V) oxide are sequentially added into three-necked flask, then in temperature be 80~85
Under the conditions of DEG C, 4~6h of heating reflux reaction, discharging obtains mixed dispersion liquid；According to parts by weight, 80~100 parts of mixing are successively taken
Dispersion liquid, the tin chloride solution that 60~80 parts of mass fractions are 5~10%, is poured into reaction kettle, in supersonic frequency be 45~
Under the conditions of 50kHz, after 30~45min of ultrasonic disperse, reactor temperature is adjusted to 65~70 DEG C, speed of agitator to 600~
Under 800r/min, Yu Hengwen stirring, precipitating reagent is added dropwise, adjusts material in reactor pH to 7.2, continue to be stirred to react 2~
It after 4h, filters, obtains filter cake, and filter cake is washed with deionized until cleaning solution is in neutrality, then it is the filter cake vacuum after washing is cold
It is lyophilized dry, obtains dry cake；Gained dry cake is transferred in tube furnace, and is passed through with 200~300mL/min rate into furnace
Inert gas, under inert gas shielding state, after being warming up to 300 DEG C with 4~6 DEG C/min rate program, continue with 0.2~
0.4 DEG C/min rate program is warming up to 500 DEG C, after 2~4h of insulation reaction, with the progress of 2~3 DEG C/min rate in air atmosphere
Slow cooling annealing discharges until being cooled to room temperature to get Magnesium ion battery specific complex nanometer vanadium pentoxide.The titanium
Acid esters is Butyl Phthalate, tetraisopropyl titanate, any one in metatitanic acid n-propyl.The alcohols solvent is methanol, ethyl alcohol, just
Any one in propyl alcohol, isopropanol.The fatty acid is linoleic acid, linolenic acid, arachidonic acid, any in ricinoleic acid
It is a kind of.The precipitating reagent is the urea liquid that mass fraction is 8~10%, the ammonium hydroxide that mass fraction is 4~6%, mass-dispersion 4
~8% sodium carbonate liquor, the sodium bicarbonate solution that mass-dispersion is 5~10%, the hydrogen-oxygen Warner that mass-dispersion is 2~4% are molten
Liquid, mass-dispersion are any one in 3~5% potassium hydroxide solution.The inert gas is nitrogen, in helium, argon gas
Any one.
Example 1
It is in mass ratio that 1:10 mixing is poured into beaker, and beaker is moved to ultrasonic disperse instrument by nano graphene oxide and water
In, it is 55 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, ultrasonic disperse 60min is kept the temperature, to the end of ultrasonic disperse, by beaker
It moves to digital display to test the speed constant temperature blender with magnetic force, and the kayexalate of graphene oxide quality 20% is added into beaker, in
Temperature is 70 DEG C, and under the conditions of revolving speed is 600r/min, after heating stirring reacts 2h, filtering obtains filter residue, and be washed with deionized
Filter residue 5 times, then by the filter residue vacuum freeze drying after washing, obtain pretreatment graphene oxide；Gained is pre-processed into oxidation stone again
Black alkene and toluene di-isocyanate(TDI) are that 1:4 mixing is poured into the three-necked flask with reflux condensing tube in mass ratio, are heated to flowing back
Afterwards, reaction 2h is successively filtered, washed and dried drying, obtains modified graphene oxide to the end of reacting；According to parts by weight, successively
Take 50 parts of Triisopropoxyvanadium(V) oxides, 5 parts of titanate esters, 100 parts of alcohols solvents, 50 parts of fatty acid, 10 parts of modified graphene oxides first will
Modified graphene oxide and alcohol solution mixing are poured into three-necked flask, under the conditions of supersonic frequency is 60kHz, ultrasonic disperse
After 50min, then fatty acid, titanate esters and Triisopropoxyvanadium(V) oxide are sequentially added into three-necked flask, then in temperature be 85 DEG C of items
Under part, heating reflux reaction 6h, discharging obtains mixed dispersion liquid；According to parts by weight, 100 parts of mixed dispersion liquids are successively taken, 80 parts
The tin chloride solution that mass fraction is 10%, is poured into reaction kettle, under the conditions of supersonic frequency is 50kHz, ultrasonic disperse 45min
Afterwards, reactor temperature is adjusted to 70 DEG C, speed of agitator to 800r/min under Yu Hengwen stirring, is added dropwise precipitating reagent, adjusts
Material in reactor pH to 7.2 continues after being stirred to react 4h, filters, obtains filter cake, and filter cake is washed with deionized until washing
Liquid is in neutrality, then by the filter cake vacuum freeze drying after washing, obtains dry cake；Gained dry cake is transferred in tube furnace,
And inert gas is passed through into furnace with 300mL/min rate, under inert gas shielding state, with 6 DEG C/min rate program liter
Temperature is to after 300 DEG C, continuing to be warming up to 500 DEG C with 0.2 DEG C/min rate program, after insulation reaction 4h, with 3 in air atmosphere
DEG C/the progress slow cooling annealing of min rate, until being cooled to room temperature, discharging is to get five oxygen of Magnesium ion battery specific complex nanometer
Change two alum.The titanate esters are Butyl Phthalate.The alcohols solvent is methanol.The fatty acid is linoleic acid.The precipitating reagent
The urea liquid for being 10% for mass fraction.The inert gas is nitrogen.
Example 2
It is in mass ratio that 1:10 mixing is poured into beaker, and beaker is moved to ultrasonic disperse instrument by nano graphene oxide and water
In, it is 55 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, ultrasonic disperse 60min is kept the temperature, to the end of ultrasonic disperse, by beaker
It moves to digital display to test the speed constant temperature blender with magnetic force, and the kayexalate of graphene oxide quality 20% is added into beaker, in
Temperature is 70 DEG C, and under the conditions of revolving speed is 600r/min, after heating stirring reacts 2h, filtering obtains filter residue, and be washed with deionized
Filter residue 5 times, then by the filter residue vacuum freeze drying after washing, obtain modified graphene oxide；According to parts by weight, 50 parts are successively taken
Triisopropoxyvanadium(V) oxide, 100 parts of alcohols solvents, 50 parts of fatty acid, 10 parts of modified graphene oxides, first by modified graphene oxide and
Alcohol solution mixing pour into three-necked flask, in supersonic frequency be 60kHz under the conditions of, after ultrasonic disperse 50min, then to three mouthfuls burn
Fatty acid and Triisopropoxyvanadium(V) oxide are sequentially added in bottle, then under the conditions of temperature is 85 DEG C, heating reflux reaction 6h, discharging,
Obtain mixed dispersion liquid；According to parts by weight, 100 parts of mixed dispersion liquids are successively taken, the stannic chloride that 80 parts of mass fractions are 10% is molten
Liquid pours into reaction kettle, under the conditions of supersonic frequency is 50kHz, after ultrasonic disperse 45min, adjusts reactor temperature to 70
DEG C, speed of agitator to 800r/min under Yu Hengwen stirring, is added dropwise precipitating reagent, adjusts material in reactor pH to 7.2, after
It is continuous be stirred to react 4h after, filter, obtain filter cake, and filter cake is washed with deionized until cleaning solution is in neutrality, then will be after washing
Filter cake vacuum freeze drying, obtains dry cake；Gained dry cake is transferred in tube furnace, and with 300mL/min rate to furnace
It is inside passed through inert gas, under inert gas shielding state, after being warming up to 300 DEG C with 6 DEG C/min rate program, is continued with 0.2
DEG C/min rate program is warming up to 500 DEG C, after insulation reaction 4h, slow cooling is carried out with 3 DEG C/min rate in air atmosphere
Annealing discharges until being cooled to room temperature to get Magnesium ion battery specific complex nanometer vanadium pentoxide.The alcohols solvent is
Methanol.The fatty acid is linoleic acid.The precipitating reagent is the urea liquid that mass fraction is 10%.The inert gas is nitrogen
Gas.
Example 3
It is in mass ratio that 1:10 mixing is poured into beaker, and beaker is moved to ultrasonic disperse instrument by nano graphene oxide and water
In, it is 55 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, ultrasonic disperse 60min is kept the temperature, to the end of ultrasonic disperse, by beaker
It moves to digital display to test the speed constant temperature blender with magnetic force, and the kayexalate of graphene oxide quality 20% is added into beaker, in
Temperature is 70 DEG C, and under the conditions of revolving speed is 600r/min, after heating stirring reacts 2h, filtering obtains filter residue, and be washed with deionized
Filter residue 5 times, then by the filter residue vacuum freeze drying after washing, obtain pretreatment graphene oxide；Gained is pre-processed into oxidation stone again
Black alkene and toluene di-isocyanate(TDI) are that 1:4 mixing is poured into the three-necked flask with reflux condensing tube in mass ratio, are heated to flowing back
Afterwards, reaction 2h is successively filtered, washed and dried drying, obtains modified graphene oxide to the end of reacting；According to parts by weight, successively
Take 50 parts of Triisopropoxyvanadium(V) oxides, 5 parts of titanate esters, 100 parts of alcohols solvents, 50 parts of water, 10 parts of modified graphene oxides will first be modified
Graphene oxide and alcohol solution mixing are poured into three-necked flask, under the conditions of supersonic frequency is 60kHz, ultrasonic disperse 50min
Afterwards, then into three-necked flask water, titanate esters and Triisopropoxyvanadium(V) oxide are sequentially added, then under the conditions of temperature is 85 DEG C, heating
Back flow reaction 6h, discharging, obtains mixed dispersion liquid；According to parts by weight, 100 parts of mixed dispersion liquids, 80 parts of mass fractions are successively taken
It for 10% tin chloride solution, pours into reaction kettle, under the conditions of supersonic frequency is 50kHz, after ultrasonic disperse 45min, adjusts anti-
Answer temperature in the kettle to 70 DEG C, speed of agitator to 800r/min under Yu Hengwen stirring, is added dropwise precipitating reagent, adjusts in reaction kettle
Material pH to 7.2 continues after being stirred to react 4h, filters, obtains filter cake, and filter cake is washed with deionized until cleaning solution is in
Property, then by the filter cake vacuum freeze drying after washing, obtain dry cake；Gained dry cake is transferred in tube furnace, and with
300mL/min rate is passed through inert gas into furnace, under inert gas shielding state, is warming up to 6 DEG C/min rate program
500 DEG C, after insulation reaction 4h, slow cooling annealing is carried out with 3 DEG C/min rate in air atmosphere, until be cooled to room temperature,
Discharging is to get Magnesium ion battery specific complex nanometer vanadium pentoxide.The titanate esters are Butyl Phthalate.The alcohols solvent is
Methanol.The precipitating reagent is the urea liquid that mass fraction is 10%.The inert gas is nitrogen.
Example 4
According to parts by weight, 50 parts of Triisopropoxyvanadium(V) oxides are successively taken, 5 parts of titanate esters, 100 parts of alcohols solvents, 50 parts of fatty acid, 10
Graphene oxide and alcohol solution are first mixed and are poured into three-necked flask by part graphene oxide, in supersonic frequency be 60kHz condition
Under, after ultrasonic disperse 50min, then fatty acid, titanate esters and Triisopropoxyvanadium(V) oxide are sequentially added into three-necked flask, then in temperature
Under the conditions of degree is 85 DEG C, heating reflux reaction 6h, discharging obtains mixed dispersion liquid；According to parts by weight, 100 parts of mixing are successively taken
Dispersion liquid, the tin chloride solution that 80 parts of mass fractions are 10%, is poured into reaction kettle, under the conditions of supersonic frequency is 50kHz, is surpassed
After sound disperses 45min, reactor temperature is adjusted to 70 DEG C, speed of agitator to 800r/min under Yu Hengwen stirring, is added dropwise
Precipitating reagent adjusts material in reactor pH to 7.2, continues after being stirred to react 4h, filters, obtains filter cake, and be washed with deionized
Filter cake is until cleaning solution is in neutrality, then by the filter cake vacuum freeze drying after washing, obtains dry cake；Gained dry cake is turned
Enter in tube furnace, and inert gas is passed through into furnace with 300mL/min rate, under inert gas shielding state, with 6 DEG C/min
After rate program is warming up to 300 DEG C, continue to be warming up to 500 DEG C with 0.2 DEG C/min rate program, after insulation reaction 4h, in air
Slow cooling annealing is carried out with 3 DEG C/min rate in atmosphere, until being cooled to room temperature, is discharged dedicated multiple to get Magnesium ion battery
Close nanometer vanadium pentoxide.The titanate esters are Butyl Phthalate.The alcohols solvent is methanol.The fatty acid is linoleic acid.
The precipitating reagent is the urea liquid that mass fraction is 10%.The inert gas is nitrogen.
Example 5
It is in mass ratio that 1:10 mixing is poured into beaker, and beaker is moved to ultrasonic disperse instrument by nano graphene oxide and water
In, it is 55 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, ultrasonic disperse 60min is kept the temperature, to the end of ultrasonic disperse, by beaker
It moves to digital display to test the speed constant temperature blender with magnetic force, and the kayexalate of graphene oxide quality 20% is added into beaker, in
Temperature is 70 DEG C, and under the conditions of revolving speed is 600r/min, after heating stirring reacts 2h, filtering obtains filter residue, and be washed with deionized
Filter residue 5 times, then by the filter residue vacuum freeze drying after washing, obtain pretreatment graphene oxide；Gained is pre-processed into oxidation stone again
Black alkene and toluene di-isocyanate(TDI) are that 1:4 mixing is poured into the three-necked flask with reflux condensing tube in mass ratio, are heated to flowing back
Afterwards, reaction 2h is successively filtered, washed and dried drying, obtains modified graphene oxide to the end of reacting；According to parts by weight, successively
Take 50 parts of Triisopropoxyvanadium(V) oxides, 5 parts of titanate esters, 100 parts of alcohols solvents, 50 parts of fatty acid, 10 parts of modified graphene oxides first will
Modified graphene oxide and alcohol solution mixing are poured into three-necked flask, under the conditions of supersonic frequency is 60kHz, ultrasonic disperse
After 50min, then fatty acid, titanate esters and Triisopropoxyvanadium(V) oxide are sequentially added into three-necked flask, then in temperature be 85 DEG C of items
Under part, heating reflux reaction 6h, discharging obtains mixed dispersion liquid；According to parts by weight, 100 parts of mixed dispersion liquids are taken, reaction is poured into
In kettle, under the conditions of supersonic frequency is 50kHz, after ultrasonic disperse 45min, reactor temperature is adjusted to 70 DEG C, speed of agitator
To 800r/min, under Yu Hengwen stirring, precipitating reagent is added dropwise, adjusts material in reactor pH to 7.2, continues to be stirred to react 4h
Afterwards, it filters, obtains filter cake, and filter cake is washed with deionized until cleaning solution is in neutrality, then by the filter cake vacuum refrigeration after washing
It is dry, obtain dry cake；Gained dry cake is transferred in tube furnace, and indifferent gas is passed through into furnace with 300mL/min rate
Body after being warming up to 300 DEG C with 6 DEG C/min rate program, continues under inert gas shielding state with 0.2 DEG C/min rate journey
Sequence is warming up to 500 DEG C, after insulation reaction 4h, carries out slow cooling annealing in air atmosphere with 3 DEG C/min rate, until cooling
To room temperature, discharge to get Magnesium ion battery specific complex nanometer vanadium pentoxide.The titanate esters are Butyl Phthalate.The alcohol
Class solvent is methanol.The fatty acid is linoleic acid.The precipitating reagent is the urea liquid that mass fraction is 10%.The inertia
Gas is nitrogen.
1 to 5 gained Magnesium ion battery specific complex nanometer vanadium pentoxide of example is subjected to performance detection, specific detection side
Method is as follows:
Using above-mentioned compound vanadium pentoxide powder as anode, battery is made, detects the charge and discharge for the first time of above-mentioned Magnesium ion battery respectively
Piezoelectric voltage, specific testing result are as shown in table 1:
Table 1: performance detection table
Had when it is found that present invention gained Magnesium ion battery specific complex nanometer vanadium pentoxide is as anode by 1 testing result of table
There is excellent chemical property, battery has obtained effective extension.
Claims (10)
1. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide, it is characterised in that specific preparation step
Are as follows:
(1) according to parts by weight, 30~50 parts of Triisopropoxyvanadium(V) oxides are successively taken, 3~5 parts of titanate esters, 80~100 parts of alcohols are molten
Agent, 30~50 parts of fatty acid, 8~10 parts of modified graphene oxides first disperse modified graphene oxide in alcohols solvent, then
Fatty acid, titanate esters and Triisopropoxyvanadium(V) oxide, 4~6h of heating reflux reaction are sequentially added, discharging obtains mixed dispersion liquid；
(2) according to parts by weight, 80~100 parts of mixed dispersion liquids are successively taken, 60~80 parts of tin chloride solutions, ultrasonic disperse is uniform
Afterwards, under Yu Hengwen stirring, precipitating reagent is added dropwise and adjusts pH to alkalescent, continues after being stirred to react 2~4h, filters, wash, do
It is dry, obtain dry cake；
(3) by gained dry cake under inert gas shielding state, 500 DEG C, after pyroreaction are to slowly warm up to, in air gas
Annealing is in atmosphere to get Magnesium ion battery specific complex nanometer vanadium pentoxide.
2. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is step (1) titanate esters for any one in Butyl Phthalate, tetraisopropyl titanate, metatitanic acid n-propyl.
3. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is step (1) alcohols solvent for any one in methanol, ethyl alcohol, normal propyl alcohol, isopropanol.
4. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is step (1) fatty acid for any one in linoleic acid, linolenic acid, arachidonic acid, ricinoleic acid.
5. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is step (1) the modified graphene oxide modifying process are as follows: by graphene oxide and water is in mass ratio 1:8~1:10
After ultrasonic disperse, the kayexalate of graphene oxide quality 10~20% is added, after heating stirring reaction, filtering is washed
It washs, it is dry, pretreatment graphene oxide is obtained, then be in mass ratio by gained pretreatment graphene oxide and toluene di-isocyanate(TDI)
After 1:4~1:6 mixing, 2~4h of heating reflux reaction, using filter, washing and drying obtain modified graphene oxide.
6. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is that step (2) described precipitating reagent is the urea liquid that mass fraction is 8~10%, the ammonium hydroxide that mass fraction is 4~6%, matter
Amount is separated into 4~8% sodium carbonate liquor, the sodium bicarbonate solution that mass-dispersion is 5~10%, the hydrogen that mass-dispersion is 2~4%
Oxygen Warner solution, mass-dispersion are any one in 3~5% potassium hydroxide solution.
7. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is step (2) the adjusting pH to alkalescent are as follows: adjusts pH to 7.2~7.4.
8. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is step (3) inert gas for any one in nitrogen, helium, argon gas.
9. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is to anneal in step (3) be set forth in air atmosphere are as follows: in air atmosphere, carries out slow cooling with 2~3 DEG C/min rate
Annealing, until being cooled to room temperature.
10. a kind of preparation method of Magnesium ion battery specific complex nanometer vanadium pentoxide according to claim 1, special
Sign is that step (3) is described and is to slowly warm up to 500 DEG C are as follows: after being warming up to 300 DEG C with 4~6 DEG C/min rate program, continue with
0.2~0.4 DEG C/min rate program is warming up to 500 DEG C.
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| CN110817958A (en) * | 2019-10-11 | 2020-02-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Carbon-coated nano vanadium pentoxide lithium battery positive electrode material and liquid-phase in-situ preparation method thereof |
| CN112225244A (en) * | 2020-10-13 | 2021-01-15 | 江曙 | Preparation method of monodisperse nano copper-zinc-tin-sulfur for solar cell |
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| CN110817958B (en) * | 2019-10-11 | 2022-07-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Carbon-coated nano vanadium pentoxide lithium battery positive electrode material and liquid-phase in-situ preparation method thereof |
| CN112225244A (en) * | 2020-10-13 | 2021-01-15 | 江曙 | Preparation method of monodisperse nano copper-zinc-tin-sulfur for solar cell |
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