CN107039622A - A kind of preparation method of the sodium-ion battery based on graphite/Prussian blue positive electrode - Google Patents
A kind of preparation method of the sodium-ion battery based on graphite/Prussian blue positive electrode Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of the sodium-ion battery based on graphite/Prussian blue positive electrode, concretely comprises the following steps:Solution of ferrous chloride and sodium ferrocyanide solution are mixed, first temperature programming is to 70 90 DEG C, then program is cooled to room temperature, washs drying, obtains prussian blue nano ball;Then prussian blue nano ball is added into graphite oxide solution stirring mixing, separation cold quenching is freezed, obtains graphite oxide cladding prussian blue nano ball, then graphite/Prussian blue is obtained through being reduced in hydrazine hydrate;Finally by graphite/Prussian blue and conductive agent, isopropanol and segregation tetrafluoroethene, grinding vacuum drying tabletting is as positive pole, using metallic sodium piece as negative pole, with NaClO4For electrolyte, chitosan film is as barrier film, and assembling forms the sodium-ion battery based on graphite/Prussian blue under argon atmosphere.Sodium-ion battery stable circulation prepared by the present invention is good, and capacity sustainment rate is up to more than 90%.
Description
Technical field
The invention belongs to sodium-ion battery field of material technology, and in particular to one kind is based on graphite/Prussian blue positive pole material
The preparation method of the sodium-ion battery of material.
Background technology
With the gradually deficient and increasingly serious environmental problem of traditional fossil energy, Development of Novel regenerative resource into
For inexorable trend.The renewable sources of energy are also made that requirements at the higher level to the highest efficiency of energy storage technology.The energy-accumulating medium in energy storage technology
Energy density and power density in terms of performance it is particularly significant.Current lithium battery and sode cell development are more rapid.Metallic sodium
Same subject element with lithium, Na/Na+ electricity to standard electrode EMF -2.71V, with Li/Li+ electricity to standard electrode EMF -
3.04V is approached, sodium-ion battery also as the operation principle of lithium ion battery, but sodium ion have than lithium ion it is bigger
Ionic radius, it is therefore desirable to bigger ion channel, therefore the not necessarily suitable sodium ion storage of storage lithium electrode material.
Prussian blue is a kind of ancient blue dyes, and glazing is used to earliest and oil painting dyestuff is done, be used to urge afterwards
Change and battery aspect.Prussian blue and its derivative has special frame structure of opening, and intracell stress is small, Stability Analysis of Structures,
Its theoretical specific capacity is 62mAh/g, is adapted to the fast transferring of alkali metal ion, can significantly improve current density, and follow
Ring stability is good.Na-like ions cell positive material and preparation method thereof disclosed in Chinese patent CN 103208628B is with answering
With, by K2Cu (CN) 3 and KCl is soluble in water obtains settled solution, MnCl2 and nickel powder are slowly added dropwise at 60 DEG C, stirring is stood,
Separation is dried to obtain sodium-ion battery Prussian-blue/metal composite positive electrode.The reaction machine of the positive electrode
Manage and reacted for bielectron, therefore with higher capacity and adjustable voltage range.Disclosed in Chinese patent CN 103441241B
A kind of preparation method and application of prussian blue complex/carbon composite material, by Na4Fe (CN) 6:HCl:Ketjen black=1:
0.1:5 molar fraction weighs raw material, adds water as solvent, 60 DEG C of heating 16h separate drying, obtain prussian blue and match somebody with somebody
Prussian blue analogues growth course is slow in compound/carbon composite, the composite, and crystalline texture is more complete, makees
High circulation volume and excellent cyclical stability are shown during for sodium-ion battery positive material.Can by above-mentioned prior art
Know, Prussian blue and its derivant material is more in the application study of field of batteries, but based on Prussian blue electrode material
Expect still have much room for improvement in terms of the stability of capacity when in use.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of sodium-ion battery based on graphite/Prussian blue positive electrode
Preparation method, by graphite/Prussian blue and conductive agent, isopropanol and segregation tetrafluoroethene, grinding vacuum drying tabletting conduct
Positive pole, using metallic sodium piece as negative pole, with NaClO4For electrolyte, chitosan film assembles shape as barrier film under argon atmosphere
Into the sodium-ion battery based on graphite/Prussian blue.Sodium-ion battery stable circulation prepared by the present invention is good, capacity sustainment rate
Up to more than 90%.
In order to solve the above technical problems, the technical scheme is that:
A kind of preparation method of the sodium-ion battery based on graphite/Prussian blue positive electrode, comprises the following steps:
(1) frerrous chloride is dissolved in deionized water, adds surfactant F127, and ultrasonic agitation is to clear liquid, is designated as
Solution A, sodium ferrocyanide is dissolved in deionized water, and ultrasonic agitation is designated as solution B to clear liquid;
(2) solution B prepared by the solution A and step (1) prepared step (1) is transferred in reactor, tightens kettle cover simultaneously
It is transferred in baking oven, first temperature programming reacts 10-30h to 70-90 DEG C, then program is cooled to room temperature, washs, at 110-130 DEG C
Under be dried in vacuum overnight, obtain prussian blue nano ball;
(3) the prussian blue nano ball for preparing step (2), which is added under graphite oxide solution, normal temperature, stirs 4h, obtains oxygen
Graphite is combined Prussian blue, centrifugation, and liquid nitrogen cold quenching freezes 48-96h, obtains graphite oxide cladding prussian blue nano
Ball, is added in hydrazine hydrate, is reacted and is stayed overnight at 50-70 DEG C, obtains graphite/Prussian blue;
(4) add chitosan into 2% acetum, constant temperature is evenly stirred until dissolving, degassing solidification 4h film forming, by film
40-60min in the sodium hydroxide solution of immersion 2%, is taken out, and washing is dried, and obtains chitosan film;
(5) graphite/Prussian blue for preparing step (3) mix with conductive agent, grinds to form pasty state, be added dropwise isopropanol with it is inclined
Polytetrafluoroethylene (PTFE), continues to be ground to drying, forms black solid, black solid is ground into film-form, be dried in vacuo tabletting, as
Positive pole, using metallic sodium piece as negative pole, with NaClO4For electrolyte, chitosan film prepared by step (4) is as barrier film, in argon gas
Assembling forms the sodium-ion battery based on graphite/Prussian blue under atmosphere.
As the preferred of above-mentioned technical proposal, in the step (1), ferrocyanide in frerrous chloride and solution B in solution A
The mol ratio of sodium is 2:1.
As the preferred of above-mentioned technical proposal, in the step (2), the temperature of temperature programming is preferably 84-86 DEG C, heating
Speed is 1-3 DEG C/min, and the rate of temperature fall of program cooling is 0.1-1 DEG C/min.
As the preferred of above-mentioned technical proposal, in the step (2), the particle diameter of prussian blue nano ball is 100-400nm.
As the preferred of above-mentioned technical proposal, in the step (3), graphite oxide solution and the liquid of prussian blue nano ball
Material is than being 150ml:200mg, the concentration of graphene oxide is 10-50%.
As the preferred of above-mentioned technical proposal, in the step (3), graphite oxide cladding prussian blue nano ball and hydration
The liquid ratio of hydrazine is 100mg:20-25ml.
As the preferred of above-mentioned technical proposal, in the step (4), the liquid ratio of chitosan and acetum is 2g:
100-150ml。
As the preferred of above-mentioned technical proposal, in the step (5), conductive agent is conductive agent Super-P, graphite/Pu Lu
The blue liquid ratio with conductive agent, isopropanol and segregation tetrafluoroethene of scholar is 70-80mg:20mg:1-2ml:10-15mg.
As the preferred of above-mentioned technical proposal, in the step (5), vacuum drying temperature is 120-130 DEG C, and vacuum is done
The dry time is 12-16h, and the pressure of tabletting is 15-25MPa, and the time of tabletting is 30-60s.
As the preferred of above-mentioned technical proposal, in the step (5), NaClO in electrolyte4Concentration be 1-1.5mol/
It is 1 also to contain volume ratio in L, electrolyte:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate.
Compared with prior art, the invention has the advantages that:
(1) using graphite/Prussian blue as just in the sodium-ion battery based on graphite/Prussian blue prepared by the present invention
The main material of pole, wherein Prussian blue is nanosphere, the self assembly of nanosphere energy is reunited, and improves the chemical property of positive pole, together
When cladding prussian blue nano ball by graphite completely, further improve the electric conductivity of nanosphere, improve Prussian blue length
The cyclical stability of phase, using graphite/Prussian blue as after positive pole, sodium-ion battery positive electrode capacity is difficult decay, and multiplying power
Performance is good.
(2) in the sodium-ion battery based on graphite/Prussian blue prepared by the present invention using chitosan film as barrier film, shell
Glycan is product of the chitin through deacetylated processing, belongs to the natural homogeneous state straight-chain polysaccharide containing amino, is carried from natural products
Take, energy natural degradation, there are a lone pair electrons on amino in chitosan molecule structure, using the teaching of the invention it is possible to provide to the unoccupied orbital on Na+, make Na
+ easily intermembranous migration, reduces charging voltage, improves discharge voltage, advantageously reduces the loss of battery, improves battery
Cyclical stability.
(3) cost of material of the sodium-ion battery based on graphite/Prussian blue prepared by the present invention is low, wide material sources, system
Preparation Method is simple, tests favorable repeatability, and the sodium-ion battery good cycling stability of preparation, the capacity after circulating 500 times is maintained
Rate is up to more than 90%.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) 4mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 2mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid, note
For solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming to 70
DEG C, heating rate is 1 DEG C/min, reacts 10h, then is cooled to room temperature with 0.1 DEG C/min rate of temperature fall program, first uses deionization
Water is with 5000rpm speed centrifuge washing 2 times, and again with methanol is with 5000rpm speed centrifuge washing 1 time, the vacuum at 110 DEG C
5h is dried, the prussian blue nano ball that particle diameter is 400nm is obtained.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 10% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 48h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 20ml hydrazine hydrates, reacts and stays overnight at 50 DEG C, obtain
To graphite/Prussian blue.
(4) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving at 60 DEG C, taken off
Curing 4h film forming, film is immersed 40min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 70mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 1ml isopropyls are added dropwise
Alcohol and 10mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, at 120 DEG C
Lower vacuum drying 12h, the film for being 0.03mm in 15MPa tablettings 30s formation thickness, as positive pole, using metallic sodium piece as negative
Pole, using concentration as 1mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 ethyl carbon
Acid esters, divinyl carbonate and fluorinated ethylene carbonate, then using chitosan film as barrier film, assembling forms base under argon atmosphere
In the sodium-ion battery of graphite/Prussian blue.
Embodiment 2:
(1) 5mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 2.5mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid,
It is designated as solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming to 84
DEG C, heating rate is 1.3 DEG C/min, reacts 12.6h, then is cooled to room temperature with 0.4 DEG C/min rate of temperature fall program, is first spent
Ionized water is with 5000rpm speed centrifuge washing 3 times, and again with methanol is with 5000rpm speed centrifuge washing 1 time, at 113.4 DEG C
Lower vacuum drying 12h, obtains the prussian blue nano ball that particle diameter is 320nm.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 40% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 54h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 25ml hydrazine hydrates, reacts and stays overnight at 52.6 DEG C,
Obtain graphite/Prussian blue.
(4) 2g chitosans are added to 150ml 2% acetum, constant temperature is evenly stirred until dissolving at 70 DEG C, taken off
Curing 4h film forming, film is immersed 60min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 80mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 2ml isopropyls are added dropwise
Alcohol and 15mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, at 130 DEG C
Lower vacuum drying 16h, the film for being 0.025mm in 25MPa tablettings 60s formation thickness, as positive pole, using metallic sodium piece as negative
Pole, using concentration as 1.5mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 ethyl
Carbonic ester, divinyl carbonate and fluorinated ethylene carbonate, then using chitosan film as barrier film, assemble and formed under argon atmosphere
Sodium-ion battery based on graphite/Prussian blue.
Embodiment 3:
(1) 6mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 3mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid, note
For solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming is extremely
84.6 DEG C, heating rate is 1.6 DEG C/min, reacts 15.1h, then is cooled to room temperature with 0.7 DEG C/min rate of temperature fall program, first
With deionized water with 5000rpm speed centrifuge washing 2 times, again with methanol with 5000rpm speed centrifuge washing 1 time,
10h is dried in vacuo at 115.7 DEG C, the prussian blue nano ball that particle diameter is 200nm is obtained.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 20% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 60h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 22ml hydrazine hydrates, reacts and stays overnight at 54.7 DEG C,
Obtain graphite/Prussian blue.
(4) 2g chitosans are added to 120ml 2% acetum, constant temperature is evenly stirred until dissolving at 65 DEG C, taken off
Curing 4h film forming, film is immersed 55min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 75mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 1.6ml is added dropwise different
Propyl alcohol and 12mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, 124
13h is dried in vacuo at DEG C, the film for being 0.03mm in 19MPa tablettings 45s formation thickness, as positive pole, using metallic sodium piece as
Negative pole, using concentration as 1.3mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 second
Base carbonic ester, divinyl carbonate and fluorinated ethylene carbonate, then chitosan film is assembled into shape as barrier film under argon atmosphere
Into the sodium-ion battery based on graphite/Prussian blue.
Embodiment 4:
(1) 4mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 2mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid, note
For solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming is extremely
85.2 DEG C, heating rate is 2.1 DEG C/min, reacts 17.7h, then is cooled to room temperature with 0.9 DEG C/min rate of temperature fall program, first
With deionized water with 5000rpm speed centrifuge washing 3 times, again with methanol with 5000rpm speed centrifuge washing 1 time,
9h is dried in vacuo at 118.2 DEG C, the prussian blue nano ball that particle diameter is 150nm is obtained.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 35% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 66h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 20-25ml hydrazine hydrates, were reacted at 57.1 DEG C
At night, obtain graphite/Prussian blue.
(4) 2g chitosans are added to 130ml 2% acetum, constant temperature is evenly stirred until dissolving at 70 DEG C, taken off
Curing 4h film forming, film is immersed 60min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 75mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 1.5ml is added dropwise different
Propyl alcohol and 15mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, 130
12h is dried in vacuo at DEG C, the film for being 0.03mm in 25MPa tablettings 30s formation thickness, as positive pole, using metallic sodium piece as
Negative pole, using concentration as 1.5mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 second
Base carbonic ester, divinyl carbonate and fluorinated ethylene carbonate, then chitosan film is assembled into shape as barrier film under argon atmosphere
Into the sodium-ion battery based on graphite/Prussian blue.
Embodiment 5:
(1) 6mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 3mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid, note
For solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming is extremely
70th, 84,84.6,85.2,85.7,86,90 DEG C, heating rate is 2.8 DEG C/min, reacts 20.1h, then with 1 DEG C/min cooling
Rate program is cooled to room temperature, and first with deionized water with 5000rpm speed centrifuge washing 3 times, again with methanol is with 5000rpm's
Speed centrifuge washing 1 time, 10h is dried in vacuo at 120.4 DEG C, obtains the prussian blue nano ball that particle diameter is 250nm.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 30% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 72h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 21ml hydrazine hydrates, reacts and stays overnight at 60.7 DEG C,
Obtain graphite/Prussian blue.
(4) 2g chitosans are added to 120ml 2% acetum, constant temperature is evenly stirred until dissolving at 62 DEG C, taken off
Curing 4h film forming, film is immersed 50min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 80mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 2ml isopropyls are added dropwise
Alcohol and 10mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, at 130 DEG C
Lower vacuum drying 12h, the film for being 0.03mm in 25MPa tablettings 30s formation thickness, as positive pole, using metallic sodium piece as negative
Pole, using concentration as 1mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 ethyl carbon
Acid esters, divinyl carbonate and fluorinated ethylene carbonate, then using chitosan film as barrier film, assembling forms base under argon atmosphere
In the sodium-ion battery of graphite/Prussian blue.
Embodiment 6:
(1) 4mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 2mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid, note
For solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming to 86
DEG C, heating rate is 3 DEG C/min, reacts 20.1h, then is cooled to room temperature with 0.7 DEG C/min rate of temperature fall program, first spend from
Sub- water is with 5000rpm speed centrifuge washing 3 times, and again with methanol is with 5000rpm speed centrifuge washing 1 time, at 124.5 DEG C
8h is dried in vacuo, the prussian blue nano ball that particle diameter is 320nm is obtained.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 25% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 81h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 22ml hydrazine hydrates, reacts and stays overnight at 64.3 DEG C,
Obtain graphite/Prussian blue.
(4) 2g chitosans are added to 150ml 2% acetum, constant temperature is evenly stirred until dissolving at 70 DEG C, taken off
Curing 4h film forming, film is immersed 50min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 80mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 2ml isopropyls are added dropwise
Alcohol and 10mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, at 130 DEG C
Lower vacuum drying 12h, the film for being 0.03mm in 20MPa tablettings 40s formation thickness, as positive pole, using metallic sodium piece as negative
Pole, using concentration as 1.3mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 ethyl
Carbonic ester, divinyl carbonate and fluorinated ethylene carbonate, then using chitosan film as barrier film, assemble and formed under argon atmosphere
Sodium-ion battery based on graphite/Prussian blue.
Embodiment 7:
(1) 4mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 2mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid, note
For solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming to 90
DEG C, heating rate is 2.1 DEG C/min, reacts 24.5h, then is cooled to room temperature with 0.7 DEG C/min rate of temperature fall program, is first spent
Ionized water is with 5000rpm speed centrifuge washing 3 times, and again with methanol is with 5000rpm speed centrifuge washing 1 time, at 126.3 DEG C
Lower vacuum drying 12h, obtains the prussian blue nano ball that particle diameter is 170nm.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 10-50% graphite oxide solutions, stirred under normal temperature
4h, obtains graphite oxide and is combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 90h, obtain graphite oxide cladding Prussia
Blue nanosphere, 100mg graphite oxides are coated in prussian blue nano ball and added in 25ml hydrazine hydrates, were reacted at 66.8 DEG C
At night, obtain graphite/Prussian blue.
(4) 2g chitosans are added to 135ml 2% acetum, constant temperature is evenly stirred until dissolving at 60 DEG C, taken off
Curing 4h film forming, film is immersed 55min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 74mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 1.3ml is added dropwise different
Propyl alcohol and 14mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, 125
15h is dried in vacuo at DEG C, the film for being 0.03mm in 20MPa tablettings 50s formation thickness, as positive pole, using metallic sodium piece as
Negative pole, using concentration as 1.1mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 second
Base carbonic ester, divinyl carbonate and fluorinated ethylene carbonate, then chitosan film is assembled into shape as barrier film under argon atmosphere
Into the sodium-ion battery based on graphite/Prussian blue.
Embodiment 8:
(1) 5mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 2.5mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid,
It is designated as solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming to 90
DEG C, heating rate is 1.6 DEG C/min, reacts 30h, then is cooled to room temperature with 0.1 DEG C/min rate of temperature fall program, first spend from
Sub- water is with 5000rpm speed centrifuge washing 3 times, and again with methanol is true at 130 DEG C with 5000rpm speed centrifuge washing 1 time
Sky dries 5h, obtains the prussian blue nano ball that particle diameter is 100nm.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 45% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 96h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 25ml hydrazine hydrates, reacts and stays overnight at 70 DEG C, obtain
To graphite/Prussian blue.
(4) 2g chitosans are added to 150ml 2% acetum, constant temperature is evenly stirred until dissolving at 60 DEG C, taken off
Curing 4h film forming, film is immersed 60min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 80mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 1ml isopropyls are added dropwise
Alcohol and 10mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, at 130 DEG C
Lower vacuum drying 16h, the film for being 0.03mm in 25MPa tablettings 30s formation thickness, as positive pole, using metallic sodium piece as negative
Pole, using concentration as 1.5mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 ethyl
Carbonic ester, divinyl carbonate and fluorinated ethylene carbonate, then using chitosan film as barrier film, assemble and formed under argon atmosphere
Sodium-ion battery based on graphite/Prussian blue.
Comparative example:
(1) 4mmol frerrous chloride is dissolved in 100ml deionized waters, adds 50mg surfactant F127, and surpassed
Sound is stirred to clear liquid, is designated as solution A, and 2mmol sodium ferrocyanides are dissolved in 100ml deionized waters, ultrasonic agitation to clear liquid, note
For solution B.
(2) solution A and solution B are transferred in reactor, tighten kettle cover and be transferred in baking oven, first temperature programming to 70
DEG C, heating rate is 1 DEG C/min, reacts 10h, then is cooled to room temperature with 0.1 DEG C/min rate of temperature fall program, first uses deionization
Water is with 5000rpm speed centrifuge washing 2 times, and again with methanol is with 5000rpm speed centrifuge washing 1 time, the vacuum at 110 DEG C
5h is dried, the prussian blue nano ball that particle diameter is 400nm is obtained.
(3) 200mg prussian blue nano balls are added into 150ml concentration for 10% graphite oxide solution, 4h are stirred under normal temperature,
Obtain graphite oxide and be combined Prussian blue, centrifugation, liquid nitrogen cold quenching freezes 48h, obtains graphite oxide and coats Prussian blue receive
Rice ball, 100mg graphite oxides are coated in prussian blue nano ball and added in 20ml hydrazine hydrates, reacts and stays overnight at 50 DEG C, obtain
To graphite/Prussian blue.
(4) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving at 60 DEG C, taken off
Curing 4h film forming, film is immersed 40min in 2% sodium hydroxide solution, taken out, washing is dried, and obtains thickness for 0.05mm
Chitosan film.
(5) 70mg graphite/Prussian blue is mixed with 20mg conductive agents Super-P, grinds to form pasty state, 1ml isopropyls are added dropwise
Alcohol and 10mg segregation tetrafluoroethene, continue to be ground to drying, form black solid, black solid is ground into film-form, at 120 DEG C
Lower vacuum drying 12h, the film for being 0.03mm in 15MPa tablettings 30s formation thickness, as positive pole, using metallic sodium piece as negative
Pole, using concentration as 1mol/L NaClO4For electrolyte, it is 1 that volume ratio is also contained wherein in electrolyte:1:0.05 ethyl carbon
Acid esters, divinyl carbonate and fluorinated ethylene carbonate, then using polypropylene screen as barrier film, assembling forms base under argon atmosphere
In the sodium-ion battery of graphite/Prussian blue.
Surveyed prepared by embodiment 1-8 and comparative example 1 based on graphite/Prussian blue sodium-ion battery by electrochemistry
Examination, the result of capacity and capacity sustainment rate after 150mAhg-1 current densities are circulated 500 times is as follows:
As seen from the above table, what prepared by the present invention tests favorable repeatability, system based on graphite/Prussian blue sodium-ion battery
Standby sodium-ion battery good cycling stability, the capacity sustainment rate after circulating 500 times is up to more than 90%.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of preparation method of the sodium-ion battery based on graphite/Prussian blue positive electrode, it is characterised in that including following
Step:
(1) frerrous chloride is dissolved in deionized water, adds surfactant F127, and ultrasonic agitation is to clear liquid, is designated as solution
A, sodium ferrocyanide is dissolved in deionized water, and ultrasonic agitation is designated as solution B to clear liquid;
(2) solution B prepared by the solution A and step (1) prepared step (1) is transferred in reactor, is tightened kettle cover and is shifted
Into baking oven, first temperature programming reacts 10-30h to 70-90 DEG C, then program is cooled to room temperature, washs, true at 110-130 DEG C
Sky is dried overnight, and obtains prussian blue nano ball;
(3) the prussian blue nano ball for preparing step (2), which is added under graphite oxide solution, normal temperature, stirs 4h, obtains aoxidizing stone
Ink is compound Prussian blue, centrifuges, liquid nitrogen cold quenching, freezes 48-96h, obtains graphite oxide cladding prussian blue nano ball, then
Add in hydrazine hydrate, react and stay overnight at 50-70 DEG C, obtain graphite/Prussian blue;
(4) add chitosan into 2% acetum, constant temperature is evenly stirred until dissolving, and degassing solidification 4h film forming immerses film
40-60min in 2% sodium hydroxide solution, is taken out, and washing is dried, and obtains chitosan film;
(5) graphite/Prussian blue for preparing step (3) is mixed with conductive agent, grinds to form pasty state, dropwise addition isopropanol and segregation four
PVF, continues to be ground to drying, forms black solid, black solid is ground into film-form, tabletting is dried in vacuo, as just
Pole, using metallic sodium piece as negative pole, with NaClO4For electrolyte, chitosan film prepared by step (4) is as barrier film, in argon atmospher
Enclose lower assembling and form the sodium-ion battery based on graphite/Prussian blue.
2. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (1), the mol ratio of sodium ferrocyanide is 2 in frerrous chloride and solution B in solution A:1.
3. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (2), the temperature of temperature programming is preferably 84-86 DEG C, and heating rate is 1-3 DEG C/min, program
The rate of temperature fall of cooling is 0.1-1 DEG C/min.
4. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (2), the particle diameter of prussian blue nano ball is 100-400nm.
5. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (3), the liquid ratio of graphite oxide solution and prussian blue nano ball is 150ml:200mg, oxygen
The concentration of graphite alkene is 10-50%.
6. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (3), the liquid ratio of graphite oxide cladding prussian blue nano ball and hydrazine hydrate is 100mg:
20-25ml。
7. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (4), the liquid ratio of chitosan and acetum is 2g:100-150ml.
8. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (5), conductive agent is conductive agent Super-P, graphite/Prussian blue and conductive agent, isopropanol and
The liquid ratio of segregation tetrafluoroethene is 70-80mg:20mg:1-2ml:10-15mg.
9. a kind of preparation method of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1,
It is characterized in that:In the step (5), vacuum drying temperature is 120-130 DEG C, and the vacuum drying time is 12-16h, pressure
The pressure of piece is 15-25MPa, and the time of tabletting is 30-60s.
10. a kind of preparation side of sodium-ion battery based on graphite/Prussian blue positive electrode according to claim 1
Method, it is characterised in that:In the step (5), NaClO in electrolyte4Concentration be 1-1.5mol/L, also contain body in electrolyte
Product is than being 1:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate.
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