CN107026283A - A kind of preparation method of nanometer Prussian Blue/chitosan complex film of low defect and its application in sodium-ion battery - Google Patents
A kind of preparation method of nanometer Prussian Blue/chitosan complex film of low defect and its application in sodium-ion battery Download PDFInfo
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- CN107026283A CN107026283A CN201710111987.8A CN201710111987A CN107026283A CN 107026283 A CN107026283 A CN 107026283A CN 201710111987 A CN201710111987 A CN 201710111987A CN 107026283 A CN107026283 A CN 107026283A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention provides a kind of preparation method of nanometer Prussian Blue/chitosan complex film of low defect and its application in sodium-ion battery, the nanometer Prussian Blue material of low defect is prepared as raw material using ferrous oxalate, sodium oxalate and sodium ferrocyanide, nanometer Prussian Blue material and chitosan and conductive agent are mixed with and obtain composite membrane again, then 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.The defect of nanometer Prussian Blue material prepared by the present invention is small, good cycling stability, dimensional controllability is good, nanometer Prussian Blue/chitosan complex film low defect, more flexible, the cost of material of the sodium-ion battery to be prepared on the basis of this is low, wide material sources, preparation method is simple, controllability is good, the sodium-ion battery good cycling stability of preparation, and the capacity sustainment rate after circulating 500 times is up to more than 90%.
Description
Technical field
The invention belongs to Prussian blue field of material technology, and in particular to a kind of nanometer Prussian Blue/shell of low defect gathers
The preparation method of sugared composite membrane and its application in sodium-ion battery.
Background technology
Chemically modified electrode is one of Disciplinary Frontiers of current most active electrochemistry and Electroanalytical Chemistry, and it is in electrode
Surface carries out MOLECULE DESIGN, and the molecule with good chemical, ion, polymer design are fixed on into electrode surface, are allowed to
With specific chemistry and electrochemical properties, the electrode material of electrochemistry is enriched, the research field of electrochemistry is extended.
Prussian blue is a kind of ancient blue dyes, is the first artificial synthesized polymer, glazing is used to earliest
With do oil painting dyestuff, its research field constantly expands afterwards, to nuclear power station Absorbent, the electrode modified material of electrochemistry,
Related in terms of electric developer and battery material.Prussian blue itself and its derivative have it is special open frame structure,
Intracell stress is small, Stability Analysis of Structures, and its theoretical specific capacity is 62mAh/g, with excellent electrochemical reversibility, is adapted to alkali
The fast transferring of metal ion, can significantly improve current density, good cycling stability, and preparation method is simple.It is Prussian blue
And its derivative has tridimensional network, with zeolite characteristic, can soon occur in hydrous solvent with alkali metal ion
Exchange, with unique stability, electric colour developing effect and electrocatalysis.
A kind of preparation method of prussian blue complex/carbon composite material disclosed in Chinese patent CN 103441241B
And application, by Na4Fe (CN) 6:HCl：Ketjen black=1:0.1:5 molar fraction weighs raw material, adds water and is used as solvent, 60 DEG C
16h is heated, drying is separated, obtains prussian blue complex/carbon composite material, Prussian blue analogues in the composite
Growth course is slow, and crystalline texture is more complete, high circulation volume is shown during as sodium-ion battery positive material and excellent
Different cyclical stability.Chinese document (" preparation of Prussian blue/chitosan/Multiwalled Carbon Nanotubes Modified Electrode and its electrochemistry
Property ", spectrographic laboratory, the 2nd phase of volume 30, in March, 2013) multi-walled carbon nanotube formation black will be added in chitosan solution
Suspension, is spun on ripple carbon electrode surface, dries naturally, is subsequently placed in Prussian blue solution and elutes, dries naturally and obtain general
Shandong scholar indigo plant/chitosan/Multiwalled Carbon Nanotubes Modified Electrode, the electrode has preferable electrochemical properties, overcomes the pure general Shandong of tradition
The deficiency of scholar's indigo plant film.From above-mentioned prior art, Prussian blue and its derivant material field of batteries application study
Through more, but based on Prussian blue the electrode material when in use stability of capacity in terms of and mechanical properties still need to be carried
It is high.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of system of nanometer Prussian Blue/chitosan complex film of low defect
Preparation Method and its application in sodium-ion battery, are prepared as raw material using ferrous oxalate, sodium oxalate and sodium ferrocyanide and received
The Prussian blue material of rice, the defect of the Prussian blue material of preparation is small, and good cycling stability, dimensional controllability is good, then will receive
The Prussian blue material of rice prepares the flexible electrode to form low defect with chitosan composite membrane-forming, the sodium ion electrode material of preparation
Good cycling stability, capacity sustainment rate is high.
In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect, including following step
Suddenly：
(1) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 0.5-1：0-1:1-2 amount, to
Ferrous oxalate and sodium oxalate are added in 0.100ml deionized water, is well mixed, ultrasonic agitation to clear liquid, solution A is formed, to
Sodium ferrocyanide is added in 0.100ml deionized water, is well mixed, surfactant is added, ultrasonic agitation to clear liquid is formed
B solution；
(2) B solution for preparing step (1) is added in the solution A of step (1) preparation, and 24- is stirred in 20-30 DEG C
96h, obtains blue precipitate, and blue precipitate is first washed through deionized water, then is washed through methanol, true at 100-130 DEG C
Sky is dried overnight, and obtains the nanometer Prussian Blue material of low defect；
(3) add chitosan into 2% acetum, constant temperature is evenly stirred until dissolving, chitosan solution formed, by shell
The nanometer Prussian Blue material and conductive agent Super-P of low defect prepared by step (2) are added in glycan solution, is well mixed,
Ultrasonic wave is deaerated, degassing solidification 4h film forming, and film is immersed to 40-60min in 2% sodium hydroxide solution, taken out, washing is dried,
Obtain nanometer Prussian Blue/chitosan complex film of low defect.
As the preferred of above-mentioned technical proposal, in the step (1), ferrous oxalate：Sodium oxalate：Mole of sodium ferrocyanide
Than for 1：0-1：2.
As the preferred of above-mentioned technical proposal, in the step (1), surfactant is surfactant F127, surface
The mass ratio of activating agent and sodium ferrocyanide is 0.001-0.01:1.
As the preferred of above-mentioned technical proposal, in the step (2), deionized water washing times are 3 times, methanol washing
Number of times is 1 time, is washed as with 5000rpm speed centrifuge washing.
As the preferred of above-mentioned technical proposal, in the step (2), vacuum drying temperature is 100-125 DEG C.
As the preferred of above-mentioned technical proposal, in the step (2), the particle diameter of the nanometer Prussian Blue material of low defect is
200-500nm。
As the preferred of above-mentioned technical proposal, in the step (3), received in nanometer Prussian Blue/chitosan complex film
The mass ratio of the Prussian blue, chitosan of rice and conductive agent is 7-10:5-8:2-3.
As the preferred of above-mentioned technical proposal, in the step (3), the thickness of nanometer Prussian Blue/chitosan complex film
For 0.03-0.05mm.
The present invention also provides a kind of nanometer Prussian Blue/chitosan complex film of low defect answering in sodium-ion battery
With comprising the following steps：
Isopropanol is added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, vacuum is done at 120-130 DEG C
Dry 12-16h, in 15MPa lower sheeting 5-15s, as positive pole, using metallic sodium piece as negative pole, with 1-1.5mol/L NaClO4
For electrolyte, using chitosan film as barrier film, assembling forms sodium-ion battery under argon atmosphere.
As the preferred of above-mentioned technical proposal, the NaClO4Containing volume ratio to be 1 in electrolyte:1:0.05 ethyl
Carbonic ester, divinyl carbonate and fluorinated ethylene carbonate.
Compared with prior art, the invention has the advantages that：
(1) nanometer Prussian Blue material prepared by the present invention is to use ferrous oxalate, sodium oxalate and sodium ferrocyanide conduct
Prepared by raw material, its oxalate and ferrous ion with what bit constant was less than ferrous cyanogen root and ferrous ion match somebody with somebody bit constant, and grass
Iron atom slowly discharges in sour ferrous iron, and ferrous cyanogen root coordination, reduces the speed of growth of Prussian blue monocrystalline, reaches the general Shandong of reduction
The purpose of scholar's indigo plant defect, and the size of Prussian blue monocrystalline can be made controllable, improve the controllability of material.
(2) nanometer Prussian Blue material prepared by the present invention is compounded to form thin-film material with chitosan material and conductive agent,
Chitosan material and conductive agent can be attached to the surface of nanometer Prussian Blue, not influence the same of nanometer Prussian Blue electric conductivity
When, the cyclical stability of positive pole is improved, chitosan is product of the chitin through deacetylated processing, belong to natural containing the equal of amino
State straight-chain polysaccharide, is extracted from natural products, energy natural degradation, has a lone pair electrons, energy on amino in chitosan molecule structure
The unoccupied orbital on Na+ is enough supplied to, makes Na+ easily intermembranous migrations, reduces charging voltage, improve discharge voltage, have
Beneficial to the loss of reduction battery, the cyclical stability of battery is improved.
(3) cost of material of sodium-ion battery prepared by the present invention is low, wide material sources, and preparation method is simple, controllability
Good, experiment repeatability is high, and Prussian blue defect is low in nanometer Prussian Blue/chitosan complex film of preparation, composite membrane
Flexible, mechanical performance is improved, and the sodium-ion battery good cycling stability prepared, and the capacity sustainment rate after circulating 500 times is high
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) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 0.75：0:1 amount, to 100ml go from
In sub- water add 1.25mmol ferrous oxalate, be well mixed, ultrasonic agitation to clear liquid, formed solution A, to 100ml go from
2mmol sodium ferrocyanides are added in sub- water, are well mixed, surfactant F127, surfactant F127 and ferrous cyanogen is added
The mass ratio for changing sodium is 0.001:1, ultrasonic agitation to clear liquid forms B solution.
(2) B solution is added in solution A, stirs 72.1h in 24.8 DEG C, blue precipitate is obtained, by blue precipitate
First with 5000rpm speed deionized water centrifuge washing 3 times, then with 5000rpm rate Methanol centrifuge washing 1 time, 120.4
12h is dried in vacuum overnight at DEG C, the nanometer Prussian Blue material Fe-HCF-NC of low defect is obtained.
(3) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving, shape at 60 DEG C
It is 70mg according to the mass ratio of nanometer Prussian Blue, chitosan and conductive agent into chitosan solution:50mg:20mg, by chitosan
The nanometer Prussian Blue material and conductive agent Super-P of low defect are added in solution, is well mixed, ultrasonic wave degassing, degassing is solid
Change 4h film forming, film is immersed to 40min in 2% sodium hydroxide solution, taken out, washing is dried, obtain thickness receiving for 0.03mm
Prussian blue/the chitosan complex film of rice.
1ml isopropanols are added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, vacuum is done at 120 DEG C
Dry 12h, in 15MPa lower sheetings 5, as positive pole, using metallic sodium piece as negative pole, with 1mol/L NaClO4For electrolyte, body
Product is than being 1:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate, using chitosan film as barrier film,
Assembling forms sodium-ion battery under argon atmosphere.
Embodiment 2：
(1) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 0.75：0.5:0:1 amount, to 100ml's
1.25mmol ferrous oxalate and 1mmol sodium oxalates is added in deionized water, is well mixed, ultrasonic agitation to clear liquid, A is formed molten
Liquid, 2mmol sodium ferrocyanides are added into 100ml deionized water, are well mixed, and add surfactant F127, and surface is lived
Property agent F127 and sodium ferrocyanide mass ratio be 0.001:1, ultrasonic agitation to clear liquid forms B solution.
(2) B solution is added in solution A, stirs 70.7h in 24.8 DEG C, blue precipitate is obtained, by blue precipitate
First with 5000rpm speed deionized water centrifuge washing 3 times, then with 5000rpm rate Methanol centrifuge washing 1 time, 120.4
5h is dried in vacuum overnight at DEG C, the nanometer Prussian Blue material Fe-HCF-NC of low defect is obtained2。
(3) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving, shape at 60 DEG C
It is 70mg according to the mass ratio of nanometer Prussian Blue, chitosan and conductive agent into chitosan solution:50mg:20mg, by chitosan
The nanometer Prussian Blue material and conductive agent Super-P of low defect are added in solution, is well mixed, ultrasonic wave degassing, degassing is solid
Change 4h film forming, film is immersed to 40min in 2% sodium hydroxide solution, taken out, washing is dried, obtain thickness receiving for 0.03mm
Prussian blue/the chitosan complex film of rice.
1ml isopropanols are added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, vacuum is done at 130 DEG C
Dry 12h, in 15MPa lower sheeting 15s, as positive pole, using metallic sodium piece as negative pole, with 1.5mol/L NaClO4For electrolysis
Liquid, volume ratio is 1:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate, using chitosan film as every
Film, assembling forms sodium-ion battery under argon atmosphere.
Embodiment 3：
(1) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 1：1:2 amount, to 0.100ml go from
2mmol ferrous oxalate and 2mmol sodium oxalates is added in sub- water, is well mixed, ultrasonic agitation to clear liquid, solution A is formed, to
4mmol sodium ferrocyanides are added in 0.100ml deionized water, are well mixed, surfactant F127, surfactant is added
The mass ratio of F127 and sodium ferrocyanide is 0.01:1, ultrasonic agitation to clear liquid forms B solution.
(2) B solution is added in solution A, in 20 DEG C stir 96h, obtain blue precipitate, by blue precipitate first with
5000rpm speed deionized water centrifuge washing 3 times, then with 5000rpm rate Methanol centrifuge washing 1 time, it is true at 100 DEG C
Sky is dried overnight 8h, obtains the nanometer Prussian Blue material Fe-HCF-NC of low defect2。
(3) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving, shape at 60 DEG C
It is 80mg according to the mass ratio of nanometer Prussian Blue, chitosan and conductive agent into chitosan solution:60mg:25mg, by chitosan
The nanometer Prussian Blue material and conductive agent Super-P of low defect are added in solution, is well mixed, ultrasonic wave degassing, degassing is solid
Change 4h film forming, film is immersed to 50min in 2% sodium hydroxide solution, taken out, washing is dried, obtain thickness receiving for 0.04mm
Prussian blue/the chitosan complex film of rice.
1ml isopropanols are added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, vacuum is done at 125 DEG C
Dry 15h, in 15MPa lower sheeting 10s, as positive pole, using metallic sodium piece as negative pole, with 1.2mol/L NaClO4For electrolysis
Liquid, volume ratio is 1:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate, using chitosan film as every
Film, assembling forms sodium-ion battery under argon atmosphere.
Embodiment 4：
(1) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 0.7：0.3:1.5 amount, to 100ml's
0.7mmol ferrous oxalate and 0.3mmol sodium oxalates is added in deionized water, is well mixed, ultrasonic agitation to clear liquid, A is formed
Solution, 1.5mmol sodium ferrocyanides are added into 0.100ml deionized water, are well mixed, and add surfactant F127,
The mass ratio of surfactant F127 and sodium ferrocyanide is 0.005:1, ultrasonic agitation to clear liquid forms B solution.
(2) B solution is added in solution A, stirs 60.7h in 28 DEG C, obtain blue precipitate, blue precipitate is first
With 5000rpm speed deionized water centrifuge washing 3 times, then with 5000rpm rate Methanol centrifuge washing 1 time, at 125 DEG C
10h is dried in vacuum overnight, the nanometer Prussian Blue material Fe-HCF-NC of low defect is obtained2。
(3) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving, shape at 60 DEG C
It is 90mg according to the mass ratio of nanometer Prussian Blue, chitosan and conductive agent into chitosan solution:60mg:30mg, by chitosan
The nanometer Prussian Blue material and conductive agent Super-P of low defect are added in solution, is well mixed, ultrasonic wave degassing, degassing is solid
Change 4h film forming, film is immersed to 60min in 2% sodium hydroxide solution, taken out, washing is dried, obtain thickness receiving for 0.05mm
Prussian blue/the chitosan complex film of rice.
1ml isopropanols are added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, vacuum is done at 130 DEG C
Dry 12h, in 15MPa lower sheeting 12s, as positive pole, using metallic sodium piece as negative pole, with 1.2mol/L NaClO4For electrolysis
Liquid, volume ratio is 1:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate, using chitosan film as every
Film, assembling forms sodium-ion battery under argon atmosphere.
Embodiment 5：
(1) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 1：0.5:1.5 amount, to 0.100ml's
4mmol ferrous oxalate and 2mmol sodium oxalates is added in deionized water, is well mixed, ultrasonic agitation to clear liquid, solution A is formed,
6mmol sodium ferrocyanides are added into 0.100ml deionized water, are well mixed, surfactant F127, surface-active is added
The mass ratio of agent F127 and sodium ferrocyanide is 0.003:1, ultrasonic agitation to clear liquid forms B solution.
(2) B solution is added in solution A, in 30 DEG C stir 96h, obtain blue precipitate, by blue precipitate first with
5000rpm speed deionized water centrifuge washing 3 times, then with 5000rpm rate Methanol centrifuge washing 1 time, it is true at 130 DEG C
Sky is dried overnight 5h, obtains the nanometer Prussian Blue material Fe-HCF-NC of low defect2。
(3) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving, shape at 60 DEG C
It is 100mg according to the mass ratio of nanometer Prussian Blue, chitosan and conductive agent into chitosan solution:80mg:30mg, shell is gathered
The nanometer Prussian Blue material and conductive agent Super-P of low defect are added in sugar juice, is well mixed, ultrasonic wave degassing, degassing
Solidify 4h film forming, film is immersed to 50min in 2% sodium hydroxide solution, taken out, washing is dried, it is 0.05mm's to obtain thickness
Nanometer Prussian Blue/chitosan complex film.
1ml isopropanols are added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, vacuum is done at 130 DEG C
Dry 16h, in 15MPa lower sheeting 10s, as positive pole, using metallic sodium piece as negative pole, with 1.5mol/L NaClO4For electrolysis
Liquid, volume ratio is 1:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate, using chitosan film as every
Film, assembling forms sodium-ion battery under argon atmosphere.
Embodiment 6：
(1) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 0.75：0.5:2 amount, to 0.100ml's
1.25mmol ferrous oxalate and 1mmol sodium oxalates is added in deionized water, is well mixed, ultrasonic agitation to clear liquid, A is formed molten
Liquid, 4mmol sodium ferrocyanides are added into 0.100ml deionized water, are well mixed, and add surfactant F127, surface
The mass ratio of activating agent F127 and sodium ferrocyanide is 0.001:1, ultrasonic agitation to clear liquid forms B solution.
(2) B solution is added in solution A, stirs 48h in 25.7 DEG C, obtain blue precipitate, blue precipitate is first
With 5000rpm speed deionized water centrifuge washing 3 times, then with 5000rpm rate Methanol centrifuge washing 1 time, at 130 DEG C
10h is dried in vacuum overnight, the nanometer Prussian Blue material Fe-HCF-NC of low defect is obtained2。
(3) 2g chitosans are added to 100ml 2% acetum, constant temperature is evenly stirred until dissolving, shape at 60 DEG C
It is 70mg according to the mass ratio of nanometer Prussian Blue, chitosan and conductive agent into chitosan solution:60mg:20mg, by chitosan
The nanometer Prussian Blue material and conductive agent Super-P of low defect are added in solution, is well mixed, ultrasonic wave degassing, degassing is solid
Change 4h film forming, film is immersed to 55min in 2% sodium hydroxide solution, taken out, washing is dried, obtain thickness receiving for 0.05mm
Prussian blue/the chitosan complex film of rice.
Isopropanol is added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, is dried in vacuo at 130 DEG C
1h, in 15MPa lower sheeting 5s, as positive pole, using metallic sodium piece as negative pole, with 1mol/L NaClO4For electrolyte, volume
Than for 1:1:0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate, using chitosan film as barrier film, in argon
Atmosphere encloses lower assembling and forms sodium-ion battery.
Comparative example：
By it is existing it is Prussian blue mixed with acetylene carbon black, be added dropwise isopropanol, 1h is dried in vacuo at 130 DEG C, in 15MPa
Lower sheeting 5s, as positive pole, using metallic sodium piece as negative pole, with 1mol/L NaClO4For electrolyte, volume ratio is 1:1:
0.05 ethyl carbonate ester, divinyl carbonate and fluorinated ethylene carbonate, using chitosan film as barrier film, under argon atmosphere
Assembling forms sodium-ion battery.
After testing, it is existing Prussian blue in the particle diameter and comparative example of nanometer Prussian Blue material prepared by embodiment 1-6
Particle diameter result it is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example | |
| The particle diameter (nm) of nanometer Prussian Blue material | 200 | 500 | 300 | 450 | 500 | 350 | 600-800 |
After testing, embodiment 1-6 prepare nanometer Prussian Blue/chitosan complex film mechanical performance and in 300mAhg-
1 current density circulate 500 times after capacity and the positive pole mechanical performance of comparative example and the result of capacity it is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example | |
| Elongation (%) | 2.6 | 3.9 | 2.8 | 3.0 | 3.2 | 3.4 | 0.3 |
| Ultimate strength (N) | 13.6 | 17.8 | 16.4 | 15.0 | 15.9 | 16.3 | 6.8 |
| Capacity ((mAhg-1)) | 106 | 98 | 103 | 99 | 102 | 104 | 60 |
After testing, capacity of the sodium-ion battery that prepared by embodiment 1-6 after 300mAhg-1 current densities are circulated 500 times
The result of conservation rate is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example | |
| Capability retention (%) | 85.2 | 84.3 | 84.6 | 85.0 | 84.7 | 85.1 | 67.0 |
As seen from the above table, the grain size stability of nanometer Prussian Blue prepared by the present invention is good, the general Shandong of nanometer of preparation
The mechanical strength of scholar's indigo plant/chitosan complex film is significantly improved, and good cycling stability, and capability retention is high.
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 preparation method of nanometer Prussian Blue/chitosan complex film of low defect, it is characterised in that bag
Include following steps：
(1) according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 0.5-1：0-1:1-2 amount, to 0.100ml's
Ferrous oxalate and sodium oxalate are added in deionized water, is well mixed, ultrasonic agitation to clear liquid, solution A is formed, to 0.100ml's
Sodium ferrocyanide is added in deionized water, is well mixed, surfactant is added, ultrasonic agitation to clear liquid forms B solution；
(2) B solution for preparing step (1) is added in the solution A of step (1) preparation, is stirred 24-96h in 20-30 DEG C, is obtained
To blue precipitate, blue precipitate is first washed through deionized water, then washed through methanol, is dried in vacuo at 100-130 DEG C
Overnight, the nanometer Prussian Blue material of low defect is obtained；
(3) add chitosan into 2% acetum, constant temperature is evenly stirred until dissolving, chitosan solution formed, by chitosan
The nanometer Prussian Blue material and conductive agent Super-P of low defect prepared by step (2) are added in solution, is well mixed, ultrasound
Ripple is deaerated, degassing solidification 4h film forming, and film is immersed to 40-60min in 2% sodium hydroxide solution, taken out, washing is dried, obtained
Nanometer Prussian Blue/chitosan complex film of low defect.
2. a kind of system of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect according to claim 1
Preparation Method, it is characterised in that：In the step (1), ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 1：0-1：2.
3. a kind of system of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect according to claim 1
Preparation Method, it is characterised in that：In the step (1), surfactant is surfactant F127, surfactant and ferrous cyanogen
The mass ratio for changing sodium is 0.001-0.01:1.
4. a kind of system of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect according to claim 1
Preparation Method, it is characterised in that：In the step (2), deionized water washing times are 3 times, and the number of times of methanol washing is 1 time, is washed
Wash as with 5000rpm speed centrifuge washing.
5. a kind of system of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect according to claim 1
Preparation Method, it is characterised in that：In the step (2), vacuum drying temperature is 100-125 DEG C.
6. a kind of system of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect according to claim 1
Preparation Method, it is characterised in that：In the step (2), the particle diameter of the nanometer Prussian Blue material of low defect is 200-500nm.
7. a kind of system of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect according to claim 1
Preparation Method, it is characterised in that：In the step (3), middle nanometer Prussian Blue, the shell of nanometer Prussian Blue/chitosan complex film
The mass ratio of glycan and conductive agent is 7-10:5-8:2-3.
8. a kind of system of the preparation method of nanometer Prussian Blue/chitosan complex film of low defect according to claim 1
Preparation Method, it is characterised in that：In the step (3), the thickness of nanometer Prussian Blue/chitosan complex film is 0.03-0.05mm.
9. a kind of application of the nanometer Prussian Blue/chitosan complex film of low defect in sodium-ion battery, it is characterised in that bag
Include following steps：
Isopropanol is added dropwise in the nanometer Prussian Blue of low defect/chitosan complex film surface, is dried in vacuo at 120-130 DEG C
12-16h, in 15MPa lower sheeting 5-15s, as positive pole, using metallic sodium piece as negative pole, with 1-1.5mol/L NaClO4For
Electrolyte, using chitosan film as barrier film, assembling forms sodium-ion battery under argon atmosphere.
10. a kind of nanometer Prussian Blue/chitosan complex film of low defect according to claim 7 is in sodium-ion battery
Application, it is characterised in that：The NaClO4Containing volume ratio to be 1 in electrolyte:1:0.05 ethyl carbonate ester, carbonic acid two
Vinyl acetate and fluorinated ethylene carbonate.
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| CN109841832A (en) * | 2017-11-29 | 2019-06-04 | 宁德时代新能源科技股份有限公司 | Positive plate and electrochemical cell |
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| CN116747832A (en) * | 2023-08-07 | 2023-09-15 | 北京师范大学珠海校区 | Two-dimensional lanthanum-based adsorption film and application thereof |
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| CN116747832A (en) * | 2023-08-07 | 2023-09-15 | 北京师范大学珠海校区 | Two-dimensional lanthanum-based adsorption film and application thereof |
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