CN109867295A - Prussian blue nano flower electrode material and the preparation method and application thereof - Google Patents
Prussian blue nano flower electrode material and the preparation method and application thereof Download PDFInfo
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- CN109867295A CN109867295A CN201910103458.2A CN201910103458A CN109867295A CN 109867295 A CN109867295 A CN 109867295A CN 201910103458 A CN201910103458 A CN 201910103458A CN 109867295 A CN109867295 A CN 109867295A
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- prussian blue
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of the prussian blue nano flower electrode material of ultrathin nanometer piece assembling, chemical formula K1.4Fe4[Fe(CN)6]3, by forming with a thickness of 5~10nm ultrathin nanometer piece, the diameter of the prussian blue nano flower is 400~600nm, specific surface area 111.8m2g‑1.Beneficial effects of the present invention: dissolution recrystallization is carried out to Prussian in acid condition, to obtain the prussian blue nano floral structure electrode material of surface self-organization, when it is as kalium ion battery positive electrode active materials, the characteristics of showing power high, good cycling stability；Secondly, low in raw material price, simple process that the present invention uses, reaction condition is mild and can be used for mass production；Finally, feasibility of the present invention is strong, it is easy to amplify, and meets the requirement of Green Chemistry, is conducive to market-oriented popularization.
Description
Technical field
The invention belongs to nanometer material and electrochemical technology fields, and in particular to a kind of Prussia of ultrathin nanometer piece assembling
Indigo plant (K1.4Fe4[Fe(CN)6]3) nano flower electrode material preparation method, it is living which can be used as novel kalium ion battery anode
Property material.
Background technique
Although lithium ion battery is because energy density is high, self-discharge rate is low etc., advantages are widely used.But consider lithium
Cost caused by scarcity of resources increases and the inhomogeneities of lithium resource distribution, is increasingly urgent to the exploitation of novel energy-storing system.
Sodium and potassium resource have richer natural reserves, thus are widely paid close attention to.In contrast, potassium ion relies on smaller water
It closes ionic radius and shows superior ionic conductivity and ion transmission power, while potassium ion has reduction more lower than sodium
Current potential can be realized higher energy density.Therefore, a kind of kalium ion battery based on potassium ion intercalation/deintercalation is gradually closed
Note.However, larger-size potassium ion causes to generate huge bulk effect in battery charge and discharge process, to the steady of electrode material
Qualitative and electric conductivity has higher requirement.Therefore research and development can overcome potassium ion deintercalation bring bulk effect, and have
There are high security, low cost, high capacity, the kalium ion battery positive electrode of long-life that there is very great meaning.
Prussian blue to be used as a kind of organic frame metallic compound, cyano and transition metal constitute open frame knot
Structure, potassium ion can freely intercalation/deintercalation, synthesis material is cheap, and synthesis technology is simple, is before extremely having in kalium ion battery
A kind of electrode material of scape.
Summary of the invention
It is an object of the invention to promote the ion diffuser efficiency of Prussian, a kind of low in cost, work is provided
The prussian blue nano flower electrode material and preparation method thereof of the simple ultrathin nanometer piece assembling of skill, and it is used for potassium ion electricity
Pond positive electrode.
The technical proposal adopted by the invention to solve the above technical problems is that: prussian blue nano flower electrode material is changed
Formula is K1.4Fe4[Fe(CN)6]3, by forming with a thickness of 5~10nm ultrathin nanometer piece, the prussian blue nano is spent straight
Diameter is 400~600nm, specific surface area 111.8m2g-1。
The preparation method of the prussian blue nano flower electrode material, comprising the following steps:
1) HCl, deionized water and DMF solution are taken first, is stirred at room temperature uniformly mixed, obtain solution A；
2) K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, is stirred at room temperature uniformly；
3) acquired solution is subjected to hydro-thermal reaction, takes out cooled to room temperature；
4) product is centrifuged, and is washed, dry, obtains prussian blue nano flower electrode material.
According to the above scheme, HCl mass percent concentration described in step 1) is 36%, wherein HCl, deionized water and DMF
Volume ratio be 1:1:5.
According to the above scheme, K described in step 2)3Fe(CN)6Dosage is 0.1~10mmol, and the volume of the solution A is
7ml~700ml.
According to the above scheme, hydrothermal temperature described in step 3) is 50~100 DEG C, and the reaction time is 24~72h.
According to the above scheme, step 4) drying temperature is 60~100 DEG C, and drying condition is vacuum environment.
Application of the prussian blue nano flower electrode material as kalium ion battery positive electrode active materials.
The invention proposes a kind of preparation method of dissolution recrystallization synthesize assembled by ultrathin nanometer piece it is Prussian blue
(K1.4Fe4[Fe(CN)6]3) nano flower electrode material, which significantly increases specific surface area to effectively increasing electrolyte
With the contact area of electrode material, ion diffuser efficiency is improved, while this loose nanometer flower structure effectively alleviates
Bulk effect of the electrode material in cyclic process.It is demonstrated experimentally that Prussian blue (the K of this ultrathin nanometer piece assembling1.4Fe4
[Fe(CN)6]3) nano flower electrode material has high rate capability and long circulation life, be the great potassium for having practical application value from
Sub- battery electrode material.
Beneficial effects of the present invention: carrying out dissolution recrystallization to Prussian in acid condition, to obtain
Prussian blue (the K of surface self-organization1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material, as kalium ion battery anode
When active material, the characteristics of showing power high, good cycling stability；Secondly, low in raw material price, technique that the present invention uses
Simply, reaction condition is mild and can be used for mass production；Finally, feasibility of the present invention is strong, it is easy to amplify, and meet Green Chemistry
Requirement, be conducive to market-oriented popularization.
Detailed description of the invention
Fig. 1 is the topographical transition schematic diagram and SEM of the prussian blue nano floral structure electrode material of the embodiment of the present invention 1
Figure；
Fig. 2 is the XRD diagram and BET figure of the prussian blue nano floral structure electrode material of the embodiment of the present invention 1；
Fig. 3 is the battery high rate performance figure and correspondence of the prussian blue nano floral structure electrode material of the embodiment of the present invention 1
Charging and discharging curve figure；
Fig. 4 is the cycle performance of battery figure of the prussian blue nano floral structure electrode material of the embodiment of the present invention 1.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
1) 10mL 36%HCl, 10mL deionized water and 50mL DMF are taken first, is stirred at room temperature uniformly mixed, are obtained
The solution A of clear；
2) 1mmol K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, 10min is stirred at room temperature and obtains faint yellow clear
Solution；
3) solution is transferred in 100mL polytetrafluoroethyllining lining and is fitted into reaction kettle at 70 DEG C after hydro-thermal 48h
It takes out, to its cooled to room temperature；
4) product is collected by centrifugation and is washed 3 times with deionized water water and dehydrated alcohol respectively, the vacuum drying at 80 DEG C.
Prussian blue (K obtained above1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material as kalium ion battery just
The application of pole material.
With the Prussian blue (K of this example product1.4Fe4[Fe(CN)6]3) for nanometer flower structure electrode material, attached drawing 1 discloses
The Forming Mechanism of Prussian blue nano flower is the process of dissolution recrystallization.It is initially formed prussian blue nano ball (Fig. 1 a),
In acid condition, Prussian blue ecto-entad gradually dissolves (Fig. 1 b), and with the continuation of reaction, the part of dissolution is again in table
Face is self-assembly of ultrathin nanometer piece (Fig. 1 c).Attached drawing 2a is the XRD diagram of product, shows the higher crystallinity of material.Attached drawing 2b
Show that the structure specific surface area of this ultrathin nanometer piece assembling is up to 111.8cm2g-1, aperture concentrates at 5~15nm.It is prepared
Ultrathin nanometer piece assembling Prussian blue (K1.4Fe4[Fe(CN)6]3) nano flower electrode material diameter be 400~600nm, receive
Rice piece thickness about 10nm, this novel hierarchical structure have big specific surface area to increase electrolyte and electrode material
Contact area, and effectively promote ion diffuser efficiency, alleviates ess-strain of the electrode material in cyclic process, so potassium from
There is high rate capability and long circulation life in sub- battery energy storage.
Resulting Prussian blue (the K of this example1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material is as kalium ion battery
The application of positive electrode active materials is as follows:
Prussian blue (K is used in the preparation of positive plate1.4Fe4[Fe(CN)6]3) nano flower is as active material, Ketjen black
As conductive agent, polytetrafluoroethylene (PTFE) is as binder.Active material, Ketjen black, polytetrafluoroethylene (PTFE) mass ratio be 60:30:10；
After they are sufficiently mixed in proportion, a small amount of isopropanol is added, uniformly, being pressed into load capacity on twin rollers is about for grinding
1.5mg cm-2Electrode slice；It is spare after the vacuum drying oven that the electrode slice prepared is placed in 80 DEG C dry a few hours.With 0.5M
KPF6Be dissolved in EC/DEC (1:1V/V), as electrolyte, and be added 5% fluorinated ethylene carbonate additive.Potassium piece conduct
Cathode, glass fibre are diaphragm, and CR2016 type stainless steel is that battery case is assembled into button kalium ion battery.Kalium ion battery
Entire assembling process carries out in Brian argon gas glove box, remaining preparation method and common button cell preparation method phase
Together.
It is Prussian blue (K shown in attached drawing 3a1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material is close in different electric currents
High rate performance under degree, in 50mA g-1、100mA g-1、200mA g-1、400mA g-1With 600mA g-1Current density under,
The first discharge specific capacity of the electrode material can respectively reach 71mAh g-1、60mAh g-1、52mAh g-1、40mAh g-1With
26mAh g-1.After experience gradient increases the charge and discharge behavior under current density, when current density is restored to 50mA g-1When,
Capacity can be restored to 63mAh g-1, capacity retention ratio reaches 89%.Attached drawing 3b show electrode material in different current densities
Under charging and discharging curve, it can be seen that apparent charge and discharge platform.These results suggest that the structural stability of material is excellent.Such as figure
Shown in 4, in 200mA g-1Current density under, discharge capacity is up to 50mAh g for the first time-1, after circulation 100 is enclosed, capacity retention ratio
Reach 76%.It should be the result shows that this Prussian blue (K1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material have it is excellent
Structural stability is the high power for extremely having application prospect, long-life kalium ion battery electrode material.
Embodiment 2
1) 10mL 36%HCl, 10mL deionized water and 50mL DMF are taken first, and uniformly mixed, preparation is stirred at room temperature
The solution A of clear；
2) 2mmol K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, 10min is stirred at room temperature and obtains faint yellow clear
Solution；
3) solution is transferred in 100mL polytetrafluoroethyllining lining and is fitted into reaction kettle at 70 DEG C after hydro-thermal 48h
It takes out, to its cooled to room temperature；
4) product is collected by centrifugation and is washed 3 times with deionized water and dehydrated alcohol respectively, the vacuum drying at 80 DEG C.
Prussian blue (K obtained above1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material as kalium ion battery just
The application of pole material.
With the resulting Prussian blue (K of the present embodiment1.4Fe4[Fe(CN)6]3) for nanometer flower structure electrode material,
200mA g-1Current density under, the initial discharge capacity of material is 53mAh g-1Discharge capacitance after circulation 100 times
It is 70%.
Embodiment 3
1) 10mL 36%HCl, 10mL deionized water and 50mL DMF are taken first, and uniformly mixed, preparation is stirred at room temperature
The solution A of clear；
2) 3mmol K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, 10min is stirred at room temperature and obtains faint yellow clear
Solution；
3) solution is transferred in 100mL polytetrafluoroethyllining lining and is fitted into reaction kettle at 70 DEG C after hydro-thermal 48h
It takes out, to its cooled to room temperature；
4) product is collected by centrifugation and is washed 3 times with deionized water and dehydrated alcohol respectively, the vacuum drying at 80 DEG C.
Prussian blue (K obtained above1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material as kalium ion battery just
The application of pole material.
With the resulting Prussian blue (K of the present embodiment1.4Fe4[Fe(CN)6]3) for nanometer flower structure electrode material,
200mA g-1Current density under, the initial discharge capacity of material is 55mAh g-1Discharge capacitance after circulation 100 times
It is 79.6%.
Embodiment 4
1) 10mL 36%HCl, 10mL deionized water and 50mL DMF are taken first, and uniformly mixed, preparation is stirred at room temperature
The solution A of clear；
2) 1mmol K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, 10min is stirred at room temperature and obtains faint yellow clear
Solution；
3) solution is transferred in 100mL polytetrafluoroethyllining lining and is fitted into reaction kettle at 100 DEG C after hydro-thermal 48h
It takes out, to its cooled to room temperature；
4) product is collected by centrifugation and is washed 3 times with deionized water and dehydrated alcohol respectively, the vacuum drying at 80 DEG C.
Prussian blue (K obtained above1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material as kalium ion battery just
The application of pole material.
With the resulting Prussian blue (K of the present embodiment1.4Fe4[Fe(CN)6]3) for nanometer flower structure electrode material,
200mA g-1Current density under, the initial discharge capacity of material is 57mAh g-1Discharge capacitance after circulation 100 times
It is 74.5%.
Embodiment 5:
1) 10mL 36%HCl, 10mL deionized water and 50mL DMF are taken first, and uniformly mixed, preparation is stirred at room temperature
The solution A of clear；
2) 1mmol K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, 10min is stirred at room temperature and obtains faint yellow clear
Solution；
3) after the solution being transferred in 100mL polytetrafluoroethyllining lining and being fitted into reaction kettle at 70 DEG C hydro-thermal for 24 hours
It takes out, to its cooled to room temperature；
4) product is collected by centrifugation and is washed 3 times with water and dehydrated alcohol respectively, the vacuum drying at 80 DEG C.
Prussian blue (K obtained above1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material as kalium ion battery just
The application of pole material.
With the resulting Prussian blue (K of this example1.4Fe4[Fe(CN)6]3) for nanometer flower structure electrode material, in 200mA
g-1Current density under, the initial discharge capacity of material is 49mAh g-1Circulation 100 times after discharge capacitance be
73.4%.
Embodiment 6
1) 10mL 36%HCl, 10mL deionized water and 50mL DMF are taken first, and uniformly mixed, preparation is stirred at room temperature
The solution A of clear；
2) 1mmol K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, 10min is stirred at room temperature and obtains faint yellow clear
Solution；
3) solution is transferred in 100mL polytetrafluoroethyllining lining and is fitted into reaction kettle at 70 DEG C after hydro-thermal 48h
It takes out, to its cooled to room temperature；
8) product is collected by centrifugation and is washed 3 times with water and dehydrated alcohol respectively, the vacuum drying at 100 DEG C.
Prussian blue (K obtained above1.4Fe4[Fe(CN)6]3) nanometer flower structure electrode material as kalium ion battery just
The application of pole material.
With the resulting Prussian blue (K of this example1.4Fe4[Fe(CN)6]3) for nanometer flower structure electrode material, in 200mA
g-1Current density under, the initial discharge capacity of material is 55mAh g-1Circulation 100 times after discharge capacitance be
74.7%.
Claims (7)
1. prussian blue nano spends electrode material, chemical formula K1.4Fe4[Fe(CN)6]3, by being received with a thickness of 5~10nm is ultra-thin
The diameter of rice piece composition, the prussian blue nano flower is 400~600nm, specific surface area 111.8m2g-1。
2. the preparation method of prussian blue nano flower electrode material described in claim 1, comprising the following steps:
1) HCl, deionized water and DMF solution are taken first, is stirred at room temperature uniformly mixed, obtain solution A；
2) K is taken3Fe(CN)6It is dissolved in above-mentioned solution A, is stirred at room temperature uniformly；
3) acquired solution is subjected to hydro-thermal reaction, takes out cooled to room temperature；
4) product is centrifuged, and is washed, dry, obtains prussian blue nano flower electrode material.
3. the preparation method of prussian blue nano flower electrode material according to claim 2, which is characterized in that step 1) institute
The HCl mass percent concentration stated is 36%, wherein HCl, and the volume ratio of deionized water and DMF are 1:1:5.
4. the preparation method of prussian blue nano flower electrode material according to claim 2, which is characterized in that step 2) institute
The K stated3Fe(CN)6Dosage is 0.1~10mmol, and the volume of the solution A is 7ml~700ml.
5. the preparation method of prussian blue nano flower electrode material according to claim 2, which is characterized in that step 3) institute
The hydrothermal temperature stated is 50~100 DEG C, and the reaction time is 24~72h.
6. the preparation method of prussian blue nano flower electrode material according to claim 2, which is characterized in that step 4) is dry
Dry temperature is 60~100 DEG C, and drying condition is vacuum environment.
7. application of the prussian blue nano flower electrode material described in claim 1 as kalium ion battery positive electrode active materials.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8382782A (en) * | 1981-05-26 | 1982-12-02 | Kabushiki Kaisha Daini Seikosha | Electrolytic production of iron (iii) hexacyanoferrate |
| US20140127592A1 (en) * | 2012-11-02 | 2014-05-08 | Alveo Energy, Inc. | Stabilization of battery electrodes using polymer coatings |
| CN105017527A (en) * | 2015-07-05 | 2015-11-04 | 桂林电子科技大学 | Preparation method and application of Prussian-blue-nanocrystal-loaded graphene composite material |
| CN105836762A (en) * | 2016-03-16 | 2016-08-10 | 西北大学 | Preparation method and application of hollow Prussian-blue nanometer cube |
| CN107082438A (en) * | 2017-04-28 | 2017-08-22 | 武汉理工大学 | Prussian blue nano floral structure material and its preparation and application |
-
2019
- 2019-02-01 CN CN201910103458.2A patent/CN109867295B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8382782A (en) * | 1981-05-26 | 1982-12-02 | Kabushiki Kaisha Daini Seikosha | Electrolytic production of iron (iii) hexacyanoferrate |
| US20140127592A1 (en) * | 2012-11-02 | 2014-05-08 | Alveo Energy, Inc. | Stabilization of battery electrodes using polymer coatings |
| CN105017527A (en) * | 2015-07-05 | 2015-11-04 | 桂林电子科技大学 | Preparation method and application of Prussian-blue-nanocrystal-loaded graphene composite material |
| CN105836762A (en) * | 2016-03-16 | 2016-08-10 | 西北大学 | Preparation method and application of hollow Prussian-blue nanometer cube |
| CN107082438A (en) * | 2017-04-28 | 2017-08-22 | 武汉理工大学 | Prussian blue nano floral structure material and its preparation and application |
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