Ultrafine iron-based Prussian blue and its analogue, preparation method and sodium-ion battery
A technology of Prussian blue and analogs, applied in the preparation of ultra-fine iron-based Prussian blue and its analogs, and the application field of cathode materials for sodium ion batteries, can solve the problems of unsuitability for large-scale production, low concentration of reactants, and kinetics. Poor performance and other problems, to achieve the effects of excellent cycle stability performance and rate performance, good rate performance and long cycle life
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[0036] The invention provides a kind of preparation method of superfine iron-based Prussian blue and its analogues, comprising the following steps:
[0037] (1) Sodium ferrocyanide and metal salts are added to the ball mill;
[0038] (2) adding an appropriate amount of solvent in the ball milling device;
[0039] (3) placing the mixed raw materials in the ball milling device for ball milling;
[0040] (4) Wash the obtained PBAs with absolute ethanol and deionized water.
[0041] (5) drying the cleaned product.
[0042] The preparation method of the ultrafine iron-based Prussian blue and its analogues of the present invention is not limited to the size of the ball mill pot, the ball milling method and the ball milling time. Metal salts include metal chloride salts (FeCl 2 、CoCl 2 , MnCl 2 etc.), metal sulfate (FeSO 4 、CoSO 4 and MnSO 4 etc.) or perchlorate (Fe(ClO 4 ) 2 , Mn(ClO 4 ) 2 , Co(ClO 4 ) 2 ), etc., the added sodium ferrocyanide and metal salt may contai...
Embodiment 1
[0046] S1: 4 mmol of sodium ferrocyanide decahydrate and 6 mmol of ferrous chloride tetrahydrate were placed in a nylon ball mill jar, and vibrated and mixed at a rate of 1200 r / min for 1 min.
[0047] S2: In a glove box filled with Ar, the above raw materials were placed in an agate ball mill jar with a ball-to-material ratio of 1:20.
[0048] S3: The agate ball mill jar was dry-milled for 12 hours in a planetary ball mill at a speed of 300 r / min.
[0049] S4: After the ball milling, the product was washed with absolute ethanol and deionized water, and dried in a vacuum oven at 80°C for 36 hours to obtain Na x Fe[Fe(CN) 6 .
[0050] figure 1 Be the XRD diffraction pattern of unwashed product after the ball milling of present embodiment example, by and Na 4 Fe(CN) 6 Standard PDF card comparison (JCPDS-1-1026), it can be seen that the unwashed product after ball milling does not contain Na 4 Fe(CN) 6 , which shows that the ball milling reaction is complete. figure 2 Fo...
Embodiment 2
[0053] S1: Put 4mmol of anhydrous sodium ferrocyanide and 4mmol of anhydrous manganous chloride in a nylon ball mill jar, vibrate and mix at a rate of 800r / min for 1min.
[0054] S2: Add 20ml of acetonitrile into the ball mill jar.
[0055] S3: Continue vibrating ball milling on a vibrating ball mill for 30 min at a vibration rate of 1200 r / min.
[0056] S4: After ball milling, filter the product, wash with absolute ethanol, and bake in a vacuum oven at 80°C for 36 hours to obtain Na x Mn[Fe(CN) 6 .
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