Preparation method and application of sodium-rich anhydrous prussian blue analogue material

A technology of Prussian blue and its analogues, which is applied in the field of anode materials for sodium ion secondary batteries, can solve the problems of Prussian analogues such as large difference in actual capacity and theoretical capacity, decrease in cycle stability and rate performance, and influence on ion redox reactions. Achieve the effect of excellent shape, good cycle performance and strong controllability

CN109292795AInactive Publication Date: 2019-02-01TIANJIN UNIV
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Patent Information

Authority / Receiving Office
CN · China
Current Assignee / Owner
Publication Date
2019-02-01
Estimated Expiration
Not applicable · inactive patent

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Abstract

The invention relates to a sodium-rich anhydrous prussian blue analogue material. The preparation method comprises the following steps: using potassium ferrocyanide or sodium ferrocyanide, sodium chloride and manganese chloride as precursors for preparing a prussian blue analogue, so that a turbid liquid is formed; collecting solid materials in the turbid liquid by using a centrifugation and suction filtration method, and carrying out water washing until no residual sodium chloride exists in the product, so that a sodium-rich prussian blue analogue is obtained; grinding the prepared sodium-rich prussian blue analogue into powder, laying the powder in a square boat, and placing the square boat in a constant-temperature zone of a tubular furnace for calcining; and taking one or a mixture ofmore selected from N2, He an Ar as an inert gas source, heating the tubular furnace to 180 DEG C at a heating speed of 1-10 DEG C / min, carrying out heat preservation for 2-3 hours to remove interstitial water, and carrying out cooling to room temperature along with the furnace after the heat preservation is finished, so that the sodium-rich anhydrous prussian blue analogue material is obtained. The prepared composite material of prussian blue analogue is applied to positive poles of sodium-ion batteries.
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Description

technical field

[0001] The invention relates to the preparation and application of a Prussian blue analogue material rich in sodium and without interstitial water, and belongs to the technical field of cathode materials for sodium ion secondary batteries. Background technique

[0002] Energy and environmental issues are the most concerned topics in the world today. At present, the annual consumption of fossil energy (coal, oil and natural gas, etc.) accounts for more than 85% of the total global energy consumption, and the reserves of fossil energy are limited. The growth of human demand for energy and the unrestrained exploitation of fossil energy will inevitably lead to the depletion of fossil energy dilemma. At the same time, the use of fossil energy will cause environmental problems such as environmental pollution, greenhouse effect, and smog, so it is urgent to explore a new energy system.

[0003] Among various energy storage methods, electrochemical energy storage i...

Examples

Embodiment 1

[0025] Weigh 1.82g sodium ferrocyanide, 36g sodium chloride and 1.20g manganese chloride, add sodium ferrocyanide to 100ml deionized water, stir for 30min to form solution A, add sodium chloride to solution A to form Saturated solution B of sodium chloride, continue to stir for 30min. Dissolve manganese chloride in 100ml of deionized water, stir evenly, add dropwise to the above saturated solution B, stir for 24 hours to form a suspension.

[0026] The solid material in the suspension was collected by a centrifuge with a centrifugal speed of 8000r / min, washed 3 times with deionized water until there was no remaining sodium chloride in the product, and suction filtered to obtain a sodium-rich Prussian blue analog material. Dry in a vacuum oven at 100°C for 24 hours.

[0027] Grind the dried sodium-rich Prussian blue analogue into powder, spread it in the ark, and place it in the constant temperature zone of the tube furnace for calcination: with Ar as the inert gas source, fir...

Embodiment 2

[0030] Weigh 1.82g sodium ferrocyanide, 34g sodium chloride and 1.20g manganese chloride, add sodium ferrocyanide to 100ml deionized water, stir for 30min to form solution A, add sodium chloride to solution A to form Saturated solution B of sodium chloride, continue to stir for 30min. Dissolve manganese chloride in 100ml of deionized water, stir evenly, add dropwise to the above saturated solution B, stir for 24 hours to form a suspension. The solid material in the suspension was collected by a centrifuge with a centrifugal speed of 8000r / min, washed 3 times with deionized water until there was no remaining sodium chloride in the product, and suction filtered to obtain a sodium-rich Prussian blue analog material. Dry in a vacuum oven at 100°C for 24 hours. The dried sodium-rich Prussian blue analogue is ground into powder, spread in the ark, and placed in the constant temperature zone of the tube furnace for calcination: with N 2 As the source of inert gas, the inert gas was...

Embodiment 3

[0032] Weigh 1.82g sodium ferrocyanide, 36g sodium chloride and 1.20g manganese chloride, add sodium ferrocyanide to 100ml deionized water, stir for 20min to form solution A, add sodium chloride to solution A to form Saturated solution B of sodium chloride, continue to stir for 20min. Dissolve manganese chloride in 100ml of deionized water, stir well, then add dropwise into the above saturated solution B, stir for 24 hours to form a suspension. The solid material in the suspension was collected by a centrifuge with a centrifugal speed of 8000r / min, washed 3 times with deionized water until there was no remaining sodium chloride in the product, and suction filtered to obtain a sodium-rich Prussian blue analog material. Dry in a vacuum oven at 100°C for 24 hours. Grind the dried sodium-rich Prussian blue analogue into powder, spread it in the ark, and place it in the constant temperature zone of the tube furnace for calcination: with He as the inert gas source, first pass the ine...