CN109775726A - A kind of preparation method of prussian blue material - Google Patents
A kind of preparation method of prussian blue material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of prussian blue material.It includes the following steps: anhydrous Prussian blue presoma P [R (CN)6] and anhydrous sodium material NaR (CN)6Mixing, reacts through solid-phase ball milling, and prussian blue material Na is madexP[R(CN)6], wherein P and R are each independently selected from transition metal element.Prussian blue material lattice water content produced by the present invention is few, and the battery capacity that is prepared when as sodium-ion battery positive material is high, good cycle, and preparation method preparation process is simple, production cost is low, nontoxic, with short production cycle, yield is high, and performance is stablized.
Description
Technical field
The present invention relates to a kind of preparation methods of prussian blue material, are reduced more particularly to one kind by being heat-treated
Forerunner's body water content, and the method that prussian blue material is prepared by the reaction of single solid-phase ball milling.
Background technique
With the continuous extension of global scale energy storage demand, resourceful, environmental-friendly sodium-ion battery technology at
For the hot spot studied at present.The high-capacity electrode material for seeking to have with exploitation quick embedding removing sodium ability is sodium-ion battery development
Key.Prussian blue material general formula is AxP[R(CN)6] (P, R are transition metal element, and A is alkali metal element), have three
Cube frame structure is tieed up, cube void size is larger (> 0.5nm) in frame, can be embedded in alkali metal ion or other types
Metal ion, be comparatively ideal storage sodium material.In recent years, application of the prussian blue material in sodium-ion battery receives
Extensive concern.Prussian blue material feedstock source is wide, and preparation is simple, and theoretical capacity has good answer up to 170mAh/g
Use prospect.This material is reported first by Goodenough seminar, is furtherd investigate later.
Prussian blue material mainly uses liquid-phase precipitation method to prepare, and generallys use salt (chloride, sulfuric acid of transition metal
One of salt, nitrate or acetate) with transition metal cyanogen salt occur in aqueous solution precipitation reaction be made.But this side
There is a large amount of vacancy in the material crystals of method synthesis, these vacancy can cause material during material embedding removing sodium ion
Structure collapses.There is also a large amount of water of coordination among material, these hydrones can seriously affect the performance of material.
Prussian blue Fe4[Fe(CN)6]3With sodium ferrocyanide Na4Fe(CN)6All it is applied to sodium-ion battery anode material
Material.But sodium ferrocyanide Na4Fe(CN)6Poorly conductive, when use, needs increasing amount conductive agent, and Prussian blue Fe4[Fe
(CN)6]3Poor sodium environment also limit its application in terms of sodium-ion battery positive material.
Therefore, the performance of prussian blue material how is effectively promoted, applies prussian blue material to further be promoted
The performance of the sodium-ion battery of material is this field technical problem urgently to be resolved.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome in the prior art prussian blue material lattice water content it is high,
The battery capacity being prepared when as sodium-ion battery positive material is low, poor circulation defect, and provides a kind of general
The preparation method of Shandong scholar's indigo plant class material.Prussian blue material lattice water content produced by the present invention is few, as sodium-ion battery
The battery capacity that is prepared when positive electrode is high, good cycle, and preparation method preparation process is simple, and production cost is low,
Nontoxic, with short production cycle, yield is high, and performance is stablized.
The purpose of the present invention is achieved through the following technical solutions.
The present invention provides a kind of preparation methods of prussian blue material comprising following steps:
By anhydrous Prussian blue presoma P [R (CN)6] and anhydrous sodium material NaR (CN)6Mixing, it is anti-through solid-phase ball milling
It answers, prussian blue material Na is madexP[R(CN)6]；
Wherein, P and R are each independently selected from transition metal element,
P[R(CN)6]+NaR(CN)6→NaxP[R(CN)6]。
In the present invention, the anhydrous Prussian blue presoma P [R (CN)6] and the anhydrous sodium material NaR (CN)6?
For solid sample, it should generally be placed in argon inert atmosphere glove box and save, to avoid water suction oxidation occurs.
In the present invention, the transition metal element can be the transition metal element of this field routine, preferably Fe, Mn, Co
Or Ni, such as Fe.
When the P is Fe, the chemical valence of the Fe is preferably+trivalent.
When the R is Fe, the chemical valence of the Fe is preferably+divalent.
In the present invention, the prussian blue material NaxP[R(CN)6] in x can be carried out according to the chemical valence of each element it is true
It is fixed, make the prussian blue material NaxP[R(CN)6] whole chemical valence is 0.
In the present invention, the Prussian blue presoma P [R (CN)6] it can be the Prussian blue presoma P [R of this field routine
(CN)6], preferably Prussian blue Fe4[Fe(CN)6]3。
In the present invention, the sodium material NaR (CN)6It can be the sodium material NaR (CN) of this field routine6, it is however generally that, institute
State sodium material NaR (CN)6Following conditions should at least be met: the 1. sodium material NaR (CN)6Operating voltage range with it is described general
Shandong scholar's indigo plant presoma P [R (CN)6] operating voltage range it is suitable；2. compared to the Prussian blue presoma P [R (CN)6], institute
State sodium material NaR (CN)6Capacity it is therewith quite or higher；3. the sodium material NaR (CN)6It can be used as the donor of sodium ion.
Preferably, the sodium material NaR (CN)6For sodium ferrocyanide Na4Fe(CN)6。
As known to those skilled in the art, it is heretofore described it is anhydrous be restriction to Moisture in Material, generally refer to
Moisture in Material is lower than 5%, and percentage refers to mass percent.
In the present invention, the anhydrous Prussian blue presoma P [R (CN)6] preparation method of this field routine can be passed through
It is made, it is preferable that by Prussian blue presoma P [R (CN)6] it is heat-treated after to get anhydrous Prussian blue presoma P [R
(CN)6]。
Wherein it is preferred to which the heat treatment carries out in a vacuum drying oven.The purpose of the heat treatment is to drop
Low Prussian blue presoma P [R (CN)6] water content.As known to those skilled in the art, it in the heat-treatment process, needs
Timing vacuumizes, and vacuum oven is discharged in time convenient for moisture, prevents from aoxidizing.
Wherein, the temperature of the heat treatment is preferably 100~150 DEG C, such as 120 DEG C.
Wherein, general to go back after visible moisture drains (after generally heating 5-6 hours) in the heat-treatment process
It need to be heated for a period of hours, to ensure material moisture content lower than 5%, percentage refers to mass percent.Preferably, the heat treatment
Time be 8~12 hours, such as 8 hours.
As the Prussian blue presoma P [R (CN)6] it is Prussian blue Fe4[Fe(CN)6]3When, the heat treatment
Temperature is preferably 120 DEG C, and the time of the heat treatment is preferably 8 hours.
In the present invention, the anhydrous sodium material NaR (CN)6It can be made by the preparation method of this field routine, preferably
Ground, by sodium material NaR (CN)6To get anhydrous sodium material NaR (CN) after heat-treated6。
Wherein it is preferred to which the heat treatment carries out in a vacuum drying oven.The purpose of the heat treatment is to drop
Low sodium material NaR (CN)6Water content.As known to those skilled in the art, in the heat-treatment process, timing is needed to take out true
Vacuum oven is discharged convenient for moisture in sky in time, prevents from aoxidizing.
Wherein, the temperature of the heat treatment is preferably 80~100 DEG C, such as 90 DEG C.
Wherein, general to go back after visible moisture drains (after generally heating 5-6 hours) in the heat-treatment process
It need to be heated for a period of hours, to ensure material moisture content lower than 5%, percentage refers to mass percent.Preferably, the heat treatment
Time be 8~12 hours, such as 8 hours.
When the sodium material NaR (CN)6For sodium ferrocyanide Na4Fe(CN)6When, the temperature of the heat treatment is preferably
90 DEG C, the time of the heat treatment is preferably 8 hours.
In the present invention, the anhydrous Prussian blue presoma P [R (CN)6] and the anhydrous sodium material NaR (CN)6's
Molar ratio can be the reaction ratio of this field routine, it is however generally that, the anhydrous sodium material NaR (CN)6In it is available
Extra sodium ion and the anhydrous Prussian blue presoma P [R (CN)6] acceptable sodium ion equimolar.
As the Prussian blue presoma P [R (CN)6] it is Prussian blue Fe4[Fe(CN)6]3, and the sodium material NaR
(CN)6For sodium ferrocyanide Na4Fe(CN)6When, the anhydrous Prussian blue presoma P [R (CN)6] and the anhydrous sodium
Material NaR (CN)6Molar ratio be preferably 1:1, under this ratio, the two fully reacting, save raw material, the following institute of reaction equation
Show:
Fe4[Fe(CN)6]3+Na4Fe(CN)6→4NaFeFe(CN)6。
In the present invention, the solid-phase ball milling reaction can react for the solid-phase ball milling of this field routine, be normally applied agate ball
As reaction vessel reaction raw materials and agate ball milling pearl is added, through ball mill ball milling in grinding jar.
Wherein, the revolving speed of the ball mill is preferably 400-500rpm, more preferably 450rpm.When the revolving speed of ball mill is small
When 400rpm, reaction is incomplete；When the revolving speed of ball mill is greater than 500rpm, ball mill heat production is excessive, is unfavorable for reaction
It carries out.
Wherein, the time of the ball milling is preferably 4~10 hours, and more preferably 6 hours.It is small less than 4 when the time of ball milling
Constantly, react insufficient；When Ball-milling Time is greater than 10 hours, the particle of reaction raw materials is too small, easily causes lattice disturbance.
Wherein it is preferred to which the drum's speed of rotation is 450rpm, the time of the ball milling is 6 hours.
As known to those skilled in the art, in the solid-phase ball milling reaction, the anhydrous Prussian blue presoma P [R
(CN)6] and the anhydrous sodium material NaR (CN)6Weighing and mixed process should all in argon inert atmosphere glove box into
Row, generally by load weighted anhydrous Prussian blue presoma P [R (CN)6] and anhydrous sodium material NaR (CN)6It is placed in ball grinder
It after mixing, is sealed and takes out glove box, then carry out solid-phase ball milling reaction through ball mill.
In the present invention, the prussian blue material NaxP[R(CN)6] water content be generally below 5%, percentage refers to
Mass percent.Preferably, by the prussian blue material NaxP[R(CN)6] be heat-treated by this field routine operation.
Wherein it is preferred to which the temperature of the heat treatment is 150~160 DEG C, such as 150 DEG C.When the temperature of heat treatment is lower than
At 150 DEG C, it is unfavorable for water in products point removal；When the temperature of heat treatment is higher than 160 DEG C, destructible product lattice structure.
Wherein it is preferred to which the time of the heat treatment is 4~12 hours, such as 5 hours.
As the prussian blue material NaxP[R(CN)6] it is ferrocyanide ferrisodium NaFeFe (CN)6When, the heat treatment
Temperature be preferably 150 DEG C, the time of the heat treatment is preferably 5 hours.
In a better embodiment of the invention, by anhydrous Prussian blue Fe4[Fe(CN)6]3With anhydrous ferrocyanide
Sodium Na4Fe(CN)6Mixing, reacts through solid-phase ball milling, and ferrocyanide ferrisodium NaFeFe (CN) is made6,
Fe4[Fe(CN)6]3+Na4Fe(CN)6→4NaFeFe(CN)6。
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
(1) the invention proposes a kind of inexpensive, nontoxic, high performance prussian blue sodium-ion battery anode materials
The preparation method of material uses Prussian blue Fe4[Fe(CN)6]3With sodium ferrocyanide Na4Fe(CN)6For raw material, gone by heat treatment
Except moisture in raw material, to reduce lattice watter defect in product, meanwhile, it overcomes because of sodium ferrocyanide Na4Fe(CN)6Low conduction
Property and Prussian blue Fe4[Fe(CN)6]3Poor sodium defect and the sodium-ion battery positive material application limitation that generates, both pass through
Single solid phase mixing ball-milling reaction, synthesized the poor prussian blue material of lattice watter, shown the material higher
Capacity and preferable cycle performance.
In addition, raw material is easy to get, at low cost, synthesis technology is simple, and subsequent without cleaning, processing is simple.Therefore present invention side
Method prepares prussian blue sodium ion battery electrode material and has a good application prospect.
(2) raw material used in prussian blue material preparation method of the invention is commercially available and cheap.This
It is prepared with outstanding chemical property when inventing the prussian blue material being prepared applied to sodium-ion battery anode
Prussian blue material 0.1C specific capacity be higher than 118.2mAh/g, 1C charge and discharge cycles 1000 enclose after still with 61.3% appearance
Measure conservation rate.
Detailed description of the invention
Fig. 1 is that embodiment 1, battery made from comparative example 1 and the preparation-obtained prussian blue material of comparative example 2 fill
Discharge cycle performance compares figure, voltage range 2.0-4.0V, and electrolyte is 1mol/L NaPF6/ PC:EMC:FEC (49:49:2),
Charging and discharging currents are 10mA/g；
Fig. 2 is that embodiment 1, battery made from comparative example 1 and the preparation-obtained prussian blue material of comparative example 2 fill
Discharge cycle performance compares figure, voltage range 2.0-4.0V, and electrolyte is 1mol/L NaPF6/ PC:EMC:FEC (49:49:2),
Charging and discharging currents are 100mA/g；
Fig. 3 is the charge and discharge cycles of battery made from embodiment 1 and the preparation-obtained prussian blue material of comparative example 3
Performance compares figure, voltage range 2.0-4.0V, and electrolyte is 1mol/L NaPF6/ PC:EMC:FEC (49:49:2), charge and discharge electricity
Stream is 100mA/g；
Fig. 4 is the thermogravimetric analysis figure of embodiment 1 and the preparation-obtained prussian blue material of comparative example 3.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.Following embodiment will be helpful to the skill of this field
Art personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the common skill of this field
For art personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to this hair
Bright protection scope.
Embodiment 1
The present embodiment is related to a kind of prussian blue material, ferrocyanide ferrisodium NaFeFe (CN)6Preparation method, including
Following steps:
(1) the Prussian blue Fe that will be bought4[Fe(CN)6]3With sodium ferrocyanide Na4Fe(CN)6Respectively in vacuum drying oven
It at 120 DEG C and 90 DEG C, heats 8 hours, removes moisture in materials, obtain the anhydrous Prussian blue Fe of solid powder A4[Fe(CN)6]3
With the anhydrous sodium ferrocyanide Na of solid powder B4Fe(CN)6。
(2) A and B is weighed by the molar ratio of 1:1, anhydrous Prussian blue Fe4[Fe(CN)6]3Quality be 2.58g, it is anhydrous
Sodium ferrocyanide Na4Fe(CN)6Quality be 0.91g.
(3) the anhydrous Prussian blue Fe for obtaining weighing4[Fe(CN)6]3With anhydrous sodium ferrocyanide Na4Fe(CN)6In Ma
Hand mix is uniform in Nao ball grinder, and ball grinder is sealed after appropriate agate ball milling pearl is added, anti-with the speed ball milling of 450rpm
It answers 6 hours, obtains solid powder product C ferrocyanide ferrisodium NaFeFe (CN)6。
(4) by above-mentioned by product C in vacuum drying oven 150 DEG C be heat-treated 5 hours, to remove water and optimize material lattice knot
Structure is to get the anhydrous ferric ferrocyanide sodium NaFeFe (CN) of the prussian blue sodium-ion battery positive material6。
Comparative example 1
This comparative example is related to a kind of prussian blue material, sodium ferrocyanide/conductive carbon mixing material Na4Fe(CN)6/
The preparation method of 40%C, includes the following steps:
(1) the sodium ferrocyanide Na that will be bought4Fe(CN)6With conductive carbon super p respectively 90 DEG C and 60 in vacuum drying oven
It at DEG C, heats 8 hours, removes moisture in materials, obtain anhydrous sodium ferrocyanide Na4Fe(CN)6With dry conductive carbon super
p。
(2) by above-mentioned anhydrous sodium ferrocyanide Na4Fe(CN)6It is weighed with conductive carbon super p by the mass ratio of 6:4, it is anhydrous
Sodium ferrocyanide Na4Fe(CN)6Quality be 1.8g, the quality of conductive carbon super p is 1.2g.
(3) the anhydrous sodium ferrocyanide Na for obtaining weighing4Fe(CN)6With conductive carbon super p hand in agate jar
It is dynamic to be uniformly mixed, ball grinder is sealed after appropriate agate ball milling pearl is added, with speed ball-milling reaction 5 hours of 450rpm, obtains
Product sodium ferrocyanide/conductive carbon mixing material.
(4) by above-mentioned product in vacuum drying oven 90 DEG C be heat-treated 5 hours, to remove water and optimize material lattice structure, i.e.,
Obtain the prussian blue sodium-ion battery positive material, sodium ferrocyanide/conductive carbon mixing material Na4Fe(CN)6/ 40%C.
Comparative example 2
This comparative example is related to a kind of prussian blue material, ferric ferrocyanide Fe4[Fe(CN)6]3Preparation method, including
Following steps:
(1) the Prussian blue Fe that will be bought4[Fe(CN)6]3It heats 8 hours, removes in material at 120 DEG C in vacuum drying oven
Moisture obtains anhydrous Prussian blue Fe4[Fe(CN)6]3。
(2) suitable anhydrous Prussian blue Fe is weighed4[Fe(CN)6]3Material is in agate jar, being added appropriate Ma
Ball grinder is sealed after Nao ball milling pearl, with speed ball milling 5 hours of 450rpm, raw material particle size is reduced by ball milling, improves material
Chemical property.
(4) by above-mentioned product in vacuum drying oven 150 DEG C be heat-treated 5 hours, to remove water and optimize material lattice structure, i.e.,
Obtain the prussian blue sodium-ion battery positive material ferric ferrocyanide Fe4[Fe(CN)6]3(referred in Figure of description with PB
Generation).
Comparative example 3
This comparative example is related to a kind of Prussian blue material, Na1.73Fe[Fe(CN)6]0.98Preparation method, including walk as follows
It is rapid:
(1) frerrous chloride and sodium ferrocyanide are weighed by the molar ratio of 1:1, frerrous chloride 0.01mol, ferrocyanide
Sodium is also 0.01mol, and weighed frerrous chloride and sodium ferrocyanide are dissolved in the deionized water of 100ml respectively, are configured to
The solution of ferrous chloride of 0.1mol/L and the sodium ferrocyanide solution of 0.1mol/L.
(2) 0.2mol sodium chloride is weighed, is dissolved in 200ml deionized water, the sodium chloride solution of 1mol/L is configured to.
(3) sodium chloride solution is placed on magnetic stirring apparatus and is stirred, by configured solution of ferrous chloride and ferrocyanide
Sodium solution uses peristaltic pump to be instilled in the sodium chloride solution of high-speed stirred dropwise respectively, and total time for adding is about 1.5 hours, finally
Mixed solution is made.
(4) mixed solution continues stirring 0.5 hour at room temperature.
(5) stop stirring, mixed solution stands 4 hours at room temperature.
(6) mixed solution cleaning centrifugation is obtained into white precipitate, obtains Pu Lu after the drying 12 hours of 120 DEG C of vacuum atmosphere
Scholar's indigo plant Na1.73Fe[Fe(CN)6]0.98Material.
Effect example 1
Respectively by prussian blue material made from embodiment 1, comparative example 2 and comparative example 3, with conductive carbon (mass ratio 1:1
Super P and Ketjen black) and binder Kynoar (PVDF) mixed by the mass ratio of 7:2:1, and suitable 1- is added
N-methyl-2-2-pyrrolidone N (NMP) solvent is evenly coated in mixture on aluminium foil slurry after stirring 4 hours in pulpous state, dry
It is washed into the round pole piece that diameter is 14mm with the aluminium foil that slicer is coated with black paste afterwards, then using tablet press machine to pole piece
Apply certain pressure and carry out tabletting, finally pole piece is put into vacuum drying oven, 120 DEG C are dried in vacuo 12 hours, and sodium ion is made
Battery positive pole piece.Using electrode slice obtained as working electrode, metallic sodium is used as to electrode, uses 1mol/L NaPF6/PC:
EMC:FEC (49:49:2) organic electrolyte is assembled into button cell in the glove box full of argon atmosphere.Then to battery
Electrochemical property test is carried out, test voltage range is 2.0~4.0V.
By (the sodium ferrocyanide/conductive carbon mixing material Na of prussian blue material made from comparative example 14Fe(CN)6/ 40%
C), mixed with binder Kynoar (PVDF) by the mass ratio of 9:1, after stirring 4 hours, slurry is evenly coated in aluminium foil
On, it is washed into the round pole piece that diameter is 14mm with the aluminium foil that slicer is coated with black paste after drying, then uses tabletting
Machine applies certain pressure to pole piece and carries out tabletting, and finally pole piece is put into vacuum drying oven, and 120 DEG C are dried in vacuo 12 hours, system
Obtain sodium-ion battery anode pole piece.Using electrode slice obtained as working electrode, metallic sodium is used as to electrode, uses 1mol/L
NaPF6/ PC:EMC:FEC (49:49:2) organic electrolyte is assembled into button cell in the glove box full of argon atmosphere.With
Electrochemical property test is carried out to battery afterwards, test voltage range is 2.0~4.0V.
(1) Fig. 1 is that embodiment 1 uses anhydrous Prussian blue Fe4[Fe(CN)6]3With anhydrous sodium ferrocyanide Na4Fe(CN)6
The anhydrous ferric ferrocyanide sodium NaFeFe (CN) of mixing and ball milling method preparation6Material, comparative example 1 use sodium ferrocyanide and conductive carbon
Sodium ferrocyanide/conductive carbon mixing material Na of mixing and ball milling preparation4Fe(CN)6/ 40%C and comparative example 2 are ground by heat balls
Standby anhydrous ferric ferrocyanide Fe4[Fe(CN)6]3The 0.1C rate charge-discharge cycle performance of material battery obtained respectively compares
Figure.
Comparison is found, using the anhydrous ferric ferrocyanide sodium NaFeFe (CN) of mixing and ball milling method preparation in embodiment 16Material
The 0.1C initial capacity of battery obtained is apparently higher than in comparative example 1 using sodium ferrocyanide and the preparation of conductive carbon mixing and ball milling
Sodium ferrocyanide/conductive carbon mixing material Na4Fe(CN)6The anhydrous ferrous iron prepared in/40%C and comparative example 2 by heating and ball-milling
Ferricyanide Fe4[Fe(CN)6]3The 0.1C initial capacity of battery made from material, 0.1C initial capacity are respectively 118.2mAh/
G, 83.1mAh/g, 92.6mAh/g (referring to table 1), and after 200 circle of circulation, anhydrous ferric ferrocyanide sodium NaFeFe in embodiment 1
(CN)6The capacity of battery made from material still has 94.9mAh/g, capacity retention ratio 80.3%.
Table 1
(2) Fig. 2 is that embodiment 1 uses anhydrous Prussian blue Fe4[Fe(CN)6]3With anhydrous sodium ferrocyanide Na4Fe(CN)6
The anhydrous ferric ferrocyanide sodium NaFeFe (CN) of mixing and ball milling method preparation6Material, comparative example 1 use sodium ferrocyanide and conductive carbon
Sodium ferrocyanide/conductive carbon mixing material Na of mixing and ball milling preparation4Fe(CN)6/ 40%C and comparative example 2 pass through heating and ball-milling
The anhydrous ferric ferrocyanide Fe of preparation4[Fe(CN)6]3The 1C rate charge-discharge cycle performance of material battery obtained respectively compares
Figure.
Comparison discovery, the anhydrous ferric ferrocyanide sodium NaFeFe (CN) that embodiment 1 is prepared using mixing and ball milling method6Material system
The 1C initial capacity of the battery obtained is apparently higher than in comparative example 1 using the ferrous iron of sodium ferrocyanide and the preparation of conductive carbon mixing and ball milling
Cymag/conductive carbon mixing material Na4Fe(CN)6The anhydrous ferrocyanide prepared in/40%C and comparative example 2 by heating and ball-milling
Iron Fe4[Fe(CN)6]3The 1C initial capacity of battery made from material, 1C initial capacity are respectively 96.8mAh/g, 73.6mAh/
G, 82.7mAh/g (referring to table 2), and after 1000 circle of circulation, anhydrous ferric ferrocyanide sodium NaFeFe (CN) in embodiment 16Material
The capacity of battery obtained still has 59.4mAh/g, capacity retention ratio 61.3%.
Table 2
(3) Fig. 3 is that embodiment 1 uses anhydrous Prussian blue Fe4[Fe(CN)6]3With anhydrous sodium ferrocyanide Na4Fe(CN)6
The anhydrous ferric ferrocyanide sodium NaFeFe (CN) of mixing and ball milling method preparation6Material, comparative example 3 are closed using the co-precipitation of common aqueous solution
1C rate charge-discharge cycle performance at the ferrocyanide ferrisodium prussian blue material battery obtained respectively of method preparation compares
Figure.
Comparison discovery, the anhydrous ferric ferrocyanide sodium NaFeFe (CN) that embodiment 1 is prepared using mixing and ball milling method6Material system
It is Prussian blue using the ferrocyanide ferrisodium of common synthetic method preparation that the 1C cyclical stability of the battery obtained is apparently higher than comparative example 3
The initial capacity of battery made from class material, the two is not much different, and is 100mAh/g or so, after 400 circle of circulation, embodiment 1
In anhydrous ferric ferrocyanide sodium NaFeFe (CN)6The capacity of battery made from material still has 73.7mAh/g, and capacity retention ratio is
76.1%, and the appearance of battery made from ferrocyanide ferrisodium prussian blue material of the comparative example 3 using the preparation of common synthetic method
Amount is 63.7mAh/g, and capacity retention ratio is only 60.8% (referring to table 3).
Table 3
Effect example 2
The anhydrous ferric ferrocyanide sodium NaFeFe (CN) of product made from Example 16, detect its water content and (pass through thermogravimetric
Analytic approach (TG) measurement).
Take the Prussian blue Na of product made from comparative example 31.73Fe[Fe(CN)6]0.98Material detects its water content, detection side
Method is same as above.
Concrete outcome can be found in Fig. 4.
According to Fig. 4 (thermogravimetric analysis, TG) it is found that the anhydrous ferric ferrocyanide sodium NaFeFe (CN) of product made from embodiment 16
Water content be 5%, and the Prussian blue Na of product made from comparative example 11.73Fe[Fe(CN)6]0.98The water content of material is
12%.That is, the anhydrous ferric ferrocyanide sodium NaFeFe (CN) of product made from embodiment 16Water content it is lower.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (10)
1. a kind of preparation method of prussian blue material, which is characterized in that it includes the following steps:
By anhydrous Prussian blue presoma P [R (CN)6] and anhydrous sodium material NaR (CN)6Mixing, reacts through solid-phase ball milling,
Prussian blue material Na is madexP[R(CN)6]；
Wherein, P and R are each independently selected from transition metal element,
P[R(CN)6]+NaR(CN)6→NaxP[R(CN)6]。
2. the preparation method of prussian blue material as described in claim 1, which is characterized in that the P and the R are respectively only
On the spot it is selected from Fe, Mn, Co or Ni, preferably Fe.
3. the preparation method of prussian blue material as described in claim 1, which is characterized in that the Prussian blue presoma
P[R(CN)6] it is Prussian blue Fe4[Fe(CN)6]3；
And/or the sodium material NaR (CN)6For sodium ferrocyanide Na4Fe(CN)6。
4. the preparation method of prussian blue material according to any one of claims 1 to 3, which is characterized in that the nothing
The Prussian blue presoma P [R (CN) of water6] water content be lower than 5%, percentage refers to mass percent；Preferably, the nothing
The Prussian blue presoma P [R (CN) of water6] be made by following preparation methods, by Prussian blue presoma P [R (CN)6] through adding
After heat treatment to get；
The heat treatment preferably carries out in a vacuum drying oven；
The temperature of the heat treatment is preferably 100~150 DEG C, and more preferably 120 DEG C；
The time of the heat treatment is preferably 4~12 hours, and more preferably 8 hours.
5. the preparation method of prussian blue material according to any one of claims 1 to 3, which is characterized in that the nothing
The sodium material NaR (CN) of water6Water content be lower than 5%, percentage refers to mass percent；Preferably, the anhydrous sodium material
Expect NaR (CN)6It is made by following preparation methods, by sodium material NaR (CN)6After heat-treated to get；
The heat treatment preferably carries out in a vacuum drying oven；
The temperature of the heat treatment is preferably 80~100 DEG C, and more preferable 90 DEG C；
The time of the heat treatment is preferably 4~12 hours, and more preferably 8 hours.
6. the preparation method of prussian blue material according to any one of claims 1 to 3, which is characterized in that the nothing
The sodium material NaR (CN) of water6In available extra sodium ion and the anhydrous Prussian blue presoma P [R (CN)6] energy
The sodium ion equimolar enough received；
As the Prussian blue presoma P [R (CN)6] it is Prussian blue Fe4[Fe(CN)6]3, and the sodium material NaR (CN)6For
Sodium ferrocyanide Na4Fe(CN)6When, the anhydrous Prussian blue presoma P [R (CN)6] and the anhydrous sodium material NaR
(CN)6Molar ratio be preferably 1:1.
7. the preparation method of prussian blue material according to any one of claims 1 to 3, which is characterized in that described solid
Phase ball-milling reaction carries out as follows: by the anhydrous Prussian blue presoma P [R (CN)6], the anhydrous sodium material
NaR(CN)6It is added in agate jar with agate ball milling pearl, through ball mill ball milling；
The revolving speed of the ball mill is preferably 400-500rpm, more preferably 450rpm；
The time of the ball milling is preferably 4~10 hours, and more preferably 6 hours.
8. the preparation method of prussian blue material according to any one of claims 1 to 3, which is characterized in that when described
Prussian blue material NaxP[R(CN)6] water content be higher than 5% when, by the prussian blue material NaxP[R(CN)6] warp
Water content is heat-treated to lower than 5%, percentage refers to mass percent.
9. the preparation method of prussian blue material as claimed in claim 8, which is characterized in that the temperature of the heat treatment is
150~160 DEG C, preferably 150 DEG C；
And/or the time of the heat treatment is 4~12 hours, preferably 5 hours；
As the prussian blue material NaxP[R(CN)6] it is ferrocyanide ferrisodium NaFeFe (CN)6When, the temperature of the heat treatment
Preferably 150 DEG C of degree, the time of the heat treatment is preferably 5 hours.
10. the preparation method of prussian blue material as described in claim 1, which is characterized in that will be anhydrous Prussian blue
Fe4[Fe(CN)6]3With anhydrous sodium ferrocyanide Na4Fe(CN)6Mixing, reacts through solid-phase ball milling, and ferrocyanide ferrisodium is made
NaFeFe(CN)6,
Fe4[Fe(CN)6]3+Na4Fe(CN)6→4NaFeFe(CN)6。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112777611A (en) * | 2021-01-11 | 2021-05-11 | 中国科学院过程工程研究所 | Rhombohedral phase Prussian blue derivative and preparation method and application thereof |
| CN114671468A (en) * | 2022-03-28 | 2022-06-28 | 温州大学碳中和技术创新研究院 | Preparation method and application of polyanion and Prussian blue composite positive electrode material |
| CN115172679A (en) * | 2022-05-24 | 2022-10-11 | 福州大学 | Novel composite Prussian blue derivative material synthesized by solid-liquid ball milling and application thereof |
| CN115863564A (en) * | 2022-11-22 | 2023-03-28 | 无锡零一未来新材料技术研究院有限公司 | Prussian blue composite cathode material and preparation method and application thereof |
| CN115974102A (en) * | 2022-12-26 | 2023-04-18 | 深圳华钠新材有限责任公司 | Preparation method and application of silver-carbon coated Prussian blue material |
| CN117430134A (en) * | 2023-12-21 | 2024-01-23 | 山东海化集团有限公司 | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
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| CN107634220A (en) * | 2017-08-04 | 2018-01-26 | 上海交通大学 | A kind of preparation method of prussian blue energy storage material |
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| CN107634220A (en) * | 2017-08-04 | 2018-01-26 | 上海交通大学 | A kind of preparation method of prussian blue energy storage material |
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| DEZHI YANG 等: ""Prussian blue without coordinated water as a"", 《CHEM.COMMUN.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112777611A (en) * | 2021-01-11 | 2021-05-11 | 中国科学院过程工程研究所 | Rhombohedral phase Prussian blue derivative and preparation method and application thereof |
| CN112777611B (en) * | 2021-01-11 | 2023-01-31 | 中国科学院过程工程研究所 | Rhombohedral phase Prussian blue derivative and preparation method and application thereof |
| CN114671468A (en) * | 2022-03-28 | 2022-06-28 | 温州大学碳中和技术创新研究院 | Preparation method and application of polyanion and Prussian blue composite positive electrode material |
| CN114671468B (en) * | 2022-03-28 | 2023-11-07 | 温州大学碳中和技术创新研究院 | Preparation method and application of polyanion and Prussian blue composite positive electrode material |
| CN115172679A (en) * | 2022-05-24 | 2022-10-11 | 福州大学 | Novel composite Prussian blue derivative material synthesized by solid-liquid ball milling and application thereof |
| CN115863564A (en) * | 2022-11-22 | 2023-03-28 | 无锡零一未来新材料技术研究院有限公司 | Prussian blue composite cathode material and preparation method and application thereof |
| CN115974102A (en) * | 2022-12-26 | 2023-04-18 | 深圳华钠新材有限责任公司 | Preparation method and application of silver-carbon coated Prussian blue material |
| CN117430134A (en) * | 2023-12-21 | 2024-01-23 | 山东海化集团有限公司 | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
| CN117430134B (en) * | 2023-12-21 | 2024-04-05 | 山东海化集团有限公司 | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
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