CN109638241A - Ultra-fine iron-based Prussian blue and the like, preparation method and sodium-ion battery - Google Patents
Ultra-fine iron-based Prussian blue and the like, preparation method and sodium-ion battery Download PDFInfo
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- CN109638241A CN109638241A CN201811459139.7A CN201811459139A CN109638241A CN 109638241 A CN109638241 A CN 109638241A CN 201811459139 A CN201811459139 A CN 201811459139A CN 109638241 A CN109638241 A CN 109638241A
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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
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention discloses a kind of ultra-fine iron-based Prussian blue and the like preparation methods, include the following steps: S1: sodium ferrocyanide and metal salt are added in ball-milling device；S2: suitable solvent is added in the ball-milling device；S3: mixed raw material is placed in ball milling in the ball-milling device；S4: the obtained mixture of step S3 is cleaned with dehydrated alcohol and deionized water；S5: the product after cleaning is dried, and is prepared iron-based Prussian blue and the like.The invention also discloses its corresponding iron-based Prussian blue and the like and sodium-ion batteries.Ultra-fine iron-based Prussian blue and the like preparation method of the invention, using the solid-to-liquid ratio for being greater than 50%, reaction is promoted to carry out by ball milling method, therefore this method yield is high, suitable for large-scale production, and ultra-fine iron-based Prussian blue and the like partial size is less than 100nm, is applied to sodium-ion battery positive material, with having extended cycle life, the features such as good rate capability.
Description
Technical field
The invention belongs to Prussian blue and the like preparation technical fields, more particularly, to a kind of ultra-fine iron-based
Prussian blue and the like preparation method and its application in terms of sodium-ion battery positive material.
Background technique
Sodium-ion battery has the characteristics that cost of material is low, resourceful, chemical property potentiality are big, therefore is expected to big
Scale energy storage field is applied, and is one of the important research direction of next-generation battery technology.Currently, the anode of sodium-ion battery
Material mainly includes transition metal oxide, phosphate, prussian blue material etc..Wherein, prussian blue material has electricity
Flattening bench is compared with high (> 3V), ion channel is big, specific capacity is big (~170mAh g-1), non-toxic inexpensive the advantages that easily preparing and become sodium
The research hotspot of ion battery positive electrode.
Iron-based Prussian blue and the like (PBAs, Na2M[Fe(CN)6], M=Fe, Co, one kind or group of Mn, Ni etc.
Close) usually there is face-centred cubic structure.In its cubic lattice, M2+With the N sixfold coordination in CN ligand, Fe2+In CN ligand
The coordination of C sixfold, form a 3D rigid frame, this makes Prussian blue and the like there are spacious lattice voids to accommodate
Sodium ion, and open transmission channel carry out the reversible transmission of sodium ion.
Currently, the synthesis of PBAs generallys use water phase coprecipitation and hydro-thermal method, patent document CN103474659B is disclosed
A kind of preparation method and application of sodium-ion battery positive material, and the Prussian blue complex for specifically disclosing its offer is multiple
Condensation material preparation method includes at least: transition metal salt, acid are dispersed in water with reducing agent obtains reaction solution, will be described
Solution is heated after a period of time under protective atmosphere up to the Prussian blue analogues material.This method is in order to guarantee product
Crystalline quality, reactant concentration is generally lower in the above method, leads to low yield, is not suitable for large-scale production.In addition, using
The PBAs particle size of mild liquid phase reactor synthesis is commonly greater than 200nm, and the native electronic conductivity of PBAs is very low
(4.08×10-9S cm-1), dynamic performance is poor when leading to it as sodium-ion battery positive material.Therefore, one kind is found
The synthesis technology of large-scale production PBAs, and promote it and store up sodium dynamic performance, it is extremely important to its practical application.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of ultra-fine iron-based Prussian blue and its class
It like the preparation method of object, uses sodium ferrocyanide and metal salt as raw material, grain has been prepared by the method for ball milling
Diameter is less than the ultra-fine PBAs of 100nm, when being used as sodium-ion battery anode, with long circulation life, the features such as high rate capability.
To achieve the goals above, according to one aspect of the present invention, a kind of ultra-fine iron-based Prussian blue and its class is provided
Like the preparation method of object, include the following steps:
S1: sodium ferrocyanide and metal salt are added in ball-milling device；
S2: suitable solvent is added in the ball-milling device；
S3: mixed raw material is placed in ball milling in the ball-milling device；
S4: the obtained mixture of step S3 is cleaned with dehydrated alcohol and deionized water；
S5: the product after cleaning is dried, and is prepared iron-based Prussian blue and the like.
Further, the revolving speed of ball milling described in step S3 be 100r/min~5000r/min, Ball-milling Time be 1min~
48 hours.
Further, the temperature of ball milling described in step S3 is 0 DEG C~80 DEG C.
Further, the partial size of mixture described in step S4 is less than or equal to 100nm.
Further, the sodium ferrocyanide and metal salt are containing the crystallization water or to be free of the crystallization water, molar ratio 1:0.5
~1:1.5.
Further, the solvent can be water or acetonitrile, ethyl alcohol, glycerol or other organic solvents.
Further, the weight ratio of the gross weight and solvent of the sodium ferrocyanide and metal salt is 100:0~100:
100。
Further, the metal salt includes metal chloride, metal sulfate or perchlorate, wherein the metal chlorine
Salt includes FeCl2、CoCl2、MnCl2One or more of them, the metal sulfate include FeSO4、CoSO4、MnSO4Wherein one
Kind is a variety of, and the perchlorate includes Fe (ClO4)2、Mn(ClO4)2、Co(ClO4)2One or more of them.
Other side according to the invention provides a kind of ultra-fine iron-based Prussian blue and the like, which is characterized in that
It is prepared using described ultra-fine iron-based Prussian blue and the like the preparation method, and described ultra-fine iron-based Prussian blue
And the like particle size be less than 100nm.
Other side according to the invention provides a kind of sodium-ion battery, including anode, cathode, electrolyte and diaphragm,
The positive electrode is ultra-fine iron-based Prussian blue and the like as claimed in claim 9.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) ultra-fine iron-based Prussian blue and the like preparation method of the invention, using the solid-to-liquid ratio for being greater than 50%,
Promote reaction to carry out by ball milling method, therefore this method yield is high, is suitable for large-scale production.
(2) ultra-fine iron-based Prussian blue and the like preparation method of the invention, ultra-fine PBAs partial size are less than
The features such as 100nm is applied to sodium-ion battery positive material, has and has extended cycle life, good rate capability.
(3) ultra-fine iron-based Prussian blue and the like preparation method of the invention, the revolving speed of ball milling is 100r/min
~5000r/min, Ball-milling Time is 1min~48 hour, so that sodium ferrocyanide and metal salt mixture are sufficiently ground
Mill, powder particle is uniform in size, and is ultra-fine circular granular, guarantees that its partial size is less than or equal to 100nm.
(4) ultra-fine iron-based Prussian blue and the like preparation method of the invention, controls according to the volatility of solvent
For the temperature of ball milling at 0 DEG C~80 DEG C, sodium ferrocyanide and metal salt mixture can be further speeded up ground by improving temperature
Reaction rate in journey substantially increases iron-based Prussian blue and the like preparation efficiency.
(5) of the invention ultra-fine iron-based Prussian blue and the like, partial size is less than 100nm, this size ratio is in water
Prussian blue and the like the particle prepared in solution wants small.
(6) sodium-ion battery of the invention, charging capacity are up to 130mAh/g, and discharge capacity has reached 116mAh/g, and
And there is excellent stable circulation performance and high rate performance.
Detailed description of the invention
Fig. 1 is the XRD curve graph in the embodiment of the present invention 1 after ball milling before product washing；
Fig. 2 is the XRD curve graph in the embodiment of the present invention 1 after ball milling after product washing；
Fig. 3 is the NaxFe [Fe (CN) that the embodiment of the present invention 1 synthesizes6] scanning electron microscope (SEM) photograph；
Fig. 4 is the NaxFe [Fe (CN) that the embodiment of the present invention 1 synthesizes6] transmission electron microscope picture；
Fig. 5 is the NaxFe [Fe (CN) synthesized with the embodiment of the present invention 16] as sodium-ion battery anode charge and discharge it is bent
Line；
Fig. 6 is the NaxFe [Fe (CN) synthesized with the embodiment of the present invention 16] cycle performance as sodium-ion battery anode
Figure；
Fig. 7 is the NaxFe [Fe (CN) synthesized with the embodiment of the present invention 16] high rate performance as sodium-ion battery anode
Figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below that
Not constituting conflict between this can be combined with each other.
The present invention provides a kind of ultra-fine iron-based Prussian blue and the like preparation method, comprising the following steps:
(1) sodium ferrocyanide and metal salt are added in ball-milling device；
(2) suitable solvent is added in the ball-milling device；
(3) mixed raw material is placed in ball milling in the ball-milling device；
(4) obtained PBAs is cleaned with dehydrated alcohol and deionized water.
(5) product after cleaning is dried.
Ultra-fine iron-based Prussian blue and the like preparation method of the invention, does not limit ball grinder size, ball milling side
Formula and Ball-milling Time.Metal salt includes metal chloride (FeCl2、CoCl2、MnCl2Deng), metal sulfate (FeSO4、CoSO4With
MnSO4Deng) or perchlorate (Fe (ClO4)2、Mn(ClO4)2、Co(ClO4)2) etc., the sodium ferrocyanide and metal salt being added
The crystallization water can be contained or without the crystallization water, molar ratio is 1:0.5~1:1.5:.The solvent being added can for water or acetonitrile, ethyl alcohol,
The weight ratio of the organic solvents such as glycerol, raw material and solvent can be 100/0 to 100/100.
Ball milling method includes planetary ball mill, vibrator, agitated ball mill, horizontal sand mill etc., essence
On be the progress for accelerating reaction by the shock, extruding, abrasive action of ball milling pearl, and refinement is played to the partial size of reaction product
Effect.The revolving speed of different ball milling methods is different, for example, planetary ball mill revolving speed usually in 100~300rpm, vibratory milling
The revolving speed of machine is usually in 1000~2000rpm, and for the revolving speed of agitating ball mill usually in 50~150rpm, the revolving speed of sand mill is usual
In 1000~5000rpm etc..
Ultra-fine iron-based Prussian blue and the like preparation method of the invention, the revolving speed of ball milling be 100r/min~
5000r/min, Ball-milling Time is 1min~48 hour, so that sodium ferrocyanide and metal salt mixture are fully ground,
Powder particle is uniform in size, and is ultra-fine circular granular, guarantees that its partial size is less than or equal to 100nm.
Embodiment 1
S1: being hydrated sodium ferrocyanide for 4mmol ten and 6mmol Iron dichloride tetrahydrate be placed in nylon ball grinder, with
The rate of 1200r/min vibrates mixing 1min.
S2: in the glove box full of Ar, above-mentioned raw materials are placed in agate jar, ratio of grinding media to material 1:20.
S3: agate jar is placed in planetary ball mill the 12h that dry grinds, revolving speed 300r/min.
S4: after ball milling, after product dehydrated alcohol and deionized water are washed, in 80 DEG C of baking 36h of vacuum drying oven, i.e.,
Obtain the Na containing the crystallization waterxFe[Fe(CN)6。
Fig. 1 be this embodiment ball milling after non-washed product XRD diffracting spectrum, by with Na4Fe(CN)6Standard PDF card
Piece compares (JCPDS-1-1026), it can be seen that does not contain Na in the non-washed product after ball milling4Fe(CN)6, this illustrates that ball milling is anti-
It should be complete.Fig. 2 be embodiment 1 in washed product XRD diffracting spectrum, by with Fe4[Fe(CN)6]3Standard PDF card pair
Than (JCPDS-1-0239), it can be seen that washed product is pure Prussian blue (NaxFe[Fe(CN)6]).Fig. 3 is embodiment 1
Prepared NaxFe[Fe(CN)6] scanning electron microscope (SEM) photograph as can be seen that prepared powder particle is uniform in size in figure be super
Thin circular granular.Fig. 4 is Na prepared by embodiment 1xFe[Fe(CN)6] transmission electron microscope picture, from transmission electron microscope picture
It can be seen that powder primary particle size is in 50nm hereinafter, this size is more Prussian blue and its similar than what is prepared in aqueous solution
Composition granule wants small.
The Na that this embodiment 1 is obtainedxFe[Fe(CN)6] tested applied to sodium-ion battery anode, it obtains as schemed
5, Fig. 6 and experimental data shown in Fig. 7.Fig. 5 is the 1st circle charging and discharging curve figure, and charging and discharging currents density is in this experiment
170mA/g.It can be seen from the figure that the charging capacity of the material has reached 130mAh/g, discharge capacity reaches 116mAh/g.Figure
6 be Na prepared by embodiment 1xFe[Fe(CN)6] it is applied to the cyclicity tested after the assembled battery of sodium-ion battery anode
It can scheme, it can be seen from the figure that as sodium-ion battery anode, NaxFe[Fe(CN)6] show excellent cyclical stability,
After 100 circle of circulation, discharge capacitance 84%, capacity retention ratio is 78.6% after circulation 200 is enclosed, after 500 circle of circulation
Capacity retention ratio is 70.3%, and capacity retention ratio is 62.6% after 1000 circle of circulation.Fig. 7 is Na prepared by embodiment 1xFe
[Fe(CN)6] it is applied to the high rate performance figure tested after the assembled battery of sodium-ion battery anode.It can be seen from the figure that making
For sodium-ion battery anode, prepared NaxFe[Fe(CN)6] show excellent high rate performance.In 0.2C, that is, 35mA/g electric current
Under, NaxFe[Fe(CN)6] discharge capacity is 111mAh/g, and under the high current of 30C, that is, 5000mA/g, discharge capacity is still protected
It holds in 97mAh/g or so, conservation rate is 87.3%.
Embodiment 2
S1: the anhydrous sodium ferrocyanide of 4mmol and the anhydrous protochloride manganese of 4mmol are placed in nylon ball grinder, with 800r/
The rate of min vibrates mixing 1min.
S2: 20ml acetonitrile is added in ball grinder.
S3: continue vibratory milling 30min, vibration rate 1200r/min on vibrator.
S4: after ball milling, product being filtered, after being washed with dehydrated alcohol, in 80 DEG C of baking 36h of vacuum drying oven to get arriving
Na without the crystallization waterxMn[Fe(CN)6。
Embodiment 3
S1: 2L deionized water is added in (belt stirrer) in the circulating tank of horizontal sand mill；
S2: ten water sodium ferrocyanide of 4mol is added in circulating tank, stirring to dissolution；
S3: then six water cobalt chloride of 6mol is added in circulating tank, ball by starting horizontal sand mill, revolving speed 3000rpm
Time consuming 2 hours.
S4: after ball milling, product being filtered, after being washed respectively with deionized water and dehydrated alcohol, in vacuum drying oven 80
DEG C dry 36h to get arrive the Na containing the crystallization waterxCo[Fe(CN)6。
The solid-to-liquid ratio greater than 50% can be used in preparation method of the present invention, promotes reaction to carry out by ball milling method, therefore should
Method yield is high, is suitable for large-scale production.As described in Example 1, even if in the absence of a solvent, can also be produced
Object.In addition, the ultra-fine PBAs partial size that the present invention synthesizes is less than 100nm, it is applied to sodium-ion battery positive material, has and follow
The features such as ring service life is long, good rate capability.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of ultra-fine iron-based Prussian blue and the like preparation method, which comprises the steps of:
S1: sodium ferrocyanide and metal salt are added in ball-milling device；
S2: suitable solvent is added in the ball-milling device；
S3: mixed raw material is placed in ball milling in the ball-milling device；
S4: the obtained mixture of step S3 is cleaned with dehydrated alcohol and deionized water；
S5: the product after cleaning is dried, and is prepared iron-based Prussian blue and the like.
2. the ultra-fine iron-based Prussian blue preparation method of one kind according to claim 1, which is characterized in that institute in step S3
The revolving speed for stating ball milling is 100r/min~5000r/min, and Ball-milling Time is 1min~48 hour.
3. the ultra-fine iron-based Prussian blue preparation method of one kind according to claim 1 or 2, which is characterized in that step S3
Described in ball milling temperature be 0 DEG C~80 DEG C.
4. the ultra-fine iron-based Prussian blue preparation method of one kind according to any one of claim 1-3, which is characterized in that
The partial size of mixture described in step S4 is less than or equal to 100nm.
5. the ultra-fine iron-based Prussian blue preparation method of one kind described in any one of -4 according to claim 1, which is characterized in that
The sodium ferrocyanide and metal salt are containing the crystallization water or to be free of the crystallization water, and molar ratio is 1:0.5~1:1.5.
6. the ultra-fine iron-based Prussian blue preparation method of one kind according to any one of claims 1-5, which is characterized in that
The solvent can be water or acetonitrile, ethyl alcohol, glycerol or other organic solvents.
7. the ultra-fine iron-based Prussian blue preparation method of one kind according to claim 1 to 6, which is characterized in that
The weight ratio of the gross weight and solvent of the sodium ferrocyanide and metal salt is 100:0~100:100.
8. the ultra-fine iron-based Prussian blue preparation method of one kind described in any one of -7 according to claim 1, which is characterized in that
The metal salt includes metal chloride, metal sulfate or perchlorate, wherein the metal chloride includes FeCl2、CoCl2、
MnCl2One or more of them, the metal sulfate include FeSO4、CoSO4、MnSO4One or more of them, the high chlorine
Hydrochlorate includes Fe (ClO4)2、Mn(ClO4)2、Co(ClO4)2One or more of them.
9. a kind of ultra-fine iron-based Prussian blue and the like, which is characterized in that application is as described in any one of claim 1-8
Ultra-fine iron-based Prussian blue and the like preparation method be prepared, and it is described ultra-fine iron-based Prussian blue and its similar
The particle size of object is less than 100nm.
10. a kind of sodium-ion battery, including anode, cathode, electrolyte and diaphragm, which is characterized in that the positive electrode is such as
It is ultra-fine iron-based Prussian blue and the like described in claim 9.
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| CN111029572A (en) * | 2019-12-10 | 2020-04-17 | 中国科学院过程工程研究所 | Prussian-like blue derivative and preparation method and application thereof |
| CN113479911A (en) * | 2021-06-21 | 2021-10-08 | 华中科技大学 | Iron-based Prussian blue, 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 |
| CN114709402A (en) * | 2022-04-21 | 2022-07-05 | 温州大学碳中和技术创新研究院 | Preparation and application of carbon-coated sodiumsulverine-based Prussian blue positive electrode material |
| CN115448327A (en) * | 2022-09-29 | 2022-12-09 | 广东邦普循环科技有限公司 | Preparation method and application of low-defect prussian blue cathode material |
| CN117430135A (en) * | 2023-12-21 | 2024-01-23 | 山东海化集团有限公司 | Method for synthesizing ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
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| CN115448327A (en) * | 2022-09-29 | 2022-12-09 | 广东邦普循环科技有限公司 | Preparation method and application of low-defect prussian blue cathode material |
| CN115448327B (en) * | 2022-09-29 | 2024-03-12 | 广东邦普循环科技有限公司 | Preparation method and application of low-defect Prussian blue positive electrode material |
| CN117430135A (en) * | 2023-12-21 | 2024-01-23 | 山东海化集团有限公司 | Method for synthesizing ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
| CN117430135B (en) * | 2023-12-21 | 2024-04-05 | 山东海化集团有限公司 | Method for synthesizing ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
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