CN108258239A - A kind of sodium-ion battery positive material and its preparation method and application - Google Patents
A kind of sodium-ion battery positive material and its preparation method and application Download PDFInfo
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- CN108258239A CN108258239A CN201810047817.2A CN201810047817A CN108258239A CN 108258239 A CN108258239 A CN 108258239A CN 201810047817 A CN201810047817 A CN 201810047817A CN 108258239 A CN108258239 A CN 108258239A
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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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 present invention provides a kind of sodium-ion battery positive materials and its preparation method and application.Positive electrode provided by the invention includes the Prussian blue of doping, and described Prussian blue containing sodium element, the positive electrode is not aqueous.Method for preparing anode material provided by the invention includes the following steps：(1) hybrid manipulation is carried out to solution A and solution B, obtains suspension, the solution A is sodium ferrocyanide and the mixed solution of sodium chloride, and the solution B is doped source and the mixed solution of complexing agent；(2) suspension for obtaining step (1) carries out separation of solid and liquid, takes solid and drying, obtains the positive electrode.It is excellent that sodium-ion battery positive material provided by the invention is presented univoltage platform, charge-discharge performance, and because its not aqueous, anode be especially suitable for solid-state sodium-ion battery.Method for preparing anode material simple process and low cost provided by the invention is honest and clean, suitable for commercial application.
Description
Technical field
The invention belongs to new energy materials fields, are related to a kind of sodium-ion battery positive material and preparation method thereof and use
On the way.
Background technology
Recently as lithium ion battery from portable electronic device to high-power electric automobile, extensive energy-accumulating power station and
The gradual development of intelligent grid etc. and application, lithium ion battery demand increasingly increase, but limited lithium resource limit lithium from
The sustainable development of sub- battery.And sodium rich reserves, sodium-ion battery will be lithium ion batteries in extensive stored energy application
Important supplement.Sodium is located at same main group with lithium, and chemical property is similar, therefore constructs the sodium similar to lithium ion battery operation principle
Ion battery is feasible.
However, either lithium ion battery or sodium-ion battery, the safety problem in charge and discharge process is most prominent
Problem.And this safety problem is solved, one of the most effective ways are exactly to develop solid ionic battery.And positive electrode is often right
There is decisive role in the cost and performance of ion secondary battery.High-performance, novel anode material at low cost are developed for hair
Solid secondary batteries are opened up, are equally the hot spots of academia.Prussian blue material can be used for reversible deintercalation sodium ion, such material
Material forms battery system with liquid electrolyte, has there is many reports, and theoretical capacity is up to 170mAh/g, and stores up sodium current potential and put down
Platform is higher (high platform 3.34V, low platform 2.96V), therefore is considered as one of extremely promising positive electrode.However Prussia
Blue and its derivative is numerous, common are that ferrimanganic base is Prussian blue, Ni-based Prussian blue, copper-based Prussian blue, the iron cobalt-based of iron of iron
It is Prussian blue, iron iron-based is Prussian blue, iron zinc-base is Prussian blue etc..And these Prussian blue ratios in liquid sodium-ion battery
Capacity is irregular, and also difference is very big for cycle performance.In addition, in the Prussian blue positive electrode reported for work at present, it can not
Accomplish to be entirely free of water, and aqueous electrode material is difficult to use in solid state battery.
CN106920964A discloses a kind of prussian blue sodium-ion battery anode of transition metal element gradient substitution
Material and preparation method thereof.The material replaces Prussia's aquamaine from transition metal element from intra-die to surface by concentration gradient
Iron ion in lattice in iron nitrogen octahedron, molecular formula NaxMyFe1-y[Fe(CN)6]z·nH2O, M are substituted element.The program
Contain the crystallization water in the prussian blue sodium-ion battery positive material of offer, it is difficult to be applied in solid-state sodium-ion battery.
Therefore, develop a kind of prussian blue positive electrode that can be applied in solid-state sodium-ion battery has in this field
Important meaning.
Invention content
For above-mentioned deficiency in the prior art, the purpose of the present invention is to provide a kind of sodium-ion battery anode materials
Material and its preparation method and application.Sodium-ion battery positive material provided by the invention is not aqueous, excellent electrochemical performance, prepares
It is of low cost, it can be applied in solid-state sodium-ion battery.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of positive electrode, the positive electrode includes the Prussian blue of doping, described general
Shandong scholar's indigo plant contains sodium element, and the positive electrode is not aqueous.
The Prussian blue sodium-ion battery positive material fault of construction of doping provided by the invention is few, and crystallization is complete, therefore
It can accomplish to be free of any type of water, that is, both do not contained Free water or do not contained the crystallization water.This characteristic causes the present invention to carry
The positive electrode of confession can meet the requirement of solid-state sodium-ion battery.
Below as currently preferred technical solution, but not as the limitation to technical solution provided by the invention, lead to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, the substance adulterated in the positive electrode is divalent transition metal element.
Preferably, the divalent transition metal element includes manganese element, cobalt element, nickel element, copper, Zn-ef ficiency or iron
In element any one or at least two combination, it is typical but be non-limiting combination and have：The group of manganese element and cobalt element
It closes, the combination of nickel element and copper, combination of Zn-ef ficiency and ferro element etc..
As currently preferred technical solution, the molecular formula of the positive electrode is NaxMyFez(CN)6, wherein M is two
Valency transition metal element, 1≤x≤2, such as 1,1.2,1.4,1.6,1.8 or 2 etc., it is not limited to cited numerical value, it should
Other unrequited numerical value are equally applicable in numberical range；0.5≤y≤1, such as 0.5,0.6,0.7,0.8,0.9 or 1 etc., but
It is not limited in cited numerical value, other unrequited numerical value are equally applicable in the numberical range；X+2 (y+z)≤6, such as x
+ 2 (y+z) are 4,4.5,5,5.5 or 6 etc., as x+2 (y+z)=6, almost without defect, and as the deviation of distance 6 becomes larger,
It can defective generation.In the present invention, z >=0.
Second aspect, the present invention provide a kind of preparation method of positive electrode as described in relation to the first aspect, the preparation method
Include the following steps：
(1) hybrid manipulation is carried out to solution A and solution B, obtains suspension, the solution A is sodium ferrocyanide and chlorination
The mixed solution of sodium, the solution B are doped source and the mixed solution of complexing agent；
(2) suspension for obtaining step (1) carries out separation of solid and liquid, takes solid and drying, obtains the positive electrode.
In the present invention, the addition of sodium chloride and complexing agent, for finally obtaining water-free sodium-ion battery positive material
It plays an important role, they play slow releasing function in Prussian blue forming process, slow down in hybrid manipulation and hang
The speed of supernatant liquid crystallization so that the positive electrode defect finally obtained is few, and crystallinity is high, exactly because these characteristics, just cause
The positive electrode that the preparation method of the present invention obtains can realize dry water removal, obtain the anode material that can meet solid state battery requirement
Material.
As currently preferred technical solution, in step (1) described suspension, the mass concentration of sodium chloride is 1wt%-
10wt%, such as 1wt%, 2wt%, 4wt%, 6wt%, 8wt% or 10wt% etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range.In the present invention, the ultimate density pair of sodium chloride in the reaction system
There is larger impact in the Prussian blue electrode anode material of generation, if the mass concentration of sodium chloride is less than in the suspension
1wt%, the Prussian blue sodium content that can lead to generation is relatively low, if the mass concentration of sodium chloride is higher than in the suspension
10wt%, what can be resulted in Prussian blue has dephasign.
Preferably, in step (1) described solution A, a concentration of 0.02mol/L-0.2mol/L of sodium ferrocyanide, such as
0.02mol/L, 0.06mol/L, 0.08mol/L, 0.1mol/L, 0.15mol/L or 0.2mol/L etc., it is not limited to listed
The numerical value of act, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, step (1) described sodium ferrocyanide is ten hydration sodium ferrocyanides.
Preferably, the solvent of step (1) described solution A is water, preferably deionized water.
Preferably, step (1) described doped source is divalent transition metal salt.
Preferably, the divalent transition metal salt includes divalent transition metal chloride and/or divalent transition metal sulfuric acid
Salt.In the present invention, the divalent transition metal chloride and/or divalent transition metal sulfate refer to：It can be divalent transitional
Metal chloride, or divalent transition metal sulfate can also be divalent transition metal chloride and divalent transitional gold
Belong to the combination of sulfate.
Preferably, the divalent transition metal salt includes arbitrary in manganese salt, cobalt salt, nickel salt, mantoquita, zinc salt or ferrous salt
It is a kind of or at least two combination, it is typical but be non-limiting combination and have：The group of the combination of manganese salt and cobalt salt, nickel salt and mantoquita
It closes, combination of zinc salt and ferrous salt etc..
Preferably, in step (1) described solution B, a concentration of 0.02mol/L-0.2mol/L of doped source, such as
0.02mol/L, 0.06mol/L, 0.08mol/L, 0.1mol/L, 0.15mol/L or 0.2mol/L etc., it is not limited to listed
The numerical value of act, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, step (1) described complexing agent includes sodium citrate, ethylenediamine tetra-acetic acid (EDTA), acetic acid or sulfo group water
In poplar acid any one or at least two combination, typical but unrestricted combination has：Sodium citrate and ethylenediamine tetrem
The combination of sour (EDTA), the combination of ethylenediamine tetra-acetic acid (EDTA) and acetic acid, combination of acetic acid and sulfosalicylic acid etc..
Preferably, the molar ratio of step (1) complexing agent and doped source is 1:1-2:1, such as 1:1、1.2:1、1.4:
1、1.6:1、1.8:1 or 2:1 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are same
Sample is applicable in.
Preferably, in step (1) described solution B, solvent is water, preferably deionized water.
It is sub- in the system being mixed to form in solution A and solution B in step (1) as currently preferred technical solution
The molar ratio of the sodium ferricyanide and doped source is 1-3, such as 1,1.5,2,2.5 or 3 etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range.
Preferably, the temperature of step (1) described hybrid manipulation be 25 DEG C -70 DEG C, such as 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C,
50 DEG C, 60 DEG C or 70 DEG C etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally suitable
With.
Preferably, step (1) described hybrid manipulation carries out under agitation.
Preferably, the rate of the stirring is 300rpm-1000rpm, such as 300rpm, 500rpm, 700rpm, 900rpm
Or 1000rpm etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, solution A and solution B is are added drop-wise in aqueous solution by step (1) described hybrid manipulation dropwise.The present invention
In, it can be preferably so that each material be uniformly mixed and controls crystallization rate so as not to too fast by the way of dropwise addition.
Preferably, the aqueous solution is water.
Preferably, the rate of addition of solution A and the rate of addition of solution B independently are 0.1mL/min-1mL/min, such as
0.1mL/min, 0.2mL/min, 0.4mL/min, 0.6mL/min, 0.8mL/min or 1mL/min etc., it is not limited to listed
The numerical value of act, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the rate of addition of solution A and the rate of addition of solution B are identical.
As currently preferred technical solution, in step (1), further include：Hydro-thermal reaction is carried out to the suspension.This
In invention, suspension is handled using the method for hydro-thermal reaction, the crystallinity for the positive electrode that can be further promoted makes it
Fault of construction is less, and performance is more preferable.
Preferably, the temperature of the hydro-thermal reaction be 150 DEG C -200 DEG C, such as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
190 DEG C or 200 DEG C etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the time of the hydro-thermal reaction is 15h-24h, such as 15h, 18h, 20h, 22h or for 24 hours etc., but not
Cited numerical value is only limitted to, other unrequited numerical value are equally applicable in the numberical range.
Preferably, the hydro-thermal reaction carries out in water heating kettle.
As currently preferred technical solution, in step (2), the separation of solid and liquid is centrifuges or filters separation.
Preferably, step (2) further includes：Separation of solid and liquid is washed with water before being dried and obtains solid.
Preferably, in step (2), the drying carries out in vacuum drying chamber.
Preferably, in step (2), the temperature of the drying is 100 DEG C -120 DEG C, for example, 100 DEG C, 105 DEG C, 110 DEG C,
115 DEG C or 120 DEG C etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, in step (2), time of the drying is -48h for 24 hours, for example, for 24 hours, 28h, 32h, 36h, 40h, 44h
Or 48h etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, in step (2), the vacuum degree of the drying is 10mTorr-15mTorr, such as 10mTorr,
11mTorr, 12mTorr, 13mTorr, 14mTorr or 15mTorr etc., it is not limited to cited numerical value, the numerical value model
Other unrequited numerical value are equally applicable in enclosing.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) under conditions of 25 DEG C -70 DEG C and rate are the stirring of 300rpm-1000rpm, by solution A and solution B with
The rate of addition of 0.1mL/min-1.0mL/min is added drop-wise in water, and solution A is identical with the rate of addition of solution B, waits to drip
Entirely, obtained suspension is placed in water heating kettle in 150 DEG C of -200 DEG C of hydro-thermal reaction 15h-24h, obtained outstanding after hydro-thermal reaction
Supernatant liquid；The solution A is dissolved into water for ten hydration sodium ferrocyanides and sodium chloride and forms mixed solution, and the solution B is mixes
Miscellaneous source and complexing agent are dissolved into the mixed solution formed in water, and the doped source is divalent transition metal chloride and/or divalent
Transition metal sulfate；
(2) separation is centrifuged or filtered to the suspension after step (1) described hydro-thermal reaction, take solid, and right
The solid of acquirement dry -48h for 24 hours under 100 DEG C -120 DEG C and 10mTorr-15mTorr of vacuum degree in vacuum drying chamber,
Obtain the positive electrode；
Wherein, in step (1) described suspension, the mass concentration of sodium chloride is 1wt%-10wt%；It is ferrous in solution A
A concentration of 0.02mol/L-0.2mol/L of Cymag；In solution B, a concentration of 0.02mol/L- of divalent transition metal ion
The molar ratio of 0.2mol/L, complexing agent and divalent transition metal ion is 1:1-2:1；In the body that solution A and solution B are mixed to form
In system, the molar ratio of sodium ferrocyanide and divalent transition metal ion is 1-3.
The third aspect, the present invention provide a kind of purposes of positive electrode as described in relation to the first aspect, and the positive electrode is used for
The anode of solid-state sodium-ion battery.
Compared with the prior art, the present invention has the advantages that：
(1) sodium-ion battery positive material crystallinity provided by the invention is high, and defect is few, and univoltage platform, charge and discharge is presented
Excellent electrical property, and because its not aqueous, anode be especially suitable for solid-state sodium-ion battery.
(2) method for preparing anode material simple process and low cost provided by the invention is honest and clean, can be with suitable for commercial application
The preparation of the positive electrode applied to other prussian blues is generalized to, synthesized material can also be generalized to other solid-states two
In the application of primary cell.
Description of the drawings
Fig. 1 is the scanning electricity of the positive electrode that is obtained after centrifugation before it is dried in 2 step of the embodiment of the present invention (2)
Sub- microscope (SEM) picture；
Fig. 2 is the scanning electron microscope (SEM) of dried positive electrode that the embodiment of the present invention 2 is finally prepared
Picture；
Fig. 3 is in 2 step of the embodiment of the present invention (2), and the positive electrode obtained after centrifugation is fabricated to electricity before it is dried
The all charging and discharging curves of head behind pond；
Fig. 4 is that the dried positive electrode that is finally prepared of the embodiment of the present invention 2 is fabricated to filling in first week after battery
Discharge curve.
Specific embodiment
For the present invention is better described, technical scheme of the present invention is easy to understand, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
But non-limiting example typical for the present invention below：
Embodiment 1
The present embodiment provides a kind of preparation method of positive electrode, specific method is：
(1) under the stirring condition of 25 DEG C and rate for 500rpm, solution A and solution B are with the dropwise addition of 0.5mL/min speed
Degree is added drop-wise in water, is waited to be added dropwise completely, is obtained suspension；The solution A is dissolved into for ten hydration sodium ferrocyanides and sodium chloride
Mixed solution is formed in water, the solution B is dissolved into the mixed solution formed in water for cobalt chloride and complexing agent sodium citrate；
(2) step (1) described suspension is centrifuged, takes solid, and to the solid of acquirement in vacuum drying chamber
In under the vacuum degree of 100 DEG C and 10mTorr dry 48h, obtain the positive electrode；
Wherein, in step (1) described suspension, the mass concentration of sodium chloride is 1wt%, in solution A, sodium ferrocyanide
A concentration of 0.02mol/L；In solution B, Co2+A concentration of 0.02mol/L, complexing agent sodium citrate and Co2+Molar ratio be
1.5:1；In the system being mixed to form in solution A and solution B, sodium ferrocyanide and Co2+Molar ratio be 2.
The molecular formula of solid-state sodium-ion battery positive material that the present embodiment obtains is Na1.68Co0.95Fe1.0(CN)6, crystallization
Degree is high, and defect is few, not aqueous.
It is excellent that univoltage platform, charge-discharge performance is presented in the positive electrode that the present embodiment obtains.
The positive electrode that the present embodiment obtains can be with amorphous carbon material, Na0.66[Li0.22Ti0.78]O2、Na0.6
[Cr0.6Ti0.4]O2、Na2Ti3O7, the negative materials such as Sn/C composite materials form solid-state sodium-ion battery.
Embodiment 2
The present embodiment provides a kind of preparation method of positive electrode, specific method is：
(1) under the stirring condition of 50 DEG C and velocity of variation for 300rpm, solution A and solution B are with the dropwise addition of 0.1mL/min
Speed is added drop-wise in water, waits to be added dropwise completely, obtained suspension is placed in water heating kettle in 175 DEG C of hydro-thermal reaction 20h, obtains water
Suspension after thermal response；The solution A is dissolved into water for ten hydration sodium ferrocyanides and sodium chloride and forms mixed solution, institute
It states solution B and is dissolved into the mixed solution formed in water for manganese chloride and complexing agent EDTA；
(2) suspension after step (1) described hydro-thermal reaction is centrifuged, takes solid, and to the solid of acquirement
36h is dried under 110 DEG C and 12.5mTorr of vacuum degree in vacuum drying chamber, obtains the positive electrode；
Wherein, in step (1) described suspension, the mass concentration of sodium chloride is 5wt%, in solution A, sodium ferrocyanide
A concentration of 0.1mol/L；In solution B, Mn2+A concentration of 0.1mol/L, complexing agent EDTA and Mn2+Molar ratio be 1:1；Molten
In the system that liquid A is mixed to form with solution B, sodium ferrocyanide and Mn2+Molar ratio be 1.
The molecular formula of solid-state sodium-ion battery positive material that the present embodiment obtains is Na2MnFe(CN)6, crystallinity is high, lacks
It falls into less, it is not aqueous.
It is excellent that univoltage platform, charge-discharge performance is presented in the positive electrode that the present embodiment obtains.
The positive electrode that the present embodiment obtains can be with amorphous carbon material, Na0.66[Li0.22Ti0.78]O2、Na0.6
[Cr0.6Ti0.4]O2、Na2Ti3O7, the negative materials such as Sn/C composite materials form solid-state sodium-ion battery.
Fig. 1 is the scanning electron microscopy of the positive electrode that is obtained after centrifugation before it is dried in the present embodiment step (2)
Monodispersity is presented by the Prussian blue crystal grain that the figure can be seen that in mirror (SEM) picture, and some has typical six
Side shape pattern.
Fig. 2 is scanning electron microscope (SEM) picture of dried positive electrode that the present embodiment is finally prepared,
Pattern does not change significantly before and after can be seen that drying by the figure.
After Fig. 3 is fabricated to battery before it is dried for the positive electrode in the present embodiment step (2), obtained after centrifugation
First week charging and discharging curve can be seen that charge and discharge polarization is bigger by the figure, and first week discharge capacity only has 92mAh/g.
Fig. 4 is all charge and discharge songs of head that the dried positive electrode that the present embodiment is finally prepared is fabricated to after battery
Line can be seen that charge and discharge electric polarization significantly reduces by the figure, and first week discharge capacity has been increased to 150mAh/g.
Embodiment 3
The present embodiment provides a kind of preparation method of positive electrode, specific method is：
(1) under the stirring condition of 70 DEG C and rate for 1000rpm, solution A and solution B are with the dropwise addition of 1.0mL/min
Speed is added drop-wise in water, waits to be added dropwise completely, obtained suspension is placed in water heating kettle in 200 DEG C of hydro-thermal reaction 15h, obtains water
Suspension after thermal response；The solution A is dissolved into water for ten hydration sodium ferrocyanides and sodium chloride and forms mixed solution, institute
It is the mixed solution formed in nickel sulfate and complexing agent acetate dissolution to water to state solution B；
(2) suspension after step (1) described hydro-thermal reaction is centrifuged, takes solid, and to the solid of acquirement
Drying for 24 hours, obtains the positive electrode under 120 DEG C and 15mTorr of vacuum degree in vacuum drying chamber；
Wherein, in step (1) described suspension, the mass concentration of sodium chloride is 10wt%, in solution A, sodium ferrocyanide
A concentration of 0.2mol/L；In solution B, Ni2+A concentration of 0.2mol/L；In the system that solution A is mixed to form with solution B, network
Mixture acetic acid and Ni2+Molar ratio be 2:1；In the system being mixed to form in solution A and solution B, sodium ferrocyanide and Ni2+'s
Molar ratio is 3.
The molecular formula of solid-state sodium-ion battery positive material that the present embodiment obtains is Na1.55Ni0.78Fe0.84(CN)6, knot
Brilliant degree is high, and defect is few, not aqueous.
It is excellent that univoltage platform, charge-discharge performance is presented in the positive electrode that the present embodiment obtains..
The positive electrode that the present embodiment obtains can be with amorphous carbon material, Na0.66[Li0.22Ti0.78]O2、Na0.6
[Cr0.6Ti0.4]O2、Na2Ti3O7, the negative materials such as Sn/C composite materials form solid-state sodium-ion battery.
Embodiment 4
The present embodiment provides a kind of preparation method of positive electrode, specific method is：
(1) under the stirring condition of 45 DEG C and rate for 800rpm, solution A and solution B are with the dropwise addition of 0.7mL/min speed
Degree is added drop-wise in water, waits to be added dropwise completely, obtained suspension is placed in water heating kettle in 150 DEG C of hydro-thermal reactions for 24 hours, obtains hydro-thermal
Suspension after reaction；The solution A is dissolved into water for ten hydration sodium ferrocyanides and sodium chloride and forms mixed solution, described
Solution B is dissolved into the mixed solution formed in water for zinc chloride and complexing agent sulfosalicylic acid；
(2) suspension after step (1) described hydro-thermal reaction is centrifuged, takes solid, and to the solid of acquirement
30h is dried under 115 DEG C and 13mTorr of vacuum degree in vacuum drying chamber, obtains the positive electrode；
Wherein, in step (1) described suspension, the mass concentration of sodium chloride is 7wt%, in solution A, sodium ferrocyanide
A concentration of 0.08mol/L；In solution B, Zn2+A concentration of 0.12mol/L, complexing agent sulfosalicylic acid and Zn2+Molar ratio be
1.5:1；In the system being mixed to form in solution A and solution B, sodium ferrocyanide and Zn2+Molar ratio be 1.5.
The molecular formula of solid-state sodium-ion battery positive material that the present embodiment obtains is Na1.69Zn0.91Fe0.83(CN)6, knot
Brilliant degree is high, and defect is few, not aqueous.
It is excellent that univoltage platform, charge-discharge performance is presented in the positive electrode that the present embodiment obtains..
The positive electrode that the present embodiment obtains can be with amorphous carbon material, Na0.66[Li0.22Ti0.78]O2、Na0.6
[Cr0.6Ti0.4]O2、Na2Ti3O7, the negative materials such as Sn/C composite materials form solid-state sodium-ion battery.
Comparative example 1
The specific steps of this comparative example are with reference to embodiment 2, and difference lies in step (1), without using sodium chloride.
As a result, the positive electrode sodium content that this comparative example obtains is low, crystallinity is poor, and defect is more, cannot pass through drying
Water removal completely, and chemical property is poor, can not be used as solid-state sodium-ion battery positive material.
For summary embodiment and comparative example it is found that positive electrode defect provided by the invention is seldom, crystallinity is high, is free of
Water, chemical property is good, available for solid-state sodium-ion battery.Comparative example does not use scheme provided by the invention, thus can not
Obtain the effect of the present invention.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc. all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of positive electrode, which is characterized in that the positive electrode includes the Prussian blue of doping, described Prussian blue containing sodium
Element, the positive electrode be not aqueous.
2. positive electrode according to claim 1, which is characterized in that the substance adulterated in the positive electrode is divalent mistake
Cross metallic element；
Preferably, the divalent transition metal element includes manganese element, cobalt element, nickel element, copper, Zn-ef ficiency or ferro element
In any one or at least two combination.
3. positive electrode according to claim 1 or 2, which is characterized in that the molecular formula of the positive electrode is NaxMyFez
(CN)6, wherein M be divalent transition metal element, 1≤x≤2,0.5≤y≤1, x+2 (y+z)≤6.
4. according to the preparation method of claim 1-3 any one of them positive electrodes, which is characterized in that the method includes with
Lower step：
(1) hybrid manipulation is carried out to solution A and solution B, obtains suspension, the solution A is sodium ferrocyanide and sodium chloride
Mixed solution, the solution B are doped source and the mixed solution of complexing agent；
(2) suspension for obtaining step (1) carries out separation of solid and liquid, takes solid and drying, obtains the positive electrode.
5. preparation method according to claim 4, which is characterized in that in step (1) described suspension, the quality of sodium chloride
A concentration of 1wt%-10wt%；
Preferably, in step (1) described solution A, a concentration of 0.02mol/L-0.2mol/L of sodium ferrocyanide；
Preferably, step (1) described sodium ferrocyanide is ten hydration sodium ferrocyanides；
Preferably, the solvent of step (1) described solution A is water, preferably deionized water；
Preferably, step (1) described doped source is divalent transition metal salt；
Preferably, the divalent transition metal salt includes divalent transition metal chloride and/or divalent transition metal sulfate；
Preferably, the divalent transition metal salt includes any one in manganese salt, cobalt salt, nickel salt, mantoquita, zinc salt or ferrous salt
Or at least two combination；
Preferably, in step (1) described solution B, a concentration of 0.02mol/L-0.2mol/L of doped source；
Preferably, step (1) described complexing agent includes appointing in sodium citrate, ethylenediamine tetra-acetic acid, acetic acid or sulfosalicylic acid
It anticipates a kind of or at least two combinations；
Preferably, the molar ratio of step (1) complexing agent and doped source is 1:1-2:1；
Preferably, in step (1) described solution B, solvent is water, preferably deionized water.
6. preparation method according to claim 4 or 5, which is characterized in that in step (1), mixed in solution A with solution B
In the system of formation, the molar ratio of sodium ferrocyanide and doped source is 1-3；
Preferably, the temperature of step (1) described hybrid manipulation is 25 DEG C -70 DEG C；
Preferably, step (1) described hybrid manipulation carries out under agitation；
Preferably, the rate of the stirring is 300rpm-1000rpm；
Preferably, solution A and solution B is are added drop-wise in aqueous solution by step (1) described hybrid manipulation dropwise；
Preferably, the aqueous solution is water；
Preferably, the rate of addition of solution A and the rate of addition of solution B independently are 0.1mL/min-1mL/min；
Preferably, the rate of addition of solution A and the rate of addition of solution B are identical.
7. according to claim 4-6 any one of them preparation methods, which is characterized in that in step (1), further include：To described
Suspension carries out hydro-thermal reaction；
Preferably, the temperature of the hydro-thermal reaction is 150 DEG C -200 DEG C；
Preferably, the time of the hydro-thermal reaction is 15h-24h；
Preferably, the hydro-thermal reaction carries out in water heating kettle.
8. according to claim 4-7 any one of them preparation methods, which is characterized in that in step (2), the separation of solid and liquid is
Centrifuge or filter separation；
Preferably, step (2) further includes：Separation of solid and liquid is washed with water before being dried and obtains solid；
Preferably, in step (2), the drying carries out in vacuum drying chamber；
Preferably, in step (2), the temperature of the drying is 100 DEG C -120 DEG C；
Preferably, in step (2), the time of the drying is -48h for 24 hours；
Preferably, in step (2), the vacuum degree of the drying is 10mTorr-15mTorr.
9. according to the preparation method described in claim 4-8, which is characterized in that the described method comprises the following steps：
(1) under conditions of the stirring of 25 DEG C -70 DEG C and rate for 300rpm-1000rpm, by solution A and solution B with 0.1mL/
The rate of addition of min-1.0mL/min is added drop-wise in water, and solution A is identical with the rate of addition of solution B, is waited to be added dropwise completely, will
Obtained suspension is placed in water heating kettle in 150 DEG C of -200 DEG C of hydro-thermal reaction 15h-24h, obtains the suspension after hydro-thermal reaction；
The solution A is dissolved into water for ten hydration sodium ferrocyanides and sodium chloride and forms mixed solution, the solution B for doped source and
Complexing agent is dissolved into the mixed solution formed in water, and the doped source is divalent transition metal chloride and/or divalent transitional gold
Belong to sulfate；
(2) separation is centrifuged or filtered to the suspension after step (1) described hydro-thermal reaction, take solid, and to obtaining
Solid in vacuum drying chamber the dry -48h for 24 hours under the vacuum degree of 100 DEG C -120 DEG C and 10mTorr-15mTorr, obtain
The positive electrode；
Wherein, in step (1) described suspension, the mass concentration of sodium chloride is 1wt%-10wt%；In solution A, ferrocyanide
A concentration of 0.02mol/L-0.2mol/L of sodium；In solution B, a concentration of 0.02mol/L- of divalent transition metal ion
The molar ratio of 0.2mol/L, complexing agent and divalent transition metal ion is 1:1-2:1；In the body that solution A and solution B are mixed to form
In system, the molar ratio of sodium ferrocyanide and divalent transition metal ion is 1-3.
10. according to the purposes of claim 1-3 any one of them positive electrodes, which is characterized in that the positive electrode is used for
The anode of solid-state sodium-ion battery.
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