CN109728292A - Prussian blue type positive electrode material for sodium ion battery, preparation method of Prussian blue type positive electrode material and sodium ion battery - Google Patents
Prussian blue type positive electrode material for sodium ion battery, preparation method of Prussian blue type positive electrode material and sodium ion battery Download PDFInfo
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Abstract
The application provides a Prussian blue positive electrode material for a sodium-ion battery, a preparation method of the Prussian blue positive electrode material and the sodium-ion battery, wherein the molecular formula of the Prussian blue positive electrode material for the sodium-ion battery is NaxM[M′(CN)6]y·zH2O, wherein M is a transition metal, M' is a transition metal, 0<x≤2，0.8≤y<1，0<z is less than or equal to 20. In an X-ray diffraction spectrum of the Prussian blue type cathode material for the sodium-ion battery, a diffraction peak at a position where 2 theta is 34 degrees +/-2 degrees is a single peak. The sodium ion battery of the application can have better cycle performance.
Description
Technical field
This application involves field of batteries more particularly to a kind of sodium-ion battery prussian blue positive electrode and its preparations
Method and sodium-ion battery.
Background technique
Since lithium ion battery commercialization, lithium ion battery is with its high-energy density, long circulation life, high security
Etc. advantages rapidly become the primary selection of the equipment energy-storage travelling wave tube such as computer, electric tool, digital camera.In recent years, with electricity
The rapid emergence in motor-car market, lithium ion battery have obtained wider application.But with the extensive use of lithium ion battery, lithium
The problems such as maldistribution of the resources, resource relative shortage, gradually highlights.
Compared with lithium, sodium resource distribution is extensive, resourceful, with the advantage in terms of resource and cost.Based on sodium
The sodium-ion battery to grow up is expected to the part city of substitution lithium ion battery because of the advantages that its manufacturing cost is low, and safety is good
, become the contenders of next battery eliminator.And sodium-ion battery positive material is the main of influence sodium-ion battery performance
Factor, therefore, to meet the market demand in large scale, it would be highly desirable to which developing one kind makes sodium-ion battery have both good electrochemistry
The positive electrode of energy and good dynamic performance.
Prussian blue material have big frame structure, for sodium ion insertion, abjection, be highly suitable as sodium from
The positive electrode of sub- battery.But it is had been found that after the material is applied to non-water system sodium-ion battery, cycle performance is poor.In view of
This, proposes the application.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of sodium-ion battery with Prussian blue
Class positive electrode and preparation method thereof and sodium-ion battery, the sodium-ion battery have preferable cycle performance.
In order to achieve the above object, in the one side of the application, this application provides a kind of sodium-ion battery Prussias
Blue class positive electrode, molecular formula NaxM[M′(CN)6]y·zH2O, wherein M is transition metal, and M ' is transition metal, 0 < x
≤ 2,0.8≤y < 1,0 < z≤20.In X ray diffracting spectrum of the sodium-ion battery with prussian blue positive electrode, in 2 θ
It is unimodal for the diffraction maximum at 34 ° ± 2 °.
In the another aspect of the application, this application provides a kind of sodium-ion battery systems of prussian blue positive electrode
Preparation Method is used to prepare the sodium-ion battery prussian blue positive electrode of the application one side, comprising steps of (1) will be golden
The six cyano sodium salts for belonging to M ' are dissolved in solvent, and inorganic sodium is then added, and obtain solution one；(2) metal M salt is dissolved in solvent
In, inorganic sodium is then added, obtains solution two；(3) solution one and solution two are sufficiently mixed at a certain temperature, are mixed
Solution is closed, sediment is obtained after ageing, sediment is washed later, dries at a certain temperature, and acquisition molecular formula is NaxM[M′
(CN)6]y·zH2The sodium-ion battery of O prussian blue positive electrode, wherein M is transition metal, and M ' is transition metal, 0 <
X≤2,0.8≤y < 1,0 < z≤20.In X ray diffracting spectrum of the sodium-ion battery with prussian blue positive electrode, 2
θ is that the diffraction maximum at 34 ° ± 2 ° is unimodal.
At the another aspect of the application, this application provides a kind of sodium-ion batteries comprising the sodium of the application one side
Ion battery prussian blue positive electrode.
Compared with the existing technology, the application has the beneficial effect that
The sodium-ion battery of the application is preferable with the crystallinity of prussian blue positive electrode and performance is stablized, and is applied to sodium
The cycle performance that sodium-ion battery can be significantly improved after in ion battery, is particularly suitable for application to using organic electrolyte system
In sodium-ion battery.
Detailed description of the invention
Fig. 1 is the cycle performance curve of embodiment 1 and comparative example 1.
Specific embodiment
The following detailed description of according to sodium-ion battery prussian blue positive electrode and preparation method thereof of the application and
Sodium-ion battery.
Illustrate the sodium-ion battery prussian blue positive electrode according to the application first aspect first.
It with the molecular formula of prussian blue positive electrode is Na according to the sodium-ion battery of the application first aspectxM[M′
(CN)6]y·zH2O, wherein M is transition metal, and M ' is transition metal, 0 < x≤2,0.8≤y < 1,0 < z≤20.The sodium ion
It is diffraction maximum at 34 ° ± 2 ° in 2 θ is unimodal in X ray diffracting spectrum of the battery with prussian blue positive electrode.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, the sodium ion
Tool occurs with prussian blue positive electrode in charge and discharge for battery, and there are two the reactions of electronics transfer, so its is with higher
Theoretical specific capacity；The sodium-ion battery is preferable with the crystallinity of prussian blue positive electrode simultaneously and performance is stablized, application
After in sodium-ion battery, significant decaying is had no by repeatedly recycling its capacity, sodium-ion battery can be made to have preferable
Cycle performance.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, it is preferable that M choosing
From one or more of Mn, Fe, Co, Ni, Cu, Zn, V, Cr, it is further preferred that M is selected from Mn or Fe.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, it is preferable that M '
Selected from one or more of Mn, Fe, Co, Ni, Cu, Zn, V, Cr, it is further preferred that M ' is selected from Fe.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, further,
It is the diffraction maximum at 24 ° ± 1 ° in 2 θ in X ray diffracting spectrum of the sodium-ion battery with prussian blue positive electrode
It is unimodal.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, further,
In X ray diffracting spectrum of the sodium-ion battery with prussian blue positive electrode, it is for the diffraction maximum at 38 ° ± 2 ° in 2 θ
It is unimodal.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, it is preferable that institute
In the X ray diffracting spectrum for stating sodium-ion battery prussian blue positive electrode, 2 θ are 34 ° ± 2 °, 2 θ are at 24 ° ± 1 °
And 2 θ be 38 ° ± 2 ° at diffraction maximum be unimodal.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, work as positive electrode
When it is unimodal that 2 θ, which are the diffraction maximum at 34 ° ± 2 °, the cycle performance of sodium-ion battery is obviously improved.Further, when
Positive electrode can further improve electrochemistry when 2 θ are 38 ° ± 2 ° and/or 2 θ be diffraction maximum at 24 ° ± 1 ° are also unimodal
The cycle performance of energy storage device, wherein when 2 θ are 24 ° ± 1 ° and 2 θ be diffraction maximum at 38 ° ± 2 ° are unimodal, sodium ion
The cycle performance of battery is optimal.
In the sodium-ion battery according to the application first aspect in prussian blue positive electrode, further to mention
The cycle performance of high sodium ion battery, the sodium-ion battery are preferably 5m with the specific surface area of prussian blue positive electrode2/
G~20m2/g.If the sodium-ion battery is excessive with the specific surface area of prussian blue positive electrode, adsorption capacity compared with
By force, sodium-ion battery generated side reaction product in charge and discharge process is easily being enriched to sodium-ion battery prussian blue just
Simultaneously further oxidation reaction occurs for pole material surface, and the product of generation can cover sodium-ion battery prussian blue anode material
Expect surface, increase anode polarization, so that part sodium-ion battery is lost activity with prussian blue positive electrode, cause sodium from
Sub- battery prussian blue positive electrode energy loss, to keep the capacity attenuation of sodium-ion battery very fast, cycle performance is fast
Speed decline；If the sodium-ion battery is too small with the specific surface area of prussian blue positive electrode, with electrolyte contacts
Area reduces, and Charge-transfer resistance increases, and the cycle performance of sodium-ion battery can be also decreased obviously.It is further preferred that described
Sodium-ion battery is preferably 5m with the specific surface area of prussian blue positive electrode2/ g~14m2/g。
Secondly illustrate the preparation method of the sodium-ion battery prussian blue positive electrode according to the application second aspect.
According to the sodium-ion battery of the application second aspect preparation method of prussian blue positive electrode, it is used to prepare
The prussian blue positive electrode of sodium-ion battery described in the application first aspect, comprising steps of
(1) the six cyano sodium salts of metal M ' are dissolved in solvent, inorganic sodium is then added, obtain solution one；
(2) metal M salt is dissolved in solvent, inorganic sodium is then added, obtain solution two；
(3) solution one and solution two are sufficiently mixed at a certain temperature, obtain mixed solution, is precipitated after ageing
Object, sediment is washed later, dries at a certain temperature, and acquisition molecular formula is NaxM[M′(CN)6]y·zH2O, wherein M is
Transition metal, M ' are transition metal, 0 < x≤2,0.8≤y < 1,0 < z≤20；Sodium-ion battery prussian blue anode
It is diffraction maximum at 34 ° ± 2 ° in 2 θ is unimodal in the X ray diffracting spectrum of material.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
In step (3), the hybrid mode of solution one and solution two is not limited specifically, can be mixed according to actual needs.Specifically
Ground, can be solution one and is added drop-wise in solution two and mixed, and be also possible to solution two and be added drop-wise in solution one mixed, also
It can be solution one and solution two while being added drop-wise in solvent and mixed.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
The type of the solvent does not limit specifically, can be selected according to actual needs, specifically the solvent can be selected from from
One or more of water, methanol, ethyl alcohol, isopropanol, ethylene glycol, diethylene glycol, glycerine, polyethylene glycol, it is preferable that step
(1), step (2), the solvent in step (3) are selected from deionized water.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
Preferably, the six cyano sodium salts of metal M ' can be selected from Na4Fe(CN)6、Na3Fe(CN)6、Na4Mn(CN)6、Na3Co(CN)6、Na4V
(CN)6、Na4Cr(CN)6、Na4Ni(CN)6One or more of, but the application is without being limited thereto.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
Preferably, metal M salt can be selected from MnCl2、FeSO4、Fe(NO3)3、FeCl3、Fe(CH3COO)2、FeCl2、Mn(NO3)2、MnSO4、
MnCl2、Mn(CH3COO)2、NiNO3、(CH3COO)2Zn、CoCl2、CuSO4、Cu(NO3)2、CuCl2、Cu(CH3COO)2、Ni
(NO3)2、NiSO4、Ni(CH3COO)2、NiCl2、Zn(NO3)2、ZnSO4、ZnCl2、Co(NO3)2、CoSO4、Co(CH3COO)2In
One or more, but the application is without being limited thereto.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
In step (1), step (2), the type of the inorganic sodium is not particularly limited, and can be selected according to actual needs, tool
Body, the inorganic sodium can be selected from NaCl, NaBr, NaI, NaNO3、Na2SO4、Na2S2O3、Na2CO3、NaHCO3One of
It is or several, it is preferable that the inorganic sodium can be selected from NaCl.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
Reducing agent can also be added at least one step in step (1), step (2), step (3), reducing agent can protect at a low price
The transition metal of state is not oxidized at higher price.The type of the reducing agent does not limit specifically, can be according to actual needs
It is selected.Specifically, the reducing agent can be selected from sodium thiosulfate, sodium citrate, citric acid, glucose, ascorbic acid,
One or more of alcohol, aldehyde, ketone.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
In step (3), the drying temperature of sediment is more than or equal to 100 DEG C and less than or equal to 200 DEG C, and drying time is more than or equal to 10 minutes
And it is less than or equal to 120 hours.Sodium-ion battery prussian blue positive electrode can be greatly increased under above-mentioned drying condition 2
θ is 34 ° ± 2 °, 2 θ are 24 ° ± 1 ° and 2 θ be diffraction maximum at 38 ° ± 2 ° are unimodal probability.
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
The solution one and solution two in the concentration and step (3) of M in the concentration, step (2) of M ' in regulating step (1) can be passed through
Mixing temperature controls the specific surface area of sodium-ion battery prussian blue positive electrode.Preferably, in step (1) M ' it is dense
Degree is 0.05mol/L~0.5mol/L.Preferably, the concentration of M is 0.05mol/L~0.5mol/L in step (2).Preferably,
The mixing temperature of solution one and solution two is 25 DEG C~100 DEG C in step (3).
In preparation method of the sodium-ion battery according to the application second aspect with prussian blue positive electrode,
In step (3), the molar ratio of M ' and M is 0.8~1.5 in mixed solution.
Illustrate the sodium-ion battery according to the application third aspect again.
Sodium-ion battery according to the application third aspect includes positive plate, negative electrode tab, electrolyte and isolation film.Anode
Piece includes plus plate current-collecting body and is set to positive diaphragm on plus plate current-collecting body and containing positive electrode.Wherein, the anode
Material includes the prussian blue positive electrode of the sodium-ion battery according to the application first aspect.
In the sodium-ion battery according to the application third aspect, it is described negative electrode tab may include negative current collector with
And be set on negative current collector and the cathode membrane containing negative electrode material, the negative electrode material be selected from carbon material, alloy material,
One or more of transition metal oxide and sulfide, phosphorous-based materials, titanate material.The negative electrode tab can also be direct
Select sodium sheet metal or sodium metal alloy film.
In the sodium-ion battery according to the application third aspect, the material of the isolation film is unrestricted, can be with
It is selected according to actual needs.Specifically, isolation film can be selected from polypropylene screen, polyethylene film, polyethylene/polypropylene/poly- second
One or more of the composite membrane of alkene, cellulosic nonwoven fabric film, glass fibre membrane.
In the sodium-ion battery according to the application third aspect, it is preferable that the electrolyte is organic electrolyte.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
(1) preparation of positive plate
By 4.84g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 29.2gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.1mol/L；By 1.97gMnCl2·4H2O dissolves in deionized water, stirs
MnCl is obtained after mixing uniformly2Concentration is the solution of 0.1mol/L；At 50 DEG C, under stiring by MnCl2Solution is slowly added drop-wise to
Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment passes through
The mode of centrifugation is collected, then washed, finally the dry hour for 24 hours at 160 DEG C, obtains positive electrode sample, and ICP and TG are surveyed
Test result shows that the molecular formula of the sample is Na1.768Mn[Fe(CN)6]0.942·2.132H2O, BET test result show the sample
Specific surface area be 12m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is at 24 ° ± 1 ° in 2 θ
Diffraction maximum be it is unimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is unimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is unimodal.
It is that 7:2:1 is mixed by above-mentioned sample, conductive agent Super P, binder Kynoar (PVDF) mass ratio,
Solvent N-methyl pyrilidone is added, stirs evenly acquisition anode sizing agent, is coated on the plus plate current-collecting body with a thickness of 15 μm later
On aluminium foil, the positive plate for being 14mm at diameter in 80 DEG C of dry backlash.
(2) preparation of negative electrode tab
Negative electrode tab is directly selected from metallic sodium piece.
(3) preparation of electrolyte
(the H in argon atmosphere glove box2O < 0.1ppm, O2< 0.1ppm), EC, PC are mixed according to volume ratio for 1:1
It closes, then by sufficiently dry sodium salt NaClO4It is dissolved in mixed organic solvents, obtains electrolyte, wherein NaClO4Concentration
For 1mol/L.
(4) preparation of isolation film
Using glass fibre membrane (Whatman production) as isolation film.
(5) preparation of button cell
Positive plate, isolation film, negative electrode tab are folded in order, make isolation film be in played between positive plate and negative electrode tab every
From effect, by the electrolyte prepared be injected into it is dry after battery core in, be assembled into CR2032 type button cell.
Embodiment 2
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 4.84g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 29.2gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.1mol/L；By 1.97gMnCl2·4H2O dissolves in deionized water, stirs
MnCl is obtained after mixing uniformly2Concentration is the solution of 0.1mol/L；At 50 DEG C, under stiring by MnCl2Solution is slowly added drop-wise to
Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment passes through
The mode of centrifugation is collected, then washed, finally the dry hour for 24 hours at 140 DEG C, obtains positive electrode sample, and ICP and TG are surveyed
Test result shows that the molecular formula of the sample is Na1.768Mn[Fe(CN)6]0.942·2.132H2O, BET test result show the sample
Specific surface area be 12m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is at 24 ° ± 1 ° in 2 θ
Diffraction maximum be it is bimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is unimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is unimodal.
Embodiment 3
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 4.84g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 29.2gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.1mol/L；By 1.97gMnCl2·4H2O dissolves in deionized water, stirs
MnCl is obtained after mixing uniformly2Concentration is the solution of 0.1mol/L；At 50 DEG C, under stiring by MnCl2Solution is slowly added drop-wise to
Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment passes through
The mode of centrifugation is collected, then washed, finally 4h hours dry at 140 DEG C, obtains positive electrode sample, and ICP and TG are surveyed
Test result shows that the molecular formula of the sample is Na1.768Mn[Fe(CN)6]0.942·2.132H2O, BET test result show the sample
Specific surface area be 12m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is at 24 ° ± 1 ° in 2 θ
Diffraction maximum be it is bimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is unimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is bimodal.
Embodiment 4
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 2.42g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 30.3gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.05mol/L；By 0.99gMnCl2·4H2O dissolves in deionized water,
MnCl is obtained after mixing evenly2Concentration is the solution of 0.05mol/L；At 80 DEG C, under stiring by MnCl2Solution is slowly added dropwise
To Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment is logical
The mode for crossing centrifugation is collected, then washed, finally the dry hour for 24 hours at 160 DEG C, obtains positive electrode sample, ICP and TG
Test result shows that the molecular formula of the sample is Na1.788Mn[Fe(CN)6]0.947·2.099H2O, BET test result show the sample
The specific surface area of product is 5m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is 24 ° ± 1 ° in 2 θ
The diffraction maximum at place be it is unimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is unimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is unimodal.
Embodiment 5
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 24.20g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 19.9gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.5mol/L；By 9.90gMnCl2·4H2O dissolves in deionized water, stirs
MnCl is obtained after mixing uniformly2Concentration is the solution of 0.5mol/L；At room temperature, under stiring by MnCl2Solution is slowly added drop-wise to
Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment passes through
The mode of centrifugation is collected, then washed, finally the dry hour for 24 hours at 160 DEG C, obtains positive electrode sample, and ICP and TG are surveyed
Test result shows that the molecular formula of the sample is Na1.728Mn[Fe(CN)6]0.932·2.298H2O, BET test result show the sample
Specific surface area be 20m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is at 24 ° ± 1 ° in 2 θ
Diffraction maximum be it is unimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is unimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is unimodal.
Embodiment 6
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 4.84g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 29.2gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.1mol/L；By 1.99gFeCl2·4H2O dissolves in deionized water, so
2.48g Na is added afterwards2S2O3, FeCl is obtained after mixing evenly2Concentration is the solution of 0.1mol/L；At 40 DEG C, under stiring
By FeCl2Solution is slowly added drop-wise to Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then
Continuing to be aged 6h, sediment is collected by way of centrifugation, and it is then washed, finally the dry hour for 24 hours at 160 DEG C, obtain
Positive electrode sample, ICP and TG test result show that the molecular formula of the sample is Na1.732Fe[Fe(CN)6]0.933·
2.269H2O, BET test result show that the specific surface area of the sample is 14m2/g.Above-mentioned material is subjected to X-ray diffraction analysis,
The results show that the sample 2 θ be diffraction maximum at 24 ° ± 1 ° be it is unimodal, 2 θ be the diffraction maximum at 34 ° ± 2 ° be it is unimodal, 2 θ are
Diffraction maximum at 38 ° ± 2 ° is unimodal.
Comparative example 1
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 4.84g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 29.2gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.1mol/L；By 1.97gMnCl2·4H2O dissolves in deionized water, stirs
MnCl is obtained after mixing uniformly2Concentration is the solution of 0.1mol/L；At 50 DEG C, under stiring by MnCl2Solution is slowly added drop-wise to
Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment passes through
The mode of centrifugation is collected, then washed, finally the dry hour for 24 hours at 80 DEG C, obtains positive electrode sample, and ICP and TG are surveyed
Test result shows that the molecular formula of the sample is Na1.768Mn[Fe(CN)6]0.942·2.132H2O, BET test result show the sample
Specific surface area be 12m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is at 24 ° ± 1 ° in 2 θ
Diffraction maximum be it is bimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is bimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is bimodal.
Comparative example 2
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 1.94g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 30.6gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.04mol/L；By 0.79gMnCl2·4H2O dissolves in deionized water,
MnCl is obtained after mixing evenly2Concentration is the solution of 0.04mol/L；At 90 DEG C, under stiring by MnCl2Solution is slowly added dropwise
To Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment is logical
The mode for crossing centrifugation is collected, then washed, finally the dry hour for 24 hours at 160 DEG C, obtains positive electrode sample, ICP and TG
Test result shows that the molecular formula of the sample is Na1.792Mn[Fe(CN)6]0.948·2.087H2O, BET test result show the sample
The specific surface area of product is 3m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is 24 ° ± 1 ° in 2 θ
The diffraction maximum at place be it is unimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is unimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is unimodal.
Comparative example 3
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 29.04g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 17.5gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.6mol/L；By 11.87gMnCl2·4H2O dissolves in deionized water,
MnCl is obtained after mixing evenly2Concentration is the solution of 0.6mol/L；At 25 DEG C, under stiring by MnCl2Solution is slowly added drop-wise to
Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then proceedes to ageing 6h, sediment passes through
The mode of centrifugation is collected, then washed, finally the dry hour for 24 hours at 160 DEG C, obtains positive electrode sample, and ICP and TG are surveyed
Test result shows that the molecular formula of the sample is Na1.720Mn[Fe(CN)6]0.930·2.316H2O, BET test result show the sample
Specific surface area be 25m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that the sample is at 24 ° ± 1 ° in 2 θ
Diffraction maximum be it is unimodal, 2 θ be diffraction maximum 34 ° ± 2 ° at be it is unimodal, 2 θ are that the diffraction maximum at 38 ° ± 2 ° is unimodal.
Comparative example 4
With embodiment 1, difference is the preparation process of button cell,
(1) preparation of positive plate
By 4.84g Na4Fe(CN)6·10H2O is dissolved in 100ml deionized water, and 29.2gNaCl is then added, stirring
Na is obtained after uniformly4Fe(CN)6Concentration is the solution of 0.1mol/L；By 1.99gFeCl2·4H2O dissolves in deionized water, so
2.48g Na is added afterwards2S2O3, FeCl is obtained after mixing evenly2Concentration is the solution of 0.1mol/L；At 40 DEG C, under stiring
By FeCl2Solution is slowly added drop-wise to Na4Fe(CN)6In solution, suitable reducing agent sodium thiosulfate is added after dripping, then
Continuing to be aged 6h, sediment is collected by way of centrifugation, and it is then washed, finally the dry hour for 24 hours at 80 DEG C, obtain just
Pole material sample, ICP and TG test result show that the molecular formula of the sample is Na1.732Fe[Fe(CN)6]0.933·2.269H2O,
BET test result shows that the specific surface area of the sample is 14m2/g.Above-mentioned material is subjected to X-ray diffraction analysis, the results show that
The sample 2 θ be diffraction maximum at 24 ° ± 1 ° be it is bimodal, 2 θ be the diffraction maximum 34 ° ± 2 ° at be it is bimodal, 2 θ is at 38 ° ± 2 °
Diffraction maximum be it is bimodal.
Next above-mentioned button cell is tested.
(1) X-ray diffraction is tested
Using the sodium-ion battery prussian blue in X-ray diffraction (XRD) characterization embodiment 1-6 and comparative example 1-4
Positive electrode sample uses the K of Cu target in testαRay (0.154056nm), sweep speed are 5 °/min.
(2) cycle performance is tested
50 cycle performance tests are carried out on Land cell tester.Size of current used is 0.1C (1C when test
=170mAh/g), charge and discharge blanking voltage is 2.0~4.0V.
The test result of table 1 embodiment 1-6 and comparative example 1-4
From the Correlative data analysis of table 1 it is found that in embodiment 1-6 and comparative example 1, in conjunction with Fig. 1, when sodium-ion battery is used
Prussian blue positive electrode 2 θ be 24 ° ± 1 °, 34 ° ± 2 °, the diffraction maximum on 38 ° of ± 2 ° of positions be unimodal when, battery
Cycle performance it is best, circulation 50 times after capacity retention ratio still have 95.3%；When sodium-ion battery prussian blue anode material
Expect that the cycle performance of battery decreases when 2 θ become bimodal for the diffraction maximum on 24 ° of ± 1 ° of positions；When sodium-ion battery is used
Prussian blue positive electrode is when 2 θ are 24 ° ± 1 °, the diffraction maximum on 38 ° of ± 2 ° of positions becomes bimodal, the circulation of battery
Performance further declines, and the capacity retention ratio after circulation 50 times maintains 80.2%；And when sodium-ion battery is with Prussian blue
Class positive electrode 2 θ be 24 ° ± 1 °, 34 ° ± 2 °, diffraction maximum is all bimodal on 38 ° of ± 2 ° of positions when, the cycle performance of battery
Decline is significant, and the capacity retention ratio after circulation 50 times only has 48.6%, cannot obviously satisfy the use demand.
As can be seen that sodium-ion battery prussian blue anode material in embodiment 1, embodiment 4-5 and comparative example 2-3
The specific surface area of material also has large effect to the cycle performance of battery.In comparative example 2, sodium-ion battery with prussian blue just
The specific surface area of pole material is too small, and the cycle performance of battery is poor, and the capacity protective rate after circulation 50 times is only 73.2%.When
When sodium-ion battery is moderate with the specific surface area of prussian blue positive electrode, such as in embodiment 1, embodiment 4-5, battery
Cycle performance available significantly improve.But if sodium-ion battery is excessive with the specific surface area of prussian blue anode, such as
Comparative example 3 can then deteriorate the cycle performance of battery, the reason is that, biggish specific surface area causes more side reaction, it is secondary anti-
Answering product to be covered on sodium-ion battery will cause its energy loss with the surface of prussian blue positive electrode, so as to cause battery
Cycle performance decline.
It is understood that the type of sodium-ion battery prussian blue positive electrode is different, to the circulation of battery
The improvement of performance is also different.For example, in embodiment 6, although specific kind of sodium-ion battery prussian blue positive electrode
Class is different from embodiment 1-5, but compared with comparative example 4,2 θ are 34 ° ± 2 °, 2 θ are 24 ° ± 1 °, 2 θ are at 38 ° ± 2 °
Diffraction maximum be it is unimodal, battery have preferable cycle performance.
In conclusion the sodium-ion battery using sodium-ion battery provided by the present application prussian blue positive electrode has
There is preferable cycle performance.
Claims (10)
1. a kind of sodium-ion battery prussian blue positive electrode, which is characterized in that
The sodium-ion battery is Na with the molecular formula of prussian blue positive electrodexM[M′(CN)6]y·zH2O, wherein M was
Metal is crossed, M ' is transition metal, 0 < x≤2,0.8≤y < 1,0 < z≤20；
It is the diffraction at 34 ° ± 2 ° in 2 θ in X ray diffracting spectrum of the sodium-ion battery with prussian blue positive electrode
Peak is unimodal.
2. sodium-ion battery according to claim 1 prussian blue positive electrode, which is characterized in that
M is selected from one or more of Mn, Fe, Co, Ni, Cu, Zn, V, Cr, it is preferable that M is selected from Mn or Fe；
M ' is selected from one or more of Mn, Fe, Co, Ni, Cu, Zn, V, Cr, it is preferable that M ' is selected from Fe.
3. sodium-ion battery according to claim 1 prussian blue positive electrode, which is characterized in that the sodium ion
It is diffraction maximum at 24 ° ± 1 ° in 2 θ is unimodal in X ray diffracting spectrum of the battery with prussian blue positive electrode.
4. sodium-ion battery according to claim 1 prussian blue positive electrode, which is characterized in that the sodium ion
It is diffraction maximum at 38 ° ± 2 ° in 2 θ is unimodal in X ray diffracting spectrum of the battery with prussian blue positive electrode.
5. sodium-ion battery according to claim 1 prussian blue positive electrode, which is characterized in that the sodium ion
It is diffraction maximum at 24 ° ± 1 ° in 2 θ is unimodal and in 2 θ in X ray diffracting spectrum of the battery with prussian blue positive electrode
It is also unimodal for the diffraction maximum at 38 ° ± 2 °.
6. sodium-ion battery according to claim 1 prussian blue positive electrode, which is characterized in that the sodium ion
Battery is 5m with the specific surface area of prussian blue positive electrode2/ g~20m2/g。
7. a kind of prepare the sodium-ion battery of any of claims 1-6 method of Prussian blue positive electrode,
It is characterized in that, comprising steps of
(1) the six cyano sodium salts of metal M ' are dissolved in solvent, inorganic sodium is then added, obtain solution one；
(2) metal M salt is dissolved in solvent, inorganic sodium is then added, obtain solution two；
(3) solution one and solution two are sufficiently mixed at a certain temperature, obtain mixed solution, obtains sediment after ageing, it
Sediment is washed afterwards, dries at a certain temperature, and acquisition molecular formula is NaxM[M′(CN)6]y·zH2The sodium-ion battery of O is used
Prussian blue positive electrode, wherein M is transition metal, and M ' is transition metal, 0 < x≤2,0.8≤y < 1,0 < z≤20；
It is the diffraction at 34 ° ± 2 ° in 2 θ in X ray diffracting spectrum of the sodium-ion battery with prussian blue positive electrode
Peak is unimodal.
8. the sodium-ion battery according to claim 7 preparation method of prussian blue positive electrode, which is characterized in that
In step (3), the mixing temperature of solution one and solution two is 25 DEG C~100 DEG C, and the drying temperature of sediment is 100 DEG C~200
℃。
9. the sodium-ion battery according to claim 7 preparation method of prussian blue positive electrode, which is characterized in that
Reducing agent is added at least one step in step (1), step (2), step (3).
10. a kind of sodium-ion battery, comprising:
Positive plate including plus plate current-collecting body and is set to positive diaphragm on plus plate current-collecting body and containing positive electrode；
Negative electrode tab；
Electrolyte；And
Isolation film；
It is characterized in that,
The positive electrode includes sodium-ion battery prussian blue anode material according to claim 1 to 6
Material.
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| WO2024026991A1 (en) * | 2022-08-01 | 2024-02-08 | 广东邦普循环科技有限公司 | Modified prussian derivative, and preparation method therefor and use thereof |
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