CN109728292A - Sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium-ion battery - Google Patents

Sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium-ion battery Download PDF

Info

Publication number
CN109728292A
CN109728292A CN201711033478.4A CN201711033478A CN109728292A CN 109728292 A CN109728292 A CN 109728292A CN 201711033478 A CN201711033478 A CN 201711033478A CN 109728292 A CN109728292 A CN 109728292A
Authority
CN
China
Prior art keywords
sodium
ion battery
positive electrode
prussian blue
blue positive
Prior art date
Application number
CN201711033478.4A
Other languages
Chinese (zh)
Inventor
苏硕剑
郭永胜
梁成都
王喜庆
王莹
刘倩
Original Assignee
宁德时代新能源科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Priority to CN201711033478.4A priority Critical patent/CN109728292A/en
Publication of CN109728292A publication Critical patent/CN109728292A/en

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The application provides a kind of sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium-ion battery, the sodium-ion battery are Na with the molecular formula of prussian blue positive electrodexM[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.It is diffraction maximum at 34 ° ± 2 ° in 2 θ is unimodal in X ray diffracting spectrum of the sodium-ion battery with prussian blue positive electrode.The sodium-ion battery of the application can have preferable cycle performance.

Description

Sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium ion Battery

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.
CN201711033478.4A 2017-10-30 2017-10-30 Sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium-ion battery CN109728292A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711033478.4A CN109728292A (en) 2017-10-30 2017-10-30 Sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium-ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711033478.4A CN109728292A (en) 2017-10-30 2017-10-30 Sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium-ion battery

Publications (1)

Publication Number Publication Date
CN109728292A true CN109728292A (en) 2019-05-07

Family

ID=66292252

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711033478.4A CN109728292A (en) 2017-10-30 2017-10-30 Sodium-ion battery prussian blue positive electrode and preparation method thereof and sodium-ion battery

Country Status (1)

Country Link
CN (1) CN109728292A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474659A (en) * 2013-08-23 2013-12-25 中国科学院化学研究所 Preparation method and application of positive pole material of sodium-ion battery
CN104282908A (en) * 2014-09-24 2015-01-14 张五星 Method for synthesizing high-sodium iron-based Prussian blue electrode material
CN104701543A (en) * 2015-02-05 2015-06-10 北京理工大学 Prussian blue analogous positive material for sodium-ion batteries and preparation method of positive material
CN104956527A (en) * 2013-01-29 2015-09-30 夏普株式会社 Transition metal hexacyanoferrate battery cathode, transition metal hexacyanoferrate cathode battery, method for synthesizing a transition metal hexacyanoferrate battery material, method for fabricating a transition metal hexacyanoferrate battery cathode electrode, and method for using a transition metal hexacyanoferrate battery
CN105990567A (en) * 2015-02-09 2016-10-05 中国科学院宁波材料技术与工程研究所 Preparation method of prussian blue analogue nano-material and use of prussian blue analogue in sodium-ion battery
CN106920964A (en) * 2017-04-05 2017-07-04 浙江大学 A kind of prussian blue sodium-ion battery positive material and preparation method thereof
CN107082438A (en) * 2017-04-28 2017-08-22 武汉理工大学 Prussian blue nano floral structure material and its preparation and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104956527A (en) * 2013-01-29 2015-09-30 夏普株式会社 Transition metal hexacyanoferrate battery cathode, transition metal hexacyanoferrate cathode battery, method for synthesizing a transition metal hexacyanoferrate battery material, method for fabricating a transition metal hexacyanoferrate battery cathode electrode, and method for using a transition metal hexacyanoferrate battery
CN103474659A (en) * 2013-08-23 2013-12-25 中国科学院化学研究所 Preparation method and application of positive pole material of sodium-ion battery
CN104282908A (en) * 2014-09-24 2015-01-14 张五星 Method for synthesizing high-sodium iron-based Prussian blue electrode material
CN104701543A (en) * 2015-02-05 2015-06-10 北京理工大学 Prussian blue analogous positive material for sodium-ion batteries and preparation method of positive material
CN105990567A (en) * 2015-02-09 2016-10-05 中国科学院宁波材料技术与工程研究所 Preparation method of prussian blue analogue nano-material and use of prussian blue analogue in sodium-ion battery
CN106920964A (en) * 2017-04-05 2017-07-04 浙江大学 A kind of prussian blue sodium-ion battery positive material and preparation method thereof
CN107082438A (en) * 2017-04-28 2017-08-22 武汉理工大学 Prussian blue nano floral structure material and its preparation and application

Similar Documents

Publication Publication Date Title
Shi et al. Mitigating voltage decay of Li-rich cathode material via increasing Ni content for lithium-ion batteries
Zhang et al. High performance of electrochemical lithium storage batteries: ZnO-based nanomaterials for lithium-ion and lithium–sulfur batteries
CN105917499B (en) The manufacturing method of negative electrode material for nonaqueous electrode secondary battery and anode active material particles
Wu et al. Synchronous Tailoring Surface Structure and Chemical Composition of Li‐Rich–Layered Oxide for High‐Energy Lithium‐Ion Batteries
Wang et al. Nanoarchitecture multi‐structural cathode materials for high capacity lithium batteries
Zhao et al. Synthesis, characterization, and electrochemistry of cathode material Li [Li0. 2Co0. 13Ni0. 13Mn0. 54] O2 using organic chelating agents for lithium-ion batteries
Ortiz et al. A novel architectured negative electrode based on titania nanotube and iron oxide nanowire composites for Li-ion microbatteries
Zheng et al. Electrochemical kinetics and performance of layered composite cathode material Li [Li0. 2Ni0. 2Mn0. 6] O2
Zheng et al. The effects of AlF3 coating on the performance of Li [Li0. 2Mn0. 54Ni0. 13Co0. 13] O2 positive electrode material for lithium-ion battery
Dedryvere et al. Contribution of X-ray photoelectron spectroscopy to the study of the electrochemical reactivity of CoO toward lithium
TWI290781B (en) Electrode active material with multi-element based oxide layers and preparation method thereof
Yang et al. Stepwise co-precipitation to synthesize LiNi1/3Co1/3Mn1/3O2 one-dimensional hierarchical structure for lithium ion batteries
Yang et al. Enhancement on the cycling stability of the layered Ni-rich oxide cathode by in-situ fabricating nano-thickness cation-mixing layers
Lu et al. Observation of electron-beam-induced phase evolution mimicking the effect of the charge–discharge cycle in Li-rich layered cathode materials used for Li ion batteries
Armstrong et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li [Ni0. 2Li0. 2Mn0. 6] O2
Wang et al. Designed strategy to fabricate a patterned V 2 O 5 nanobelt array as a superior electrode for Li-ion batteries
CN105304936B (en) A kind of lithium rechargeable battery
JP4859487B2 (en) Nonaqueous electrolyte secondary battery
Ming et al. Gradient V2O5 surface-coated LiMn2O4 cathode towards enhanced performance in Li-ion battery applications
Zhao et al. An Ion‐Exchange Promoted Phase Transition in a Li‐Excess Layered Cathode Material for High‐Performance Lithium Ion Batteries
CN103296277B (en) A kind of graphite intercalation compound lithium ion battery cathode material and its preparation method and application
CN104008893B (en) The preparation method of lithium ion hybrid capacitors and lithium ion hybrid capacitors thereof
US20150104708A1 (en) Oxide cathode material for lithium ion battery having high energy density and preparation process thereof
US10050263B2 (en) Modified lithium ion battery anode material having high energy density, and manufacturing method thereof
Liu et al. Degradation and structural evolution of xLi2MnO3·(1–x) LiMn1/3Ni1/3Co1/3O2 during cycling

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination