CN109244459A - A kind of codope flexibility sodium-ion battery positive material and preparation method thereof - Google Patents
A kind of codope flexibility sodium-ion battery positive material and preparation method thereof Download PDFInfo
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- CN109244459A CN109244459A CN201811207508.3A CN201811207508A CN109244459A CN 109244459 A CN109244459 A CN 109244459A CN 201811207508 A CN201811207508 A CN 201811207508A CN 109244459 A CN109244459 A CN 109244459A
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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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- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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Abstract
The invention discloses a kind of codope flexibility sodium-ion battery positive materials and preparation method thereof.This codope flexibility sodium-ion battery positive material, chemical formula Na2NimMnFe(CN)6；In formula, at least one of M Mn, Co, Ti, Fe, Cu, Zn, Cr；0≤m≤1,0≤n≤1.The preparation method of this codope flexibility sodium-ion battery positive material is also disclosed simultaneously.The resulting flexible composite electrode material of the present invention has the chemical properties advantage such as high capacity and high circulation stability, meanwhile, there is excellent flexibility and mechanical tensile strength, and preparation process is very simple, low in cost, environment friendly and pollution-free, it is suitble to a large amount of preparations, there is splendid market application value.
Description
Technical field
The present invention relates to a kind of codope flexibility sodium-ion battery positive materials and preparation method thereof.
Background technique
The successful commercialization of lithium ion battery, while bringing many convenient for daily life, security performance
Poor, the problem of higher cost, also becomes researchers and makes great efforts improved reason.Compared to lithium ion battery, sodium-ion battery
As energy storage carrier, although being slightly not so good as in cycle performance, efficiency, energy density, sodium-ion battery raw material sodium
It is from a wealth of sources, it is cheap, and resource distribution is without geographical restrictions, therefore has great resource and cost advantage, Er Qiegui
The safety and cost factor of battery system are more valued in the energy storage of modelling.
The Prussian blue sodium ion positive electrode as a kind of with apparent Three-dimensional Open and rigid frame structure, can
Big ion channel is provided in order to the quick insertion of sodium ion and the structure deviate from without changing material, while also there is charge and discharge
Level platform is high, and energy density is big, at low cost, easily prepares, and advantages of environment protection, these advantages determine that it can meet well
Large-scale application.However, Prussian blue materials synthesis low yield, obvious with electrolyte side reaction, electric conductivity is poor, these problems
Polarization is big when will lead to material storage sodium, and discharge capacity is low, and stable circulation performance is poor.Therefore, in order to better solve Prussia
Indigo plant is used as the problem of sodium-ion battery positive material, and researchers expand to Prussian blue derivative and probe into.Prussia
Indigo plant has numerous analogs, they are referred to as Prussian blue similar object, brilliant because of the presence for the transient metal complex that appraises at the current rate
There are two redox active sites for lattice tool, so that their theoretical specific capacity can achieve 170mAh/g, and electrochemistry
It can be different.In view of it is Prussian blue be Open architecture, ferrous iron and two kinds of new transition metal elements can be allowed at cyano both ends
Staggeredly it is connected, forming properties more preferably new material.CN104701543A discloses a kind of Prussian blue similar object of sodium-ion battery
Positive electrode and preparation method thereof, the Na obtained using coprecipitation2Ni0.4Co0.6Fe(CN)6Positive electrode needs to use cobalt,
Preparation cost is higher, and fails for flexible electrode.
In order to preferably meet pursuit of the people to good life, wearable portable flexible battery is seasonable and gives birth to.It is flexible
Battery will meet do not damage electronics on the basis of can be carried out it is any bending, fold and stretching, extension, this just proposes the production of battery material
New challenge is gone out.The key of flexible battery is flexible electrode, and electrode is needed not occur electricity while meeting flexible demand
Phenomena such as pole piece picking, fracture.CN106549139A discloses a kind of flexible self-supporting nanofiber electrode and preparation method thereof
And active material is embedded into carbon nano-fiber substrate by lithium sodium-ion battery, the technical solution using method of electrostatic spinning, system
Preparation Method is complex.Therefore, there is presently a need to find the sodium ions of a kind of chemical property having had simultaneously and flexible effect
The novel preparation method of battery combination electrode.
Summary of the invention
The purpose of the present invention is to provide a kind of codope flexibility sodium-ion battery positive materials and preparation method thereof, are related to
New energy battery direction, for improving the chemical property of flexible sodium-ion battery.
The technical solution used in the present invention is:
A kind of codope flexibility sodium-ion battery positive material, chemical formula Na2NimMnFe(CN)6；In formula, M Mn,
At least one of Co, Ti, Fe, Cu, Zn, Cr；0≤m≤1,0≤n≤1.
Preferably, this codope flexibility sodium-ion battery positive material, chemical formula Na2NimMnFe(CN)6；In formula, M
For at least one of Mn, Co, Ti；0≤m≤1,0≤n≤1 and m+n=1.
The preparation method of this codope flexibility sodium-ion battery positive material, comprising the following steps:
1) nickel salt solution and transition metal salt solution are mixed, obtains mixing salt solution；
2) by mixing salt solution and the Na that conductive flexible substrate is housed4Fe(CN)6Solution mixing, is protected from light, and is aged；
3) the composite and flexible substrate that reaction obtains is extracted, is washed, dry, compacting obtains codope flexibility sodium-ion battery
Positive electrode.
In the step 1) of preparation method, the concentration of nickel salt solution or transition metal salt solution be 0.005mol/L~
0.2mol/L。
In the step 1) of preparation method, the dosage of nickel salt and transition metal salt is based on the chemistry of Ni and transition metal M element
Amount is than being 0≤Ni/M≤10.
In the step 1) of preparation method, nickel salt, transition metal salt are respectively the chlorate, sulfate, nitric acid of respective metal
At least one of salt, acetate.
In the step 2) of preparation method, mixing salt solution and the Na that conductive flexible substrate is housed4Fe(CN)6Liquor capacity ratio
For 1:1.
In the step 2) of preparation method, the Na equipped with conductive flexible substrate4Fe(CN)6Na in solution4Fe(CN)6Concentration
For 0.01mol/L~0.2mol/L.
In the step 2) of preparation method, conductive flexible substrate is poly- for conductive carbon cloth, carbon nano-tube film, graphene film, conduction
At least one of compound film.
A kind of flexibility sodium-ion battery, codope flexibility sodium-ion battery positive material just extremely above-mentioned.
The beneficial effects of the present invention are:
Gained flexible compound electrode of the invention has the chemical properties advantage such as high capacity and high circulation stability, meanwhile,
With excellent flexibility and mechanical tensile strength, and preparation process is very simple, low in cost, environment friendly and pollution-free, is suitble to big
Amount preparation, has splendid market application value.
Compared with prior art, advantages of the present invention is as follows:
1) the Prussian blue similar object NiHCF synthesized after transition metal element Ni doping is with good stable circulation
Property, high capacity retention ratio can be brought, but its practical storage sodium capacity is poor；What the successful doping of transition metal element Mn was formed
Prussian blue similar object MnHCF is than former Prussian blue material Fe2+/Fe3+Additionally a Mn can be provided more2+/Mn3+Electronics transfer, from
And the storage sodium capacity of material can be effectively promoted, but its cyclical stability is poor；Codope Ni and Mn are formed new Prussian blue
Analog MnNiHCF can effectively combine the advantage of the two, make it while possessing stable cycle performance and coulombic efficiency, again
Possess higher specific capacity；
2) MnNiHCF is grown in conductive flexible substrate, and the flexible compound electrode formed through roll-in can not need to glue
It ties agent and is attached on conductive fiber well, and directly provide electron transport route between active material and collector,
The presence of carbon cloth substrate also makes electrode have excellent flexibility and mechanical tensile strength simultaneously, can meet wearable electricity well
The needs of son.
Detailed description of the invention
Fig. 1 is positive electrode XRD diagram made from embodiment 1；
Fig. 2 is the SEM figure that flexible compound electrode is synthesized in embodiment 1；
Fig. 3 is the composite material charging and discharging curve figure that embodiment 1,2 and comparative example 2 synthesize；
Fig. 4 is the composite material charging and discharging curve figure that embodiment 3,4 and comparative example 1 synthesize；
Fig. 5 is composite material stable circulation performance figure obtained by embodiment and comparative example.
Specific embodiment
A kind of codope flexibility sodium-ion battery positive material, chemical formula Na2NimMnFe(CN)6；In formula, M Mn,
At least one of Co, Ti, Fe, Cu, Zn, Cr；0≤m≤1,0≤n≤1.
Preferably, this codope flexibility sodium-ion battery positive material, chemical formula Na2NimMnFe(CN)6；In formula, M
For at least one of Mn, Co, Ti；0≤m≤1,0≤n≤1 and m+n=1.
It is further preferred that this codope flexibility sodium-ion battery positive material, chemical formula Na2NimMnFe(CN)6；
In formula, M Mn, Co or Ti；M+n=1, m/n=0~10.
The preparation method of this codope flexibility sodium-ion battery positive material, comprising the following steps:
1) nickel salt solution and transition metal salt solution are mixed, obtains mixing salt solution；
2) by mixing salt solution and the Na that conductive flexible substrate is housed4Fe(CN)6Solution mixing, is protected from light, and is aged；
3) the composite and flexible substrate that reaction obtains is extracted, is washed, dry, compacting obtains codope flexibility sodium-ion battery
Positive electrode, chemical formula Na2NimMnFe(CN)6, the value range of m, n is as previously described.
Preferably, in the step 1) of preparation method, the concentration of nickel salt solution or transition metal salt solution is 0.005mol/L
~0.2mol/L.
Preferably, in the step 1) of preparation method, the dosage of nickel salt and transition metal salt is by Ni and transition metal M element
Stoichiometric ratio is 0≤Ni/M≤10；Still further preferably, in the step 1) of preparation method, nickel salt and transition metal salt
Dosage is 1:(0.1~9 by the stoichiometric ratio of Ni and transition metal M element).Transition metal M be Mn, Co, Ti, Fe, Cu, Zn,
At least one of Cr.
Preferably, in the step 1) of preparation method, nickel salt, transition metal salt are respectively the chlorate of respective metal, sulfuric acid
At least one of salt, nitrate, acetate；I.e. nickel salt be the chlorate of nickel, sulfate, nitrate, in acetate at least
It is a kind of；Transition metal salt be the chlorate of Mn, Co, Ti, Fe, Cu, Zn, Ca or Cr, sulfate, nitrate, in acetate extremely
Few one kind；It is further preferred that nickel salt is the chlorate of nickel, transition metal salt is the chlorate of manganese, the chlorate of cobalt or titanium
Chlorate；Still further preferably, nickel salt NiCl2；Transition metal salt is MnCl2、CoCl2Or TiCl3。
Preferably, in the step 2) of preparation method, mixing salt solution and the Na that conductive flexible substrate is housed4Fe(CN)6Solution
Volume ratio is 1:1.
Preferably, in the step 2) of preparation method, the Na equipped with conductive flexible substrate4Fe(CN)6Na in solution4Fe
(CN)6Concentration is 0.01mol/L~0.2mol/L；It is further preferred that being equipped with the Na of conductive flexible substrate4Fe(CN)6In solution
Na4Fe(CN)6Concentration is 0.03mol/L~0.1mol/L.
Preferably, in the step 2) of preparation method, conductive flexible substrate be conductive carbon cloth, carbon nano-tube film, graphene film,
At least one of conductive polymer membrane.
Preferably, it in the step 2) of preparation method, is protected from light as ultrasonic reaction 2h~8h in light protected environment.
Preferably, in the step 2) of preparation method, the time of ageing is 18h~36h.
Preferably, it in the step 2) of preparation method, is aged to be aged at room temperature.
Preferably, in the step 3) of preparation method, washing is specially with dehydrated alcohol and deionized water alternately washing 1~3
It is secondary.
Preferably, in the step 3) of preparation method, it is dry for 18h dry in 50 DEG C~80 DEG C of vacuum oven~
36h。
Preferably, in the step 3) of preparation method, compacting is specially roll-in.
Nickel salt solution described in preparation method, transition metal salt solution, the Na equipped with conductive flexible substrate4Fe(CN)6Solution
It is the aqueous solution of respective substance.
A kind of flexibility sodium-ion battery, codope flexibility sodium-ion battery positive material just extremely above-mentioned.
It is multiple that the present invention discloses a kind of sodium-ion battery flexibility that codope transition metal element synthesizes Prussian blue similar object
Close positive electrode and preparation method thereof.Two kinds of transition metal salt solution are mainly added to dress using coprecipitation by this method
Have in the fewrricyanic acid sodium solution of conductive flexible substrate, small-power ultrasonic mixing is reacted under the conditions of being protected from light, separation, washing, dry, roller
Press two kinds of transition metal element codopes Novel Prussian blue analog Na2NimMnFe(CN)6Flexible electrode.
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1
0.129g NiCl is taken according to the ratio of Ni and Mn stoichiometric ratio 1:42With 0.503g MnCl2It is dissolved in respectively
In 50mL deionized water, then two kinds of solution are evenly mixed in 350mL beaker and are denoted as mixed liquor A；Separately take 2.42gNa4Fe
(CN)6·10H2O is dissolved in 100mL deionized water, is denoted as solution B, and adding one piece of quality in solution B is 0.182g, side length
For the square conductive carbon cloth of 40mm；Mixed liquor A is slowly dropped in solution B in light protected environment again, use during this
100W small-power ultrasound 2h, then after being aged 20h, isolate composite and flexible substrate at this time and sediment powder, use dehydrated alcohol
It is put into 60 DEG C of vacuum ovens for 24 hours with after deionized water alternately washing 3 times, composite and flexible carbon cloth obtains Prussian blue after roll-in
Analog Na2Ni0.2Mn0.8Fe(CN)6Sodium-ion battery flexible compound positive electrode, the material that embodiment 1 obtains are denoted as
NiMnHCF (20%).
Embodiment 2
0.065g NiCl is taken according to the ratio of Ni and Mn stoichiometric ratio 1:92With 0.566g MnCl2It is dissolved in respectively
In 50mL deionized water, then two kinds of solution are evenly mixed in 350mL beaker and are denoted as mixed liquor A；Separately take 2.42gNa4Fe
(CN)6·10H2O is dissolved in 100mL deionized water, is denoted as solution B, and adding one piece of quality in solution B is 0.182g, side length
For the square conductive carbon cloth of 40mm；Mixed liquor A is slowly dropped in solution B in light protected environment again, use during this
100W small-power ultrasound 6h, then after being aged 18h, take out composite and flexible substrate at this time and sediment powder, with dehydrated alcohol and
Deionized water is put into 60 DEG C of vacuum ovens for 24 hours after alternately washing 3 times, and composite and flexible carbon cloth obtains prussian blue after roll-in
Like object Na2Ni0.1Mn0.9Fe(CN)6Sodium-ion battery flexible compound positive electrode, the material that embodiment 2 obtains are denoted as NiMnHCF
(10%).
Embodiment 3
0.259g NiCl is taken according to the ratio of Ni and Mn stoichiometric ratio 2:32With 0.378g MnCl2It is dissolved in respectively
In 50mL deionized water, then two kinds of solution are evenly mixed in 350mL beaker and are denoted as mixed liquor A；Separately take 2.42gNa4Fe
(CN)6·10H2O is dissolved in 100mL deionized water, is denoted as solution B, and adding one piece of quality in solution B is 0.182g, side length
For the square conductive carbon cloth of 40mm；Mixed liquor A is slowly dropped in solution B in light protected environment again, use during this
100W small-power ultrasound 5h, then after being aged for 24 hours, take out composite and flexible substrate at this time and sediment powder, with dehydrated alcohol and
Deionized water is put into 60 DEG C of vacuum ovens for 24 hours after alternately washing 3 times, and composite and flexible carbon cloth obtains prussian blue after roll-in
Like object Na2Ni0.4Mn0.6Fe(CN)6Sodium-ion battery flexible compound positive electrode, the material that embodiment 3 obtains are denoted as NiMnHCF
(40%).
Embodiment 4
0.389g NiCl is taken according to the ratio of Ni and Mn stoichiometric ratio 3:22With 0.252g MnCl2It is dissolved in respectively
In 50mL deionized water, then two kinds of solution are evenly mixed in 350mL beaker and are denoted as mixed liquor A；Separately take 2.42gNa4Fe
(CN)6·10H2O is dissolved in 100mL deionized water, is denoted as solution B, and adding one piece of quality in solution B is 0.182g, side length
For the square conductive carbon cloth of 40mm；Mixed liquor A is slowly dropped in solution B in light protected environment again, use during this
100W small-power ultrasound 8h, then after being aged 36h, take out composite and flexible substrate at this time and sediment powder, with dehydrated alcohol and
Deionized water is put into 60 DEG C of vacuum ovens for 24 hours after alternately washing 3 times, and composite and flexible carbon cloth obtains prussian blue after roll-in
Like object Na2Ni0.6Mn0.4Fe(CN)6Sodium-ion battery flexible compound positive electrode, the material that embodiment 4 obtains are denoted as NiMnHCF
(60%).
Embodiment 5
0.129g NiCl is taken according to the ratio of Ni and Co stoichiometric ratio 1:42With 0.519g CoCl2It is dissolved in respectively
In 50mL deionized water, then two kinds of solution are evenly mixed in 350mL beaker and are denoted as mixed liquor A；Separately take 2.42gNa4Fe
(CN)6·10H2O is dissolved in 100mL deionized water, is denoted as solution B, and adding one piece of quality in solution B is 0.136g, side length
For the square carbon nano-tube film of 40mm；Mixed liquor A is slowly dropped in solution B in light protected environment again, this makes in the process
With 100W small-power ultrasound 5h, then after being aged 30h, composite and flexible carbon nano-tube film and sediment powder at this time is taken out, with nothing
Water-ethanol and deionized water are put into 60 DEG C of vacuum ovens for 24 hours after alternately washing 3 times, and composite and flexible carbon nano-tube film is through roll-in
Afterwards Prussian blue similar object NiCoHCF sodium-ion battery flexible compound positive electrode.
Embodiment 6
0.129g NiCl is taken according to the ratio of Ni and Ti stoichiometric ratio 1:42With 0.905g TiCl3·4H2O difference is molten
Solution is in 50mL deionized water, then two kinds of solution are evenly mixed in 350mL beaker and are denoted as mixed liquor A；Separately take
2.42gNa4Fe(CN)6·10H2O is dissolved in 100mL deionized water, is denoted as solution B, and is added one piece of quality in solution B and be
0.118g, side length are the square graphene film of 40mm；Again in light protected environment, at 60 DEG C, mixed liquor A is slowly dropped to molten
100W small-power ultrasound 4h is used in liquid B, during this, then after being aged 28h, takes out compounded flexible graphite alkene film at this time and heavy
Starch powder is put into 60 DEG C of vacuum ovens for 24 hours, composite and flexible stone after alternately being washed 3 times with dehydrated alcohol and deionized water
Black alkene film obtains Prussian blue similar object NiTiHCF sodium-ion battery flexible compound positive electrode after roll-in.
Comparative example 1
Take 0.648g NiCl2It is dissolved in 100mL deionized water, is denoted as solution A；Separately take 2.42g Na4Fe(CN)6·
10H2O is dissolved in 100mL deionized water, is denoted as solution B, and adding one piece of quality in solution B is 0.182g, side length 40mm
Square conductive carbon cloth；Mixed liquor A is slowly dropped in solution B in light protected environment again, this uses 100W small in the process
Power ultrasound 4h, then after being aged for 24 hours, composite and flexible substrate at this time and sediment powder are taken out, with dehydrated alcohol and deionization
Water is put into 60 DEG C of vacuum ovens for 24 hours after alternately washing 3 times, and Prussian blue similar object Na is obtained after roll-in2NiFe(CN)6(note
For NiHCF) sodium-ion battery flexible compound positive electrode.
Comparative example 2
Take 0.629g MnCl2It is dissolved in 100mL deionized water, is denoted as solution A；Separately take 2.42g Na4Fe(CN)6·
10H2O is dissolved in 100mL deionized water, is denoted as solution B, and adding one piece of quality in solution B is 0.182g, side length 40mm
Square conductive carbon cloth；Mixed liquor A is slowly dropped in solution B in light protected environment again, this uses 100W small in the process
Power ultrasound 4h, then it is aged composite and flexible substrate and the sediment powder taken out for 24 hours at this time, with dehydrated alcohol and deionized water
It is put into 60 DEG C of vacuum ovens for 24 hours after alternately washing 3 times, obtains Prussian blue similar object Na2MnFe(CN)6(being denoted as MnHCF) sodium
Ion battery flexible compound positive electrode.
For the specimen material prepared in embodiment and comparative example, Inductiyely coupled plasma-atomic emission spectrometry instrument is utilized
ICP-AES test can determine Na and [Fe (CN) in the Prussian blue similar object with analytical calculation6]4-Content ratio, the chemistry
Measuring the Prussian blue similar object molecular formula than under is Na2NimMnFe(CN)6, wherein the value of m and n can use Ni and M (Mn, Co
Or Ti) stoichiometric ratio determine, and m+n=1.
Carry out XRD test after dry to precipitating powder washing obtained in embodiment 1, and with Prussian blue standard card
JCPDSNO:52-1907 comparison, it can be found that the Prussian blue similar object crystal diffraction angle after containing transition metal is slightly to the right
Offset, but still be prussian blue cubic structure, as shown in Fig. 1.Attached drawing 2 is flexible compound obtained in embodiment 1
The SEM of electrode schemes.NiMnHCF crystal is at cubic in Fig. 2, is the Prussian blue structure of standard, partial size at 0.8-1.5 μm,
And it is attached on the conductive carbon fibre of carbon cloth well, convenient for the transmitting of electronics between active material and collector.
By the sliced machine-cut of flexible electrode obtained in embodiment 1-4 and comparative example 1-2 at the round pole piece of diameter 14mm,
Then directly as the anode of sodium-ion battery after 85 DEG C of vacuum drying, metallic sodium piece is as cathode, by 1M NaClO4Dissolution
Add 5% additive fluorinated ethylene carbonate FEC 1:1 mixing by volume outside ethylene carbonate EC and diethyl carbonate DEC
As electrolyte, be assembled into the button cell of CR2032 in the glove box of argon atmosphere, and to its blue electrical testing cabinet (5V,
Electrochemical property test is carried out on 5mA).Under 0.1C multiplying power, the 3rd charging and discharging curve such as 3 He of attached drawing corresponding when recycling
Shown in attached drawing 4, it can be found that the MnHCF flexible material in comparative example 2 has highest specific discharge capacity 121.3mAh/g, comparison
1 specific discharge capacity of example is minimum.Attached drawing 5 is battery obtained by embodiment 1-4 and comparative example 1-2 at 0.1C, recycles 50 institutes
Corresponding stable circulation performance curve graph.It is apparent that from Fig. 5, the cyclical stability of embodiment 1NiMnHCF (20%)
Preferably, while it is higher than the sample capacity of other doping ratios.
Claims (10)
1. a kind of codope flexibility sodium-ion battery positive material, it is characterised in that: chemical formula Na2NimMnFe(CN)6；In formula,
M is at least one of Mn, Co, Ti, Fe, Cu, Zn, Cr；0≤m≤1,0≤n≤1.
2. a kind of codope flexibility sodium-ion battery positive material according to claim 1, it is characterised in that: positive electrode
In chemical formula, at least one of M Mn, Co, Ti；0≤m≤1,0≤n≤1 and m+n=1.
3. a kind of preparation method of codope flexibility sodium-ion battery positive material, it is characterised in that: the following steps are included:
1) nickel salt solution and transition metal salt solution are mixed, obtains mixing salt solution；
2) by mixing salt solution and the Na that conductive flexible substrate is housed4Fe(CN)6Solution mixing, is protected from light, and is aged；
3) the composite and flexible substrate that reaction obtains is extracted, is washed, dry, compacting obtains codope of any of claims 1 or 2
Flexible sodium-ion battery positive material.
4. a kind of preparation method of codope flexibility sodium-ion battery positive material according to claim 3, feature exist
In: in step 1), the concentration of nickel salt solution or transition metal salt solution is 0.005mol/L~0.2mol/L.
5. a kind of preparation method of codope flexibility sodium-ion battery positive material according to claim 4, feature exist
In: in step 1), the dosage of nickel salt and transition metal salt by the stoichiometric ratio of Ni and transition metal M element be 0≤Ni/M≤
10。
6. a kind of preparation method of codope flexibility sodium-ion battery positive material, feature according to claim 3 or 5
Be: in step 1), nickel salt, transition metal salt be respectively the chlorate of respective metal, sulfate, nitrate, in acetate
It is at least one.
7. a kind of preparation method of codope flexibility sodium-ion battery positive material according to claim 3, feature exist
In: in step 2), mixing salt solution and the Na that conductive flexible substrate is housed4Fe(CN)6Liquor capacity ratio is 1:1.
8. a kind of preparation method of codope flexibility sodium-ion battery positive material according to claim 7, feature exist
In: in step 2), the Na equipped with conductive flexible substrate4Fe(CN)6Na in solution4Fe(CN)6Concentration be 0.01mol/L~
0.2mol/L。
9. a kind of preparation method of codope flexibility sodium-ion battery positive material, feature according to claim 3 or 8
Be: in step 2), conductive flexible substrate be conductive carbon cloth, carbon nano-tube film, graphene film, in conductive polymer membrane at least
It is a kind of.
10. a kind of flexibility sodium-ion battery, it is characterised in that: codope flexibility sodium ion just extremely of any of claims 1 or 2
Cell positive material.
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