CN109244459B - Codoped flexible sodium-ion battery positive electrode material and preparation method thereof - Google Patents
Codoped flexible sodium-ion battery positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a codoped flexible sodium-ion battery positive electrode material and a preparation method thereof. The codoped flexible sodium-ion battery cathode material has a chemical formula of Na2NimMnFe(CN)6(ii) a Wherein M is at least one of Mn, Co, Ti, Fe, Cu, Zn and Cr; m is more than or equal to 0 and less than or equal to 1, and n is more than or equal to 0 and less than or equal to 1. Meanwhile, a preparation method of the codoped flexible sodium-ion battery positive electrode material is also disclosed. The flexible composite electrode material obtained by the invention has the advantages of high capacity, high cycle stability and other electrochemical properties, and meanwhile, has excellent flexibility and mechanical tensile strength, and the preparation process is very simple, low in cost, environment-friendly and pollution-free, is suitable for mass preparation, and has excellent market application value.
Description
Technical Field
The invention relates to a codoped flexible sodium-ion battery positive electrode material and a preparation method thereof.
Background
The successful commercialization of lithium ion batteries brings great convenience to daily life of people, and the problems of poor safety performance and high cost also become the motivation for researchers to improve. Compared with a lithium ion battery, the sodium ion battery is used as an energy storage carrier, although the cycle performance, the efficiency and the energy density are slightly poor, the sodium ion battery raw material sodium is wide in source and low in price, and the resource distribution is not limited by regions, so that the sodium ion battery has great resource and cost advantages, and the large-scale energy storage pays more attention to the safety and cost factors of a battery system.
Prussian blue serving as a sodium ion anode material with an obvious three-dimensional open and rigid frame structure can provide a large ion channel so as to facilitate rapid embedding and releasing of sodium ions without changing the structure of the material, and has the advantages of high charge and discharge platform, high energy density, low cost, easiness in preparation, environmental friendliness and the like, and the advantages determine that the Prussian blue can well meet large-scale application. However, prussian blue material has low synthesis yield, obvious side reaction with electrolyte and poor conductivity, and the problems of large polarization, low discharge capacity and poor cycle stability when the material stores sodium are caused. Therefore, in order to better solve the problem of prussian blue as a positive electrode material of a sodium ion battery, researchers have conducted extensive research on prussian blue derivatives. Prussian blue has a plurality of analogues, which are collectively called as Prussian blue analogues, because the valence-variable transition metal complex exists, the crystal lattice of the Prussian blue has two redox active sites, so that the theoretical specific capacity of the Prussian blue can reach 170mAh/g, and the Prussian blue has different electrochemical properties. Because the Prussian blue is an open structure, ferrous iron and two new transition metal elements can be connected in a staggered mode at two ends of a cyano group, and a new material with better performance is formed. CN104701543A discloses Prussian blue analogue positive electrode material of sodium ion battery and preparation method thereof, and Na obtained by coprecipitation method2Ni0.4Co0.6Fe(CN)6The anode material needs cobalt, has high preparation cost and cannot be used for a flexible electrode.
In order to better meet the pursuit of people for good life, the wearable portable flexible battery is worn out at any time. The flexible battery is required to be capable of being bent, folded and stretched freely on the basis of not damaging electrons, and therefore, a new challenge is brought to the manufacturing of battery materials. The key of the flexible battery is the flexible electrode, and the electrode is required to meet the flexible requirement without the phenomena of electrode plate powder falling, breakage and the like. CN106549139A discloses a flexible self-supporting nanofiber electrode, a preparation method thereof and a lithium sodium ion battery. Therefore, a new method for preparing a sodium-ion battery composite electrode with good electrochemical performance and flexibility is needed.
Disclosure of Invention
The invention aims to provide a codoped flexible sodium-ion battery positive electrode material and a preparation method thereof, relates to the direction of new energy batteries, and is used for improving the electrochemical performance of a flexible sodium-ion battery.
The technical scheme adopted by the invention is as follows:
a codoped flexible positive electrode material for sodium-ion battery with chemical formula of Na2NimMnFe(CN)6(ii) a Wherein M is at least one of Mn, Co, Ti, Fe, Cu, Zn and Cr; m is more than or equal to 0 and less than or equal to 1, and n is more than or equal to 0 and less than or equal to 1.
Preferably, the codoped flexible positive electrode material for the sodium-ion battery has a chemical formula of Na2NimMnFe(CN)6(ii) a In the formula, M is at least one of Mn, Co and Ti; m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and m + n is equal to 1.
The preparation method of the codoped flexible sodium-ion battery positive electrode material comprises the following steps:
1) mixing a nickel salt solution and a transition metal salt solution to obtain a mixed salt solution;
2) mixing the mixed salt solution with Na filled with conductive flexible substrate4Fe(CN)6Mixing the solutions, reacting in dark and aging;
3) and extracting the composite flexible substrate obtained by the reaction, washing, drying and pressing to obtain the co-doped flexible sodium-ion battery positive electrode material.
In the step 1) of the preparation method, the concentration of the nickel salt solution or the transition metal salt solution is 0.005 mol/L-0.2 mol/L.
In the step 1) of the preparation method, the dosage of the nickel salt and the transition metal salt is more than or equal to 0 and less than or equal to 10 according to the stoichiometric ratio of Ni to the transition metal M.
In the step 1) of the preparation method, the nickel salt and the transition metal salt are respectively at least one of chloride, sulfate, nitrate and acetate of respective metals.
In step 2) of the preparation method, a salt solution is mixed with Na provided with a conductive flexible substrate4Fe(CN)6The volume ratio of the solution is 1: 1.
In step 2) of the preparation method, Na provided with a conductive flexible substrate4Fe(CN)6Na in solution4Fe(CN)6The concentration is 0.01 mol/L-0.2 mol/L.
In the step 2) of the preparation method, the conductive flexible substrate is at least one of conductive carbon cloth, a carbon nanotube film, a graphene film and a conductive polymer film.
The positive electrode of the flexible sodium-ion battery is the co-doped flexible sodium-ion battery positive electrode material.
The invention has the beneficial effects that:
the flexible composite electrode obtained by the invention has the advantages of high capacity, high cycle stability and other electrochemical properties, and meanwhile, has excellent flexibility and mechanical tensile strength, and the preparation process is very simple, low in cost, environment-friendly and pollution-free, is suitable for mass preparation, and has excellent market application value.
Compared with the prior art, the invention has the following advantages:
1) the Prussian blue analogue NiHCF synthesized after the transition metal element Ni is doped has good circulation stability and can bring high capacity retention rate, but the actual sodium storage capacity is poor; prussian blue analogue MnHCF formed by successfully doping transition metal element Mn is larger than original Prussian blue material Fe2+/Fe3+Can additionally provide one more Mn2+/Mn3+Electron transfer can effectively improve the sodium storage capacity of the material, but the cycling stability is poor; the novel Prussian blue analogue MnNiHCF formed by co-doping Ni and Mn can effectively combine the advantages of Ni and Mn, so that the novel Prussian blue analogue has stable cycle performance and coulombic efficiency and higher specific capacity;
2) MnNiHCF grows on a conductive flexible substrate, a flexible composite electrode formed by rolling can be well attached to conductive fibers without a binder, an electron transfer path is directly provided between an active material and a current collector, and meanwhile, the electrode has excellent flexibility and mechanical tensile strength due to the existence of the carbon cloth substrate, and the requirements of wearable electronics can be well met.
Drawings
FIG. 1 is an XRD pattern of a positive electrode material obtained in example 1;
FIG. 2 is an SEM photograph of the synthetic flexible composite electrode of example 1;
FIG. 3 is a graph showing the charge and discharge curves of the composite materials synthesized in examples 1 and 2 and comparative example 2;
FIG. 4 is a graph showing the charge and discharge curves of the composite materials synthesized in examples 3 and 4 and comparative example 1;
FIG. 5 is a graph showing the cycle stability of the composite materials obtained in examples and comparative examples.
Detailed Description
A codoped flexible positive electrode material for sodium-ion battery with chemical formula of Na2NimMnFe(CN)6(ii) a Wherein M is at least one of Mn, Co, Ti, Fe, Cu, Zn and Cr; m is more than or equal to 0 and less than or equal to 1, and n is more than or equal to 0 and less than or equal to 1.
Preferably, the codoped flexible positive electrode material for the sodium-ion battery has a chemical formula of Na2NimMnFe(CN)6(ii) a In the formula, M is at least one of Mn, Co and Ti; m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and m + n is equal to 1.
Further preferably, the codoped flexible positive electrode material for the sodium-ion battery has a chemical formula of Na2NimMnFe(CN)6(ii) a Wherein M is Mn, Co or Ti; m + n is 1, and m/n is 0-10.
The preparation method of the codoped flexible sodium-ion battery positive electrode material comprises the following steps:
1) mixing a nickel salt solution and a transition metal salt solution to obtain a mixed salt solution;
2) mixing the mixed salt solution with Na filled with conductive flexible substrate4Fe(CN)6Mixing the solutions, reacting in dark and aging;
3) extracting the composite flexible substrate obtained by the reaction, washing, drying and pressing to obtain the codoped flexible sodium-ion battery positive electrode materialOf the chemical formula Na2NimMnFe(CN)6The value ranges of m and n are as described above.
Preferably, in step 1) of the preparation method, the concentration of the nickel salt solution or the transition metal salt solution is 0.005mol/L to 0.2 mol/L.
Preferably, in the step 1) of the preparation method, the dosage of the nickel salt and the transition metal salt is 0 to 10 of Ni/M according to the stoichiometric ratio of Ni to the transition metal M; still further preferably, in step 1) of the preparation method, the nickel salt and the transition metal salt are used in a ratio of 1: (0.1 to 9). The transition metal M is at least one of Mn, Co, Ti, Fe, Cu, Zn and Cr.
Preferably, in step 1) of the preparation method, the nickel salt and the transition metal salt are at least one of chloride, sulfate, nitrate and acetate of respective metals; the nickel salt is at least one of chloride, sulfate, nitrate and acetate of nickel; the transition metal salt is at least one of chloride, sulfate, nitrate and acetate of Mn, Co, Ti, Fe, Cu, Zn, Ca or Cr; further preferably, the nickel salt is a chloride salt of nickel, and the transition metal salt is a chloride salt of manganese, cobalt or titanium; still more preferably, the nickel salt is NiCl2(ii) a The transition metal salt is MnCl2、CoCl2Or TiCl3。
Preferably, in step 2) of the preparation method, the salt solution is mixed with Na loaded with the conductive flexible substrate4Fe(CN)6The volume ratio of the solution is 1: 1.
Preferably, in step 2) of the preparation method, Na is loaded on the conductive flexible substrate4Fe(CN)6Na in solution4Fe(CN)6The concentration is 0.01 mol/L-0.2 mol/L; further preferred is Na provided with a conductive flexible substrate4Fe(CN)6Na in solution4Fe(CN)6The concentration is 0.03 mol/L-0.1 mol/L.
Preferably, in step 2) of the preparation method, the conductive flexible substrate is at least one of a conductive carbon cloth, a carbon nanotube film, a graphene film and a conductive polymer film.
Preferably, in the step 2) of the preparation method, the light-shielding reaction is ultrasonic reaction for 2 to 8 hours in a light-shielding environment.
Preferably, in the step 2) of the preparation method, the aging time is 18-36 h.
Preferably, in step 2) of the preparation process, the aging is carried out at room temperature.
Preferably, in the step 3) of the preparation method, the washing is specifically performed by alternately washing with absolute ethyl alcohol and deionized water for 1-3 times.
Preferably, in the step 3) of the preparation method, the drying is carried out for 18 to 36 hours in a vacuum drying oven at the temperature of between 50 and 80 ℃.
Preferably, in step 3) of the preparation method, the pressing is specifically roll pressing.
The preparation method comprises the steps of preparing the nickel salt solution, the transition metal salt solution and Na provided with the conductive flexible substrate4Fe(CN)6The solutions are aqueous solutions of the respective substances.
The positive electrode of the flexible sodium-ion battery is the co-doped flexible sodium-ion battery positive electrode material.
The invention discloses a sodium ion battery flexible composite anode material codoped with transition metal elements to synthesize Prussian blue analogues and a preparation method thereof. The method mainly comprises the steps of adding two transition metal salt solutions into a sodium ferricyanate solution filled with a conductive flexible substrate by using a coprecipitation method, carrying out low-power ultrasonic mixed reaction under the condition of keeping out of the sun, separating, washing, drying and rolling to obtain the novel Prussian blue analogue Na co-doped with two transition metal elements2NimMnFe(CN)6A flexible electrode.
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1
Taking 0.129g NiCl according to the ratio of 1:4 of the stoichiometric ratio of Ni to Mn2And 0.503g MnCl2Respectively dissolving the two solutions in 50mL of deionized water, and uniformly mixing the two solutions in a 350mL beaker to obtain a mixed solution A; in additionTaking 2.42gNa4Fe(CN)6·10H2Dissolving O in 100mL of deionized water, marking as a solution B, and adding a square conductive carbon cloth with the mass of 0.182g and the side length of 40mm into the solution B; slowly dripping the mixed solution A into the solution B in a light-proof environment, performing 100W low-power ultrasonic treatment for 2h in the process, aging for 20h, separating out the composite flexible substrate and precipitate powder, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, putting into a vacuum drying box at 60 ℃ for 24h, and rolling the composite flexible carbon cloth to obtain the Prussian blue analogue Na2Ni0.2Mn0.8Fe(CN)6The material obtained in example 1 was designated as NiMnHCF (20%).
Example 2
Taking 0.065g NiCl according to the stoichiometric ratio of Ni to Mn of 1:92And 0.566g of MnCl2Respectively dissolving the two solutions in 50mL of deionized water, and uniformly mixing the two solutions in a 350mL beaker to obtain a mixed solution A; another 2.42g Na is taken4Fe(CN)6·10H2Dissolving O in 100mL of deionized water, marking as a solution B, and adding a square conductive carbon cloth with the mass of 0.182g and the side length of 40mm into the solution B; slowly dripping the mixed solution A into the solution B in a light-proof environment, performing 100W low-power ultrasound for 6 hours in the process, aging for 18 hours, taking out the composite flexible substrate and precipitate powder, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, putting into a vacuum drying oven at 60 ℃ for 24 hours, and rolling the composite flexible carbon cloth to obtain the Prussian blue analogue Na2Ni0.1Mn0.9Fe(CN)6The sodium-ion battery flexible composite positive electrode material obtained in example 2 was designated as NiMnHCF (10%).
Example 3
Taking 0.259g NiCl according to the ratio of the stoichiometric ratio of Ni to Mn of 2:32And 0.378g MnCl2Respectively dissolving the two solutions in 50mL of deionized water, and uniformly mixing the two solutions in a 350mL beaker to obtain a mixed solution A; another 2.42g Na is taken4Fe(CN)6·10H2O is dissolved in 100mL of deionized water and is marked as solution B, and a square with the mass of 0.182g and the side length of 40mm is added into the solution BForming a conductive carbon cloth; slowly dripping the mixed solution A into the solution B in a light-proof environment, performing 100W low-power ultrasound for 5 hours in the process, aging for 24 hours, taking out the composite flexible substrate and precipitate powder, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, putting into a vacuum drying oven at 60 ℃ for 24 hours, and rolling the composite flexible carbon cloth to obtain the Prussian blue analogue Na2Ni0.4Mn0.6Fe(CN)6The sodium-ion battery flexible composite positive electrode material obtained in example 3 was designated as NiMnHCF (40%).
Example 4
Taking 0.389g NiCl according to the ratio of 3:2 of the stoichiometric ratio of Ni to Mn2And 0.252g MnCl2Respectively dissolving the two solutions in 50mL of deionized water, and uniformly mixing the two solutions in a 350mL beaker to obtain a mixed solution A; another 2.42g Na is taken4Fe(CN)6·10H2Dissolving O in 100mL of deionized water, marking as a solution B, and adding a square conductive carbon cloth with the mass of 0.182g and the side length of 40mm into the solution B; slowly dripping the mixed solution A into the solution B in a light-proof environment, performing 100W low-power ultrasonic treatment for 8 hours in the process, aging for 36 hours, taking out the composite flexible substrate and precipitate powder, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, putting into a vacuum drying oven at 60 ℃ for 24 hours, and rolling the composite flexible carbon cloth to obtain the Prussian blue analogue Na2Ni0.6Mn0.4Fe(CN)6The sodium-ion battery flexible composite positive electrode material obtained in example 4 was designated as NiMnHCF (60%).
Example 5
Taking 0.129g NiCl according to the ratio of 1:4 of the stoichiometric ratio of Ni to Co2And 0.519g CoCl2Respectively dissolving the two solutions in 50mL of deionized water, and uniformly mixing the two solutions in a 350mL beaker to obtain a mixed solution A; another 2.42g Na is taken4Fe(CN)6·10H2Dissolving O in 100mL of deionized water, marking as a solution B, and adding a square carbon nanotube film with the mass of 0.136g and the side length of 40mm into the solution B; slowly dripping the mixed solution A into the solution B in a light-proof environment, performing 100W low-power ultrasound for 5 hours in the process, aging for 30 hours, and taking out the composite flexible carbon nanoAnd alternately washing the nanotube film and the precipitate powder with absolute ethyl alcohol and deionized water for 3 times, putting the washed substances into a vacuum drying oven at 60 ℃ for 24 hours, and rolling the composite flexible carbon nanotube film to obtain the Prussian blue analogue NiCoHCF sodium-ion battery flexible composite anode material.
Example 6
Taking 0.129g NiCl according to the ratio of 1:4 of the stoichiometric ratio of Ni to Ti2And 0.905g TiCl3·4H2Dissolving O in 50mL of deionized water respectively, and then uniformly mixing the two solutions in a 350mL beaker to obtain a mixed solution A; another 2.42g Na is taken4Fe(CN)6·10H2Dissolving O in 100mL of deionized water, marking as a solution B, and adding a square graphene film with the mass of 0.118g and the side length of 40mm into the solution B; and slowly dropwise adding the mixed solution A into the solution B at 60 ℃ in a light-proof environment, carrying out 100W low-power ultrasound for 4h in the process, aging for 28h, taking out the composite flexible graphene film and precipitate powder, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then putting into a vacuum drying oven at 60 ℃ for 24h, and rolling the composite flexible graphene film to obtain the Prussian blue analogue NiTiHCF sodium ion battery flexible composite anode material.
Comparative example 1
0.648g of NiCl was taken2Dissolving in 100mL of deionized water, and marking as a solution A; another 2.42g of Na is taken4Fe(CN)6·10H2Dissolving O in 100mL of deionized water, marking as a solution B, and adding a square conductive carbon cloth with the mass of 0.182g and the side length of 40mm into the solution B; slowly dripping the mixed solution A into the solution B in a light-proof environment, performing 100W low-power ultrasonic treatment for 4 hours in the process, aging for 24 hours, taking out the composite flexible substrate and precipitate powder, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, putting into a vacuum drying oven at 60 ℃ for 24 hours, and rolling to obtain Prussian blue analogue Na2NiFe(CN)6(record as NiHCF) sodium ion battery flexible composite anode material.
Comparative example 2
Taking 0.629g of MnCl2Dissolving in 100mL of deionized water, and marking as a solution A; another 2.42g of Na is taken4Fe(CN)6·10H2Dissolving O in 100mL of deionized water, marking as a solution B, and adding a square conductive carbon cloth with the mass of 0.182g and the side length of 40mm into the solution B; slowly dripping the mixed solution A into the solution B in a light-proof environment, performing 100W low-power ultrasonic treatment for 4h in the process, aging for 24h, taking out the composite flexible substrate and precipitate powder, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and putting into a vacuum drying oven at 60 ℃ for 24h to obtain Prussian blue analogue Na2MnFe(CN)6(noted as MnHCF) sodium-ion battery flexible composite anode material.
For the sample materials prepared in examples and comparative examples, Na and [ Fe (CN) ] in the Prussian blue analogue can be determined by ICP-AES test of inductively coupled plasma atomic emission spectrometer and analytical calculation6]4-The molecular formula of the Prussian blue analogue in the stoichiometric ratio is Na2NimMnFe(CN)6Where the values of M and n can be determined using the stoichiometric ratio of Ni and M (Mn, Co or Ti), and M + n is 1.
XRD test is carried out on the precipitated starch powder obtained in the example 1 after washing and drying, and compared with the Prussian blue standard card JCPDSNO:52-1907, the crystal diffraction angle of the Prussian blue analogue doped with the transition metal is slightly shifted to the right, but the Prussian blue analogue still has a cubic crystal structure, as shown in an attached figure 1. Fig. 2 is an SEM image of the flexible composite electrode obtained in example 1. In the figure 2, the NiMnHCF crystal is in a cubic shape and is in a standard Prussian blue structure, the grain diameter is 0.8-1.5 mu m, and the NiMnHCF crystal is well attached to the conductive carbon fiber of the carbon cloth, so that the transmission of electrons between an active material and a current collector is facilitated.
The flexible electrodes obtained in examples 1-4 and comparative examples 1-2 were cut into circular pole pieces with a diameter of 14mm by a microtome, and then dried at 85 ℃ in vacuum to be used directly as the positive electrode of a sodium ion battery, a metal sodium sheet as the negative electrode, and 1M NaClO4The electrolyte solution of fluoroethylene carbonate FEC dissolved in ethylene carbonate EC and diethyl carbonate DEC with the addition of 5 percent of additive fluoroethylene carbonate FEC is mixed according to the volume ratio of 1:1, the button cell of CR2032 is assembled in a glove box in argon atmosphere, and the button cell is tested on a blue test cabinet (5V, 5mA)And (4) testing the electrochemical performance. At the 0.1C rate, the charging and discharging curves corresponding to the 3 rd cycle are shown in the attached figures 3 and 4, and the MnHCF flexible material in the comparative example 2 can be found to have the highest specific discharge capacity of 121.3mAh/g, and the specific discharge capacity of the comparative example 1 is the lowest. FIG. 5 is a graph showing the cycle stability of the batteries manufactured in examples 1 to 4 and comparative examples 1 to 2 at 0.1C for 50 cycles. It is apparent from fig. 5 that the cycling stability of example 1NiMnHCF (20%) is the best, while the capacity is higher than that of the samples with other doping ratios.
Claims (8)
1. The utility model provides a flexible sodium ion battery cathode material of codope which characterized in that: has a chemical formula of Na2NimMnFe(CN)6(ii) a In the formula, M is Mn; m + n =1, m/n = 0-10, m is more than 0 and less than 1, and n is more than 0 and less than 1;
the co-doped flexible sodium-ion battery positive electrode material is prepared by the following preparation method:
1) mixing a nickel salt solution and a transition metal salt solution to obtain a mixed salt solution;
2) mixing the mixed salt solution with Na filled with conductive flexible substrate4Fe(CN)6Mixing the solutions, reacting in dark and aging;
3) extracting the composite flexible substrate obtained by the reaction, washing, drying and pressing to obtain a co-doped flexible sodium-ion battery positive electrode material;
in the step 2), the conductive flexible substrate is at least one of conductive carbon cloth, a carbon nanotube film, a graphene film and a conductive polymer film;
in the step 3), the pressing is specifically rolling.
2. The preparation method of the co-doped flexible sodium-ion battery positive electrode material of claim 1 is characterized by comprising the following steps: the method comprises the following steps:
1) mixing a nickel salt solution and a transition metal salt solution to obtain a mixed salt solution;
2) mixing the mixed salt solution with Na filled with conductive flexible substrate4Fe(CN)6Mixing the solutions and reacting in the darkAging;
3) extracting the composite flexible substrate obtained by the reaction, washing, drying and pressing to obtain the co-doped flexible sodium-ion battery positive electrode material;
in the step 2), the conductive flexible substrate is at least one of conductive carbon cloth, a carbon nanotube film, a graphene film and a conductive polymer film;
in the step 3), the pressing is specifically rolling.
3. The preparation method of the co-doped flexible sodium-ion battery positive electrode material according to claim 2, characterized in that: in the step 1), the concentration of the nickel salt solution or the transition metal salt solution is 0.005 mol/L-0.2 mol/L.
4. The preparation method of the co-doped flexible sodium-ion battery positive electrode material according to claim 3, characterized by comprising the following steps: in the step 1), the dosage of the nickel salt and the transition metal salt is more than 0 and less than or equal to 10 according to the stoichiometric ratio of Ni to the transition metal M.
5. The preparation method of the co-doped flexible sodium-ion battery positive electrode material according to claim 2 or 4, characterized in that: in the step 1), the nickel salt and the transition metal salt are respectively at least one of chloride, sulfate, nitrate and acetate of respective metals.
6. The preparation method of the co-doped flexible sodium-ion battery positive electrode material according to claim 2, characterized in that: in step 2), mixing the salt solution with Na provided with a conductive flexible substrate4Fe(CN)6The volume ratio of the solution is 1: 1.
7. The preparation method of the co-doped flexible sodium-ion battery positive electrode material according to claim 6, characterized in that: in step 2), Na with a conductive flexible substrate is filled4Fe(CN)6Na in solution4Fe(CN)6The concentration is 0.01mol/L to 0.2 mol/L.
8. A flexible sodium ion battery, characterized by: the positive electrode is the co-doped flexible sodium-ion battery positive electrode material in the claim 1.
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