CN110416489A - The nanofiber storage sodium positive electrode preparation of nano particle assembling and application method - Google Patents
The nanofiber storage sodium positive electrode preparation of nano particle assembling and application method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Nanofiber storage sodium positive electrode preparation and application method the invention discloses a kind of assembling of nano particle.1) polyvinylpyrrolidone (PVP) is dissolved in deionized water, glacial acetic acid is added and adjusts pH value of solution wiring solution-forming A, then soluble sodium salt, nickel salt, manganese salt are added in solution A successively in proportion, stirring forms homogeneous solution B.2) solution prepared is prepared into composite nano fiber using electrostatic spinning technique, calcining decomposes polyvinylpyrrolidone and forms porous structure, obtains Na2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling.The invention has the advantages that preparation process is simple, reproducible, reaction condition is easily controllable.Resulting materials are the nanofiber of nano particle assembling, nanoparticle size is 20-90nm, nanofiber diameter is 200-600nm, fiber, which is cross-linked with each other, to be formed three-dimensional network skeleton and enhances the structural stability of material, the quick embedding de- of sodium ion is promoted simultaneously, so that storage sodium capacity, high rate performance and cycle life are significantly improved, have a good application prospect.
Description
Technical field
The invention belongs to sodium-ion battery technical fields, in particular to Na2/3Ni1/3Mn2/3O2The nanometer of nano particle assembling
Fiber stores up the preparation of sodium positive electrode and application method.
Background technique
Recently as electric car, the rapid development of smart grid and the mankind to intermittent renewable clean energy resource
The increasingly favor of (such as solar energy, wind energy, tide energy, geothermal energy), it is imperative to develop extensive energy storage device.Although lithium ion
Battery performance is excellent, but reserves are limited on earth, be unevenly distributed, price is higher has become in its road for development for lithium resource
Bottleneck.Sodium ion is resourceful, widely distributed, cheap, and sodium and lithium belong to same main group, has similar physics and chemistry
Matter, battery charging and discharging principle is almost the same, is all " rocking chair type " battery, thus sodium-ion battery is considered next-generation extensive
One ideal chose of energy storage technology.
Sodium ion has biggish radius and quality compared with lithium ion, causes its transport kinetics slow, sodium ion electricity
The fast charging and discharging ability in pond is seriously restricted.In addition, storage sodium process be easy to cause the biggish volume change of electrode material, even
Irreversible structural phase transition is induced, the cyclical stability of battery is influenced.Furthermore the current potential of sodium is higher compared to lithium, can reduce battery
Operating voltage and energy density.Factors above is all the important original for causing sodium-ion battery to have not been achievable large-scale commercial
Cause.Therefore, the host material that quick, stable storage sodium is capable of in exploitation is the key that promote one of sodium-ion battery performance.
In sodium-ion battery positive material, layered oxide is convieniently synthesized, and two-dimentional transmission channel can effectively facilitate
Sodium ion quickly transmits.And the compacted density of stratified material is higher, and sodium-ion battery is made to possess higher specific energy, so by
It is considered one of the positive electrode of most prospect.Delmas etc. is according to Na+In the arrangement mode of transition metal interlayer, by stratiform
NaxMO2(M is transition metal) is broadly divided into two class of O3 type and P2 type.Wherein the O of On type refers to sodium ion and oxonium ion is octahedral
Body coordination, the P of Pn type refer to sodium ion and oxonium ion for triangular prism coordination, and n represents transition metal ions and occupies different location
Number, determined by the accumulation mode of oxonium ion, if O3 type is arranged in ABCABCABC mode, P2 type is arranged in ABBAABBA mode
Column.Studies have shown that the stratified material of the stratified material ratio O3 type structure of P2 type structure has better chemical property, O3 type is living
Property the most charging and discharging capacity of material it is lower and it is easy occur O3 to P3 between phase transformation.The reason is that P2 compared to O3 phase have it is bigger
Sodium ion stores site, Na in P2 phase+Positioned at prism position, the Na in migration+The shared rectangle face of two prisms need to only be crossed i.e.
It can；And the Na in O3 phase+Migration will pass through the small tetrahedron between two adjacent octahedrons.Therefore, the Na in P2 phase+Migration
A possibility that path is shorter, and activates the little energy needed, and potential barrier when diffusion is lower, undergoes phase transition is smaller.P2 phase material with
By means of higher reversible capacity and cycle life, become a kind of very promising sodium-ion battery positive material.
In existing research, the layered oxide material of the compositions such as transition metal iron, manganese, nickel is received significant attention, and
Very likely realize large-scale commercial application, but its pattern tissue is substantially based on irregular particle, there are high rate performance compared with
The disadvantages of difference, unstable circulation.Such as NaxMnO2Although the theoretical specific capacity of the material is very high, since there are stronger
Jahn-Teller effect, cycle performance is very poor, farther out from practical application；Na for another examplexFeO2, the material price is very low
It is honest and clean, there is high oxidation-reduction potential, but its synthesis condition is complicated, generally requires and uses sodium oxide molybdena or sodium peroxide, it is uncomfortable
Close industrialized production；NaxNiO2Due to Ni2+/Ni3+/Ni4+High potential and there is very strong attraction, but its air stability
It is poor.
Therefore, the modification mode that cation replaces is come into being, by a variety of transition metal elements (such as Ni, Fe, Mn, Co)
It is entrained in same material, using the synergistic effect of variety classes element, eliminates or reduce the defect of single oxide, reduce
Multiphase transformation promotes average working voltage, and then improves chemical property.At the same time, nano-electrode material often have compared with
Big specific surface area can expose active site abundant, while be able to bear high deformational stress, shorten Ion transfer road
Diameter accelerates kinetics.Therefore, nanostructure is widely used in storing up sodium, and shows huge advantage.Wherein, a wiener
Rice material relies on high reactivity, and ion, electron-transport path and the strong ability of anti-deformation of orientation are expected to greatly improve
The high rate performance and cyclical stability of layered metal oxide.
Based on this, the present invention provides Na2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling stores up sodium positive electrode system
Standby and application method.Electrostatic spinning technique is applied to P2 type stratiform Na2/3Ni1/3Mn2/3O2The preparation of positive electrode, this method
It is simple and easy, reproducible, be easy to volume production, tiny Na can be obtained2/3Ni1/3Mn2/3O2Particle assembling at nanofiber knot
Structure.Wherein, the size of nano particle is 20-90nm, and the diameter of nanofiber is 200-600nm, and nanofiber integrality is good
It is good, it is evenly distributed, interconnecting to form the reversible deintercalation that three-dimensional network skeleton promotes sodium ion, and the structure for enhancing material is steady
Qualitative while high specific surface area makes it that can expose more active sites in actual use, so that storage sodium capacity, forthright again
It can be significantly improved with cycle life.
Summary of the invention
The purpose of the present invention is to provide Na2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling stores up sodium positive electrode
Preparation and application method.
Based on above-mentioned purpose, this invention takes following technical solutions:
Na2/3Ni1/3Mn2/3O2The nanofiber storage sodium positive electrode preparation of nano particle assembling and application method, including with
Lower step:
1) polyvinylpyrrolidone (PVP) is dissolved in deionized water, glacial acetic acid adjustment is added to after being completely dissolved for stirring
PH value of solution wiring solution-forming A；
2) soluble sodium salt, nickel salt, manganese salt are added in solution A successively in proportion, are formed under continuing magnetic force stirring equal
Even solution B；
3) solution B is transferred in syringe, with 12-15 μ L min-1Fltting speed be injected to reception aluminium foil, syringe
It is 15-20cm with distance between aluminium foil is received, while applies the high-pressure electrostatic of 16-18kV between syringe and reception aluminium foil
, the spinning time is 10-15 hours, and it is 30-50 μm that collection, which obtains Electrospun film thickness,；
4) by the above-mentioned Electrospun film being collected into air atmosphere, 500 DEG C are warming up to the heating rate of 2 DEG C/min
Heat preservation 2h decomposes PVP and forms porous structure, is continuously heating to 700-900 DEG C and keeps the temperature 6h, is cooled to 500 with 5 DEG C/min
Temperature fall after DEG C, to obtain P-2Na2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling, so with acetylene black, viscous
Agent polyvinylidene fluoride (PVDF) mixing is tied, sodium-ion battery positive plate is made.
Further, the mass percent of polyvinylpyrrolidone (PVP) in the solution is in the step (1)
12.8%.
Further, the positive plate material is the layered oxide structure of P2 phase.
Further, the soluble nickel salt in the step (2) is positive divalent nickel salt, and positive divalent nickel salt is nickel nitrate, vinegar
Any one of sour nickel, nickel sulfate；The soluble manganese salt is positive manganous salt, positive manganous salt be manganese nitrate, manganese acetate,
Any one of manganese sulfate；The soluble sodium salt is any one of sodium nitrate, sodium acetate.
Further, by P2-Na2/3Ni1/3Mn2/3O2Powder, acetylene black, binder polyvinylidene fluoride (PVDF) press 75:
The mixing of 15:10 mass ratio, sodium-ion battery anode is made in smear, drying after grinding uniformly.
P2-Na as described above2/3Ni1/3Mn2/3O2Application of the nanofiber of nano particle assembling as storage sodium positive electrode
Method, it is characterised in that: with Na2/3Ni1/3Mn2/3O2The nanofiber and acetylene black, binder of nano particle assembling gather inclined difluoro
The sodium-ion battery positive plate that ethylene (PVDF) is mixed is anode, is to electrode with metallic sodium, concentration is 1mol/L's
NaClO4The fluorinated ethylene carbonate (FEC) that 5vol% is added in/PC is electrolyte, and diaphragm is glass fibre, in argon atmosphere
Model CR2032 button cell is assembled into glove box.
Compared with the existing technology, present invention has the advantage that
Na is synthesized by the method for electrostatic spinning2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling stores up sodium anode material
Material, can carry out the microscopic appearance tissue of controlled material by adjusting spinning parameter and the subsequent heat treatment process to spinning film to reach
To demand.
Preparation process of the present invention is simple, reaction condition is easily controllable, repetitive rate is high, is easy to volume production, can obtain tiny
Na2/3Ni1/3Mn2/3O2Particle assembling at nanofibrous structures, the size of nano particle is 20-90nm, the diameter of nanofiber
For 200-600nm.The integrality of nanofiber is good, is evenly distributed, and the three-dimensional network skeleton for the presentation that is cross-linked with each other enhances material
The structural stability of material promotes ion, electronics conduction, while high-specific surface area makes it in actual use and can expose more
Active site, so that storage sodium capacity, high rate performance and cycle life are significantly improved.
Detailed description of the invention
Fig. 1 is Na in the embodiment of the present invention 12/3Ni1/3Mn2/3O2Nano particle is assembled into the XRD diagram of nanofiber；
Fig. 2 is Na in the embodiment of the present invention 12/3Ni1/3Mn2/3O2Nano particle is assembled into the SEM shape appearance figure of nanofiber；
Fig. 3 is Na in the embodiment of the present invention 22/3Ni1/3Mn2/3O2Nano particle is assembled into the TEM figure and SEM of nanofiber
Mapping distribution diagram of element；
Fig. 4 is Na in the embodiment of the present invention 32/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling is as storage sodium anode
The charging and discharging curve and cycle performance figure of material；
Specific embodiment
The invention will be further described by the following examples.
Embodiment 1:
1) 4.4g polyvinylpyrrolidone (PVP) is dissolved in 30mL deionized water, 3mL is added to after being completely dissolved in stirring
It is 4~5 that glacial acetic acid, which adjusts pH value of solution, wiring solution-forming A；
2) by 0.4462g sodium nitrate (NaNO3) (5% is excessive), 0.727g nickel nitrate (Ni (NO3)2·6H2O)、1.2255g
Manganese acetate (Mn (CH3COOH)2·4H2O it) is added in solution A successively, forms homogeneous solution B under continuing magnetic force stirring；
3) above-mentioned solution B is transferred in syringe, with 12-15 μ L min-1Fltting speed be injected to reception aluminium foil, infuse
Distance is 15-20cm between emitter and reception aluminium foil, while the high pressure of application 16-18kV is quiet between syringe and reception aluminium foil
Electric field, spinning time are 10-15h, and it is 30-50 μm that collection, which obtains Electrospun film thickness,；
4) by the above-mentioned Electrospun film being collected into air atmosphere, 500 DEG C are warming up to the heating rate of 2 DEG C/min
Heat preservation 2h decomposes PVP and forms porous structure, is continuously heating to 700-900 DEG C and keeps the temperature 6h, is cooled to 400 with 5 DEG C/min
Temperature fall after DEG C, to obtain Na2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling.
The Na obtained by embodiment 12/3Ni1/3Mn2/3O2The nano-fiber material that particle is assembled into is made as follows
Electrode:
By P2-Na2/3Ni1/3Mn2/3O2Powder, acetylene black, binder polyvinylidene fluoride (PVDF) press 75:15:10 mass
Than mixing, grind uniformly after be coated on aluminium foil on, drying sodium-ion battery positive plate is made, with metallic sodium be to electrode, it is dense
Degree is the NaClO of 1mol/L4The fluorinated ethylene carbonate (FEC) that 5vol% is added in/PC is electrolyte, and diaphragm is glass fibers
Dimension, is assembled into model CR2032 button cell in argon atmosphere glove box.
Fig. 1 is Na in the embodiment of the present invention 12/3Ni1/3Mn2/3O2Particle is assembled into the XRD diagram of nanofiber, by with mark
Quasi- diffraction card comparison, it is P3 phase that 6h resulting materials are kept the temperature at 700 DEG C；It increases temperature and to 800 DEG C and keeps the temperature 6h, resulting materials
For the mixed phase of P2+P3；It is warming up to 850 DEG C of heat preservation 6h and remains as P2+P3 mixed phase, but P2 phase peak intensity enhances, P3 phase intensity
Weaken；900 DEG C of heat preservation 6h are continuously heating to, pure P2 type Na can be obtained2/3Ni1/3Mn2/3O2Material, and sample is made under this condition
Diffraction lines it is very smooth, diffraction maximum is sharp, and crystallinity is good.
Fig. 2 is Na in the embodiment of the present invention 12/3Ni1/3Mn2/3O2Particle is assembled into the SEM shape appearance figure of nanofiber: figure (a)
For the spinning film SEM photograph without calcining, show that fibre diameter is 200-600nm in figure, continuity is good, mutually criss-cross
Spatially reticular structure；Figure (b) is to be warming up to 500 DEG C of heat preservation 2h from 2 DEG C/min of room temperature, is continuously heating to 900 DEG C of heat preservation 6h institutes
The Na obtained2/3Ni1/3Mn2/3O2Particle is assembled into the SEM photograph of nanofiber, shows that tiny nanoparticle is assembled into directly in figure
Diameter is the limb shape nanofiber of 200-600nm, and fiber is evenly distributed, and still maintains the three-dimensional net structure being interweaved.
Embodiment 2:
1) 4.4g polyvinylpyrrolidone (PVP) is dissolved in the deionized water of 30mL, stirs to being completely dissolved, is made into molten
Liquid A；
2) by 0.4462g sodium nitrate (NaNO3) (5% is excessive), 0.727g nickel nitrate (Ni (NO3)2·6H2O)、1.250g
Manganese nitrate (Mn (NO3)2·4H2O it) is added in solution A successively, forms homogeneous solution B under continuing magnetic force stirring；
3) above-mentioned solution B is transferred in syringe, with 12-15 μ L min-1Fltting speed be injected to reception aluminium foil, infuse
Distance is 15-20cm between emitter and reception aluminium foil, while the high pressure of application 16-18kV is quiet between syringe and reception aluminium foil
Electric field, spinning time are 10-15h, and it is 30-50 μm that collection, which obtains Electrospun film thickness,；
4) by the above-mentioned Electrospun film being collected into air atmosphere, 500 DEG C are warming up to the heating rate of 2 DEG C/min
Heat preservation 2h decomposes PVP and forms porous structure, is continuously heating to 700-900 DEG C and keeps the temperature 6h, is cooled to 400 with 5 DEG C/min
Temperature fall after DEG C, to obtain Na2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling.
The Na obtained by embodiment 22/3Ni1/3Mn2/3O2The nano-fiber material that particle is assembled into is by embodiment 1
Model CR2032 button cell is made in method.
(a)-(c) is Na in the embodiment of the present invention 2 in Fig. 32/3Ni1/3Mn2/3O2Particle is assembled into the TEM figure of nanofiber,
It (d) is SEM Mapping distribution diagram of element.Show in figure: Na2/3Ni1/3Mn2/3O2Particle size is 20-90nm, and each element exists
It is uniformly distributed in fiber skeleton, no segregation phenomenon occurs.
Embodiment 3:
1) 4.4g polyvinylpyrrolidone (PVP) is dissolved in 30mL deionized water, 3mL is added to after being completely dissolved in stirring
It is 4~5 that glacial acetic acid, which adjusts pH value of solution, wiring solution-forming A；
2) by 0.7144g sodium acetate (CH3COONa·3H2O) (5% is excessive), 0.6218g nickel acetate (Ni
(CH3COOH)2·4H2O), 1.2255g manganese acetate (Mn (CH3COOH)2·4H2O it) is added in solution A, is stirred in continuing magnetic force successively
Mix lower formation homogeneous solution B；
3) above-mentioned solution B is transferred in syringe, with 12-15 μ L min-1Fltting speed be injected to reception aluminium foil, infuse
Distance is 15-20cm between emitter and reception aluminium foil, while the high pressure of application 16-18kV is quiet between syringe and reception aluminium foil
Electric field, spinning time are 10-15h, and it is 30-50 μm that collection, which obtains Electrospun film thickness,；
4) by the above-mentioned Electrospun film being collected into air atmosphere, 500 DEG C are warming up to the heating rate of 2 DEG C/min
Heat preservation 2h decomposes PVP and forms porous structure, is continuously heating to 700-900 DEG C and keeps the temperature 6h, is cooled to 400 with 5 DEG C/min
Temperature fall after DEG C, to obtain Na2/3Ni1/3Mn2/3O2The nanofiber of nano particle assembling.
The Na obtained by embodiment 32/3Ni1/3Mn2/3O2The nano-fiber material that particle is assembled into is by embodiment 1
Model CR2032 button cell is made in method.
Fig. 4 is Na in the embodiment of the present invention 32/3Ni1/3Mn2/3O2The nanofiber that particle is assembled into is as storage sodium anode material
The charging and discharging curve and cycle performance figure of material are such as schemed shown in (a), and the material is in 1.5-4.0V (vs.Na+/ Na) voltage window
It is interior, 0.1C (1C=173mAg-1) the initial reversible capacity under multiplying power reaches 165.3mAh g-1, with its theoretical capacity 172.6mAh g-1It is very nearly the same；After recycling 10 weeks, reversible capacity is about 157.4mAh g-1.As shown in figure (b), circulation after 50 weeks, omit by specific capacity
It is micro- to drop to 153.3mAh g-1, capacity retention ratio is up to 92.7%, and the material has very high coulombic efficiency (100% left side
It is right).With the conventional P2-Na for using Solid phase synthesis2/3Ni1/3Mn2/3O2It compares, reversible capacity, high rate performance and cyclical stability
It is all more superior.
Think finally, it is noted that the explanation of above example is merely used to help understand method and its core of the invention
Think.The substantial technological context being not intended to limit the invention, those skilled in the art can be on this basis to this hairs
It is bright to make various improvement to optimize this programme.Without departing from the principle of the present invention, any modification and modification etc. of progress
It should be included in the range of the claims in the present invention.
Claims (7)
1. a kind of nanofiber of nano particle assembling stores up sodium method for preparing anode material, it is characterised in that the following steps are included:
1) polyvinylpyrrolidone (PVP) is dissolved in deionized water, glacial acetic acid is added to after being completely dissolved and adjusts solution for stirring
PH wiring solution-forming A；
2) soluble sodium salt, nickel salt, manganese salt are added in solution A successively in proportion, stirring forms homogeneous solution B；
3) solution B is transferred in syringe, with 12-15 μ L min-1Fltting speed be injected to reception aluminium foil, syringe with connect
Receiving distance between aluminium foil is 15-20cm, while applying the high-voltage electrostatic field of 16-18kV between syringe and reception aluminium foil, is spun
The silk time is 10-15 hours, and it is 30-50 μm that collection, which obtains Electrospun film thickness,；
4) it by the above-mentioned Electrospun film being collected into air atmosphere, is warming up at 500 DEG C and is protected with the heating rate of 2 DEG C/min
Warm 2h decomposes PVP and forms porous structure, is continuously heating to 700-900 DEG C and keeps the temperature 6h, is cooled to 400 DEG C with 5 DEG C/min
Temperature fall afterwards, to obtain P2-Na2/3Ni1/3Mn2/3O2Nano particle assembling nanofiber, and then with acetylene black, bonding
Agent polyvinylidene fluoride (PVDF) mixing, is made sodium-ion battery positive plate.
2. the nanofiber of nano particle assembling stores up sodium method for preparing anode material according to claim 1, which is characterized in that
The molar ratio of atom Na:Ni:Mn is 2:1:2 in the molecular formula of the positive plate material.
3. the preparation method of the nanofiber storage sodium positive electrode of nano particle assembling, feature exist according to claim 2
In the positive plate material is the layered oxide structure of P2 phase.
4. the nanofiber of nano particle assembling stores up sodium method for preparing anode material according to claim 1, it is characterised in that:
The mass percent of polyvinylpyrrolidone (PVP) in the solution is 12.8% in the step 1).
5. the nanofiber of nano particle assembling stores up sodium method for preparing anode material according to claim 1, which is characterized in that
The soluble nickel salt is positive divalent nickel salt, and positive divalent nickel salt is any one of nickel nitrate, nickel acetate, nickel sulfate；It is described
Soluble manganese salt be positive manganous salt, positive manganous salt is any one of manganese nitrate, manganese acetate, manganese sulfate；Described can
Dissolubility sodium salt is any one of sodium nitrate, sodium acetate.
6. the nanofiber of nano particle assembling stores up sodium method for preparing anode material according to claim 1, it is characterised in that:
By P2-Na2/3Ni1/3Mn2/3O2Powder, acetylene black, binder polyvinylidene fluoride (PVDF) are mixed by 75:15:10 mass ratio,
It is coated in aluminum foil current collector after grinding uniformly, sodium-ion battery positive plate is made in drying.
7. a kind of application method of the nanofiber storage sodium positive electrode of nano particle assembling as described in claim 1, feature
It is: with P2-Na2/3Ni1/3Mn2/3O2The nanofiber and acetylene black, binder polyvinylidene fluoride of nano particle assembling
(PVDF) the sodium-ion battery positive plate being mixed is anode, is to electrode with metallic sodium, concentration is the NaClO of 1mol/L4/
The fluorinated ethylene carbonate (FEC) that 5vol% is added in PC is electrolyte, and diaphragm is glass fibre, in argon atmosphere glove box
It is assembled into model CR2032 button cell.
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| CN114122382A (en) * | 2021-11-24 | 2022-03-01 | 西安交通大学 | Layered positive electrode material of P3 type sodium-ion battery and preparation method and application thereof |
| CN114122382B (en) * | 2021-11-24 | 2024-04-02 | 西安交通大学 | Layered positive electrode material of P3 type sodium ion battery, and preparation method and application thereof |
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