CN109755565A - Transient metal doped sodium-ion battery positive electrode and its preparation and application - Google Patents
Transient metal doped sodium-ion battery positive electrode and its preparation and application Download PDFInfo
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Abstract
It is prepared the present invention relates to a kind of transient metal doped sodium-ion battery with positive electrode and its application in sodium-ion battery field, the group of the positive electrode becomes Na3V2‑xMx(PO4)2F3/ C, 0.001≤x≤0.5, M are transition metal.Na of the invention3V2‑xMx(PO4)2F3/ the C and Na not adulterated3V2(PO4)2F3/ C is compared, and band gap is smaller, and electronics is easier from valence to conduction band, and is adulterated and be will form local defect, and conductivity is made to get a promotion；Meanwhile the transition metal ions of doping is in Na3V2(PO4)2F3In play pillar, larger ionic radius it is transition element doped after, Na+Diffusion admittance become larger, deintercalation speed of the Na in crystal becomes larger, and improves the structural stability of material, material is made not occur structural distortion, deformation, collapsing in long-term charge and discharge process, improve the cyclical stability of material.Prepared Na3V2‑xMx(PO4)2F3/ C-material shows the specific discharge capacity close to theoretical specific capacity, excellent high rate performance and cycle performance by electrochemical property test.
Description
Technical field
The present invention relates to sodium ion battery electrode material field, in particular to a kind of transient metal doped sodium-ion battery
With method for preparing anode material and application.
Background technique
The energy is the important impetus of social development, and the used energy is broadly divided into renewable energy (wind energy, water at present
Energy, solar energy etc.) and non-renewable energy resources (coal, petroleum, natural gas etc.).Due to non-renewable energy resources shortage of resources and to environment
It is seriously polluted, the development of renewable energy has been to be concerned by more and more people, but renewable energy is discontinuous, unstable, will
Its direct grid-connected can generate very big impact to power grid.Energy storage technology is the key that solution renewable energy is discontinuous, unstable
Technology.In numerous energy storage technologies, lithium ion battery has many advantages, such as that energy density is high, has extended cycle life, and is widely answered
For in various portable electronic devices and electric car, but lithium resource reserves are limited, are unevenly distributed, and limit lithium-ion electric
The large-scale development in pond.
Sodium and lithium have a similar chemistry, physical property, and the rich reserves (abundance of Na be Li 1000 times) of Na, point
Cloth is extensive, and cost is relatively low, and the development of sodium-ion battery can effectively alleviate the limited problem of lithium resource.The appearance of sodium-ion battery
Amount is limited to positive electrode, and developing positive electrode is the key that realize sodium-ion battery large-scale application, and fluorophosphoric acid vanadium sodium has
NASICON (Na super ionic conductor) structure, sodium ion deintercalation fast speed, stable structure, and voltage platform with higher and
Theoretical specific capacity is a kind of positive electrode for having very much application potential.From the point of view of current report, fluorophosphoric acid vanadium sodium show compared with
Good cycle performance, but its high rate performance is poor.High rate performance is mainly by Na+Deintercalation speed and the conductivity of electronics determine
Fixed, fluorophosphoric acid vanadium sodium has NASICON structure, and sodium ion transmission is very fast, limits the key factor of fluorophosphoric acid vanadium sodium high rate performance
It is its conductivity.In fluorophosphoric acid vanadium, due to the insulating properties of phosphate radical, keep its conductivity lower, some researchers pass through carbon packet
It covers and reduces particle size to improve its conductivity, but these methods all only improve the bulk electrical conductivity of material, to material
Intrinsic conductivity there is no any improvement.
Summary of the invention
It is prepared the present invention relates to a kind of sodium-ion battery with transient metal doped positive electrode and its is led in sodium-ion battery
Application in domain.
The group of the transient metal doped positive electrode becomes Na3V2-xMx(PO4)2F3/ C, wherein M is transition metal, x model
It encloses for 0.001-0.5；
The preparation step of the transient metal doped positive electrode includes:
1) in molar ratio be 3:(2-x): x:2:3:2) weigh sodium salt (such as sodium acetate, sodium sulphate, sodium oxalate, sodium citrate,
One of sodium nitrate, sodium fluoride, sodium carbonate, sodium bicarbonate or two kinds or more), vanadium source is (in ammonium metavanadate, vanadic anhydride
One or both mixing), transistion metal compound (titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper
(Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium
(Hf), the metal of one or more of tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt) and gold (Au)
One of halide, metal oxide, nitrate, carbonate, acetate, oxalates or two kinds or more), phosphate (phosphoric acid
One of ammonium dihydrogen, sodium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, potassium phosphate and sodium phosphate or two kinds or more), fluorine
Salt (one of ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride and hydrofluoric acid or two kinds or more) and carbon source (oxalic acid, Vitamin C
One of acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, glucose, sucrose, malic acid, ethanedioic acid, adipic acid or two
Kind or more) quality；
2) sodium salt of step 1), vanadium source, transistion metal compound, phosphate, villiaumite and carbon source are added in ball grinder,
Add agate ball (agate ball and raw material quality ratio be 2~15:1), be added solvent (water, acetone, ethyl alcohol, in ethylene glycol
One or two or more kinds, and raw material and solvent quality ratio are 1:2~10), ball milling 4-24h (revolving speed 400-2000rpm).It is former
Material is carbon source, sodium salt, vanadium source, transistion metal compound, phosphate and villiaumite.
3) mixture (removing agate ball) that step 2) obtains is poured into beaker, cleans agate bead with deionized water, it will be clear
Washing lotion pours into beaker, cleans 2-5 times.Add magneton to stir, vapor away solvent at 70-95 DEG C, places into 100-150 DEG C of baking
1-20h is kept in case, obtains precursor A.
4) precursor A is pre-sintered under the conditions of inert atmosphere (nitrogen and/or argon atmosphere) is through 250-450 DEG C 1-10h,
600-900 DEG C of high temperature sintering 4-20h, up to the positive electrode Na of doped transition metal ions after cooling3V2-xMx(PO4)2F3/C。
By prepared Na3V2-xMx(PO4)2F3/ C-material is made as anode, metallic sodium piece as cathode, glass fibre membrane
For diaphragm, solute 1MNaClO4, solvent EC (ethylene carbonate) and DEC (diethyl carbonate) mixture (mass ratio 1:1) add
Add agent be mass fraction be 2% FEC as electrolyte, aluminium foil is as collector plate, by CR2016 button shell according to cathode
Shell, negative electrode, electrolyte, diaphragm, electrolyte, anode electrode, collector anode pole housing sequence successively stack compression
It is assembled into sodium-ion battery.
Beneficial effects of the present invention
By the present invention in that effectively improving the intrinsic conductivity of fluorophosphoric acid vanadium sodium with doped transition metal ions, expand sodium
Ion diffusion admittance improves the high rate performance of material.Moreover, after doped transition metal ions, the structure of fluorophosphoric acid vanadium sodium
More stable, grain diameter is smaller, makes its specific capacity close to theoretical specific capacity and shows excellent cycle performance.Cyclicity
Can, high rate performance, the raising of specific capacity enables fluorophosphoric acid vanadium sodium preferably in electronic equipment, electric car, scale energy storage
It is applied.
Na of the invention3V2-xMx(PO4)2F3/ the C and Na not adulterated3V2(PO4)2F3/ C is compared, and band gap is smaller, electronics
It more easily from valence to conduction band, and adulterates and will form local defect, conductivity is made to get a promotion；Meanwhile the mistake of doping
Metal ion is crossed in Na3V2(PO4)2F3In play pillar, larger ionic radius it is transition element doped after, Na+Diffusion
Channel becomes larger, and deintercalation speed of the Na in crystal becomes larger；Secondly, the presoma of doped chemical can effectively prevent material from tying
Agglomeration during crystalline substance makes the partial size of material become smaller, and specific surface area becomes larger, and shortens Na+Diffusion path and increase material
With the contact area of electrolyte, be conducive to Na+Deintercalation, significantly reduce material interface transmission resistance, significantly improve
The high rate performance of material.In addition, more stable M-O key is improved instead of V-O key after doped transition metal ions
The structural stability of material, makes material not occur structural distortion, deformation, collapsing in long-term charge and discharge process, improves
The cyclical stability of material.Prepared Na3V2-xMx(PO4)2F3/ C-material shows to approach reason by electrochemical property test
By the specific discharge capacity of specific capacity, excellent high rate performance and cycle performance.
Detailed description of the invention
Fig. 1 is comparative example and the AC impedance of embodiment 1, embodiment 2 and embodiment 3 under the conditions of 0.1Hz-100kHz
Figure.
Fig. 2 is the high rate performance figure of comparative example and embodiment 1, embodiment 2 and embodiment 3.
Fig. 3 is comparative example and cycle performance figure of the embodiment 1 at 1C.
Fig. 4 is comparative example and cycle performance figure of the embodiment 2 at 1C.
Fig. 5 is comparative example and cycle performance figure of the embodiment 3 at 1C.
Specific embodiment
Embodiment 1:(transition metal Ti doping preparation Na3V1.9Ti0.1(PO4)2F3/C)
Weigh 2.520g sodium fluoride (both doing Fluorine source, also do sodium source), 4.445g ammonium metavanadate, 0.159g titanium dioxide,
4.601g ammonium dihydrogen phosphate and 8.406g citric acid (both doing carbon source, also make reducing agent), are added to the agate jar of 250mL
In, the agate ball and 60ml deionized water of 80g are added, ball grinder is placed in ball mill, with the revolving speed ball milling of 580rpm
12h.Gained mixed solution (removing agate ball) pours into beaker, cleans agate bead with deionized water, cleaning solution is poured into beaker, clearly
It washes 3 times, magneton is added to stir, vapor away solvent at 80 DEG C, place into 120 DEG C of baking oven and keep 8h, obtain precursor A.
Precursor A is pre-sintered 5h, 750 DEG C of high temperature sintering 8h in a nitrogen atmosphere under the conditions of 350 DEG C, up to transition metal after cooling
The positive electrode Na of doping3V1.9Ti0.1(PO4)2F3/C。
Embodiment 2:(transition-metal Fe doping preparation Na3V1.95Fe0.05(PO4)2F3/C)
Weigh 2.520g sodium fluoride (both doing Fluorine source, also do sodium source), 4.562g ammonium metavanadate, 0.407g (FeNO3)3·
9H2O, 4.601g ammonium dihydrogen phosphate and 8.406g citric acid (both doing carbon source, also make reducing agent), are added to the agate ball of 250mL
In grinding jar, the agate ball and 60ml deionized water of 80g are added, ball grinder is placed in ball mill, with the revolving speed ball of 580rpm
Grind 12h.Gained mixed solution (removing agate ball) pours into beaker, cleans agate bead with deionized water, cleaning solution is poured into beaker,
Cleaning 3 times, adds magneton to stir, vapors away solvent at 80 DEG C, place into 120 DEG C of baking oven and keep 8h, obtain presoma
A.Precursor A is pre-sintered 5h, 750 DEG C of high temperature sintering 8h in a nitrogen atmosphere under the conditions of 350 DEG C, it is golden up to transition after cooling
Belong to the positive electrode Na of doping3V1.95Fe0.05(PO4)2F3/C。
Embodiment 3:(transition metal Ni doping preparation Na3V1.93Ni0.07(PO4)2F3/C)
Weigh 2.520g sodium fluoride (both doing Fluorine source, also do sodium source), 4.515g ammonium metavanadate, 0.404gNi (NO3)2·
6H2O, 4.601g ammonium dihydrogen phosphate and 8.406g citric acid (both doing carbon source, also make reducing agent), are added to the agate ball of 250mL
In grinding jar, the agate ball and 60ml deionized water of 80g are added, ball grinder is placed in ball mill, with the revolving speed ball of 580rpm
Grind 12h.Gained mixed solution (removing agate ball) pours into beaker, cleans agate bead with deionized water, cleaning solution is poured into beaker,
Cleaning 3 times, adds magneton to stir, vapors away solvent at 80 DEG C, place into 120 DEG C of baking oven and keep 8h, obtain presoma
A.Precursor A is pre-sintered 5h, 750 DEG C of high temperature sintering 8h in a nitrogen atmosphere under the conditions of 350 DEG C, it is golden up to transition after cooling
Belong to the positive electrode Na of doping3V1.93Ni0.07(PO4)2F3/C。
Comparative example: (undoped Na3V2(PO4)2F3/C)
Weigh 2.520g sodium fluoride (both doing Fluorine source, also do sodium source), 4.679g ammonium metavanadate, 4.601g ammonium dihydrogen phosphate and
8.406g citric acid (both does carbon source, also make reducing agent), is added in the agate jar of 250mL, adds the agate ball of 80g
With 60ml deionized water, ball grinder is placed in ball mill, with the revolving speed ball milling 12h of 580rpm.Gained mixed solution (removes agate
Ball) beaker is poured into, agate bead is cleaned with deionized water, cleaning solution is poured into beaker, cleans 3 times, adds magneton to stir, at 80 DEG C
It is lower to vapor away solvent, it places into 120 DEG C of baking oven and keeps 8h, obtain precursor A.Precursor A is passed through in a nitrogen atmosphere
5h, 750 DEG C of high temperature sintering 8h are pre-sintered under the conditions of 350 DEG C, up to undoped positive electrode Na after cooling3V2(PO4)2F3/C。
After suitable transition metal Ti doping, the conductivity and sodium ion deintercalation rate of material are improved, with comparative example institute
The Na of preparation3V2(PO4)2F3/ C is compared, Na prepared by embodiment 13V1.9Ti0.1(PO4)2F3/ C is transmitted with smaller charge
Resistance (Rct), show higher specific capacity, better high rate performance and cyclical stability.As seen from Figure 1, with comparison
Na prepared by example3V2(PO4)2F3/ C is compared, Na prepared by embodiment 13V1.9Ti0.1(PO4)2F3/ C is passed with smaller charge
(slope of 1 low frequency range straight line of embodiment is significantly greater than comparative example low frequency range straight line with bigger sodium ion deintercalation rate for transmission of electricity resistance
Slope).As seen from Figure 2, Na prepared by embodiment 13V1.9Ti0.1(PO4)2F3/ C is shown under low range
The specific capacity of 113mAh g-1 improves about 20mAh g-1 compared with comparative example.Under the high magnification of 40C, Na3V1.9Ti0.1(PO4)2F3/ C still shows the specific capacity of 90mAh g-1, much higher than specific capacity (12mAh g-1) of the comparative example at 40C, thus may be used
To find out, after appropriate Ti doping, Na3V1.9Ti0.1(PO4)2F3The high rate performance of/C is significantly improved, this is mainly due to Ti
Doping is to Na3V2(PO4)2F3The raising of/C intrinsic conductivity and sodium ion deintercalation rate.By Fig. 3 it will be seen that embodiment 1
Prepared Na3V1.9Ti0.1(PO4)2F3/ C has more stable cycle performance, at 1C after 200 charge and discharge cycles,
Capacity retention ratio is 67.8%, improves 30 percentage points compared with comparative example.
After suitable transition-metal Fe doping, the conductivity and sodium ion deintercalation rate of material are improved, with comparative example institute
The Na of preparation3V2(PO4)2F3/ C is compared, Na prepared by embodiment 23V1.95Fe0.05(PO4)2F3/ C is transmitted with smaller charge
Resistance (Rct), show higher specific capacity, better high rate performance and cyclical stability.As seen from Figure 1, with comparison
Na prepared by example3V2(PO4)2F3/ C is compared, Na prepared by embodiment 23V1.95Fe0.05(PO4)2F3/ C is passed with smaller charge
(slope of 1 low frequency range straight line of embodiment is significantly greater than comparative example low frequency range straight line with bigger sodium ion deintercalation rate for transmission of electricity resistance
Slope).As seen from Figure 2, Na prepared by embodiment 23V1.95Fe0.05(PO4)2F3/ C is shown under low range
The specific capacity of 123mAh g-1 improves about 30mAh g-1 compared with comparative example.Under the high magnification of 40C, Na3V1.95Fe0.05(PO4)2F3/ C still shows the specific capacity of 98mAh g-1, much higher than specific capacity (12mAh g-1) of the comparative example at 40C, thus may be used
To find out, after appropriate Fe doping, Na3V1.95Fe0.05(PO4)2F3The high rate performance of/C is significantly improved, this is mainly due to Fe
Doping is to Na3V2(PO4)2F3The raising of/C intrinsic conductivity and sodium ion deintercalation rate.By Fig. 4 it will be seen that embodiment 2
Prepared Na3V1.95Fe0.05(PO4)2F3/ C has more stable cycle performance, at 1C after 200 charge and discharge cycles,
Capacity retention ratio is 76.8%, improves 40 percentage points compared with comparative example.
After suitable transition metal Ni doping, the conductivity of material is improved, with Na prepared by comparative example3V2(PO4)2F3/ C is compared, the Na of the doping preparation of transition metal Ni prepared by embodiment 33V1.93Ni0.07(PO4)2F3/ C has smaller electricity
Lotus transmits resistance (Rct), show higher specific capacity, better high rate performance and cyclical stability.As seen from Figure 1,
With Na prepared by comparative example3V2(PO4)2F3/ C is compared, Na prepared by embodiment 33V1.93Ni0.07(PO4)2F3/ C has smaller
Charge transmits resistance.As seen from Figure 2, Na prepared by embodiment 33V1.93Ni0.07(PO4)2F3/ C is shown under low range
The specific capacity of 128.5mAh g-1, it is close with theoretical specific capacity (128mAh g-1), about 35mAh g- is improved compared with comparative example
1.Under the high magnification of 40C, Na3V1.93Ni0.07(PO4)2F3/ C still shows the specific capacity of 100mAh g-1, much higher than comparison
Specific capacity (12mAh g-1) of the example at 40C, it can thus be seen that after appropriate Ni doping, Na3V1.93Ni0.07(PO4)2F3/ C's
High rate performance is significantly improved, this is mainly due to Ni doping to Na3V2(PO4)2F3/ C intrinsic conductivity improves.By Fig. 5 I
As can be seen that embodiment 3 prepared by Na3V1.93Ni0.07(PO4)2F3/ C has more stable cycle performance, passes through at 1C
After 200 charge and discharge cycles, capacity retention ratio 81.3% improves 45 percentage points compared with comparative example.
Claims (9)
1. transient metal doped sodium-ion battery positive electrode, it is characterised in that: the group of the positive electrode becomes Na3V2- xMx(PO4)2F3/ C, 0.001≤x≤0.5, M are transition metal.
2. according to positive electrode described in claim 1, it is characterised in that: the transition metal is titanium (Ti), chromium (Cr), manganese
(Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium
(Rh), palladium (Pd), silver-colored (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt) and gold
One of (Au) or two kinds or more, the mass content of support C is 1%-20% in positive electrode.
3. a kind of preparation method of positive electrode as claimed in claim 1 or 2, it is characterised in that: positive electrode passes through following steps
It is prepared:
1) by sodium: vanadium: transition metal: phosphate radical, fluorine molar ratio are 3:(2-x): x:2:3 weighs sodium salt, vanadium source, transition metal
Close object, phosphate, villiaumite and carbon source；Carbon source quality is above-mentioned sodium salt, vanadium source, transistion metal compound, phosphate and villiaumite
The 10-30% of gross mass, X=0.001-0.5；
2) solvent, ball milling 4-24h, revolving speed 400-2000rpm is added in the mixture of step 1)；
3) mixed liquor for obtaining step 2) pours into jar agitation, vapors away solvent at 70-95 DEG C, places into 100-150
DEG C baking oven in keep 1-20h, obtain precursor A；
4) precursor A is pre-sintered to 1-10h, 600-900 DEG C of high temperature sintering 4-20h under the conditions of inert atmosphere is through 250-450 DEG C,
The positive electrode Na of the doped transition metal ions carried after cooling up to carbon3V2-xMx(PO4)2F3/C。
4. the preparation method of positive electrode according to claim 3, it is characterised in that: sodium salt described in step 1) is vinegar
One of sour sodium, sodium sulphate, sodium oxalate, sodium citrate, sodium nitrate, sodium fluoride, sodium carbonate, sodium bicarbonate or two kinds or more；
The vanadium source is one of ammonium metavanadate, vanadic anhydride or two kinds of mixing；The phosphate is ammonium dihydrogen phosphate, di(2-ethylhexyl)phosphate
One of hydrogen sodium, diammonium hydrogen phosphate, disodium hydrogen phosphate, potassium phosphate and sodium phosphate or two kinds or more；The transition metal compound
Object is one of the metal halide of transition metal, metal oxide, nitrate, carbonate, acetate, oxalates or two kinds
More than；The villiaumite is one of ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride and hydrofluoric acid or two kinds or more.
5. the preparation method of positive electrode according to claim 3 or 4, it is characterised in that: the transition metal is titanium
(Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium
(Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium
(Ir), one or more of platinum (Pt) and golden (Au) one or two or more kinds.
6. the preparation method of positive electrode according to claim 3, it is characterised in that: carbon source described in step 1) is grass
Acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, glucose, sucrose, malic acid, ethanedioic acid, in adipic acid
It is one or two or more kinds of.
7. the preparation method of positive electrode according to claim 3, it is characterised in that: solvent described in step 2) is
One of water, acetone, ethyl alcohol, ethylene glycol or two kinds or more, and raw material and solvent quality ratio are 1:2~10, raw material are
Carbon source, sodium salt, vanadium source, transistion metal compound, phosphate and villiaumite.
8. the preparation method of positive electrode according to claim 3, it is characterised in that: inert atmosphere is nitrogen in step 4)
And/or argon gas.
9. a kind of application of positive electrode as claimed in claim 1 or 2, the positive electrode Na3V2-xMx(PO4)2F3/ C is applied to sodium
In ion battery.
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