CN106532114A - NASICON (Na Super Ion Conductors) structure-based sodium ion solid electrolyte composite material and preparation method and application thereof - Google Patents
NASICON (Na Super Ion Conductors) structure-based sodium ion solid electrolyte composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an NASICON (Na Super Ion Conductors) structure-based sodium ion solid electrolyte composite material and a preparation method and application thereof. The general formula of the sodium ion solid electrolyte composite material is (x)Na<3>La(PO<4>)<2>/Na<3-2x>Zr<2-x>Si<2>P<1-2x>O<12-8x>, wherein x is more than 0 but less than or equal to 0.5. The composite material is synthesized respectively by employing a traditional solid phase reaction method and a sol-gel method. The preparation method is simple and practical, is low in cost and can be suitably used for fabrication on a large scale. The sodium ion solid electrolyte composite material is excellent in thermal stability, is a non-pollution inorganic green material and can be used as a key part-solid electrolyte in a sodium all-solid-state battery. A secondary battery employing the sodium ion solid electrolyte material is excellent in cycle performance and good in safety performance, has a great practical value and can be used for solar power generation, wind power generation, intelligent peak regulation in a power grid, power station distribution, an emergency power supply or large-scale intelligent equipment of a communication base station.
Description
Technical field
The present invention relates to a kind of sodion solid electrolytes composite based on NASICON structures and
Its preparation method and its application in all-solid sodium ion battery.
Background technology
Lithium rechargeable battery have specific energy density big, operating temperature range width, discharge and recharge life-span length,
The advantages of self discharge is little, memory-less effect is little, its mass energy density can reach 280Wh/kg, quilt
It is considered most promising electrochmical power source.Since nineteen ninety Sony, company was by its commercialization, no
Only consumer electronics sector is moved in 4C such as notebook computer, mobile phone, video camera, digital cameras
Occupy leading position (Nature, 2002,419 (6907):553-555), and in recent years in electrokinetic cell
The development prospect that attracts people's attention is shown all with energy-storage battery field.
But, tellurian lithium resource does not enrich, and abundance of the elemental lithium in the earth's crust is only
0.0065%, and be distributed it is also very uneven, as following electric automobile, intelligent grid epoch arrive
Come, the price of lithium resource shortage and costliness necessarily becomes the key factor of its development of restriction.Therefore, need
Want the energy-storage battery system of Development of Novel.Abundance of the sodium in the earth's crust is up to 2.64%, cheap, and
Sodium ion has similar embedded mechanism with lithium ion, therefore sodium ion secondary battery is received again in recent years
To the concern of people.
On the other hand, liquid organic electrolyte being adopted secondary cell traditional at present more, leakage easily occur
The problems such as liquid, electrode corrosion, at an excessive temperature, in some instances it may even be possible to explode.Although using electrostrictive polymer
Solution matter can alleviate these problems to a certain extent, but fundamentally can not solve.And use inorganic
Solid electrolyte, not only can exclude the leakage problem that electrolyte brings, and there is no liquid electrolyte
The resolution problem of matter so that all-solid-state battery security performance it is higher (Nature, 2008,451 (7179):
652-657,Nature,2001,414(6861):359-367), the longer (J.Power of cycle life
Sources,2005,147(1-2):269-281).Additionally, development all-solid-state battery, also helps battery
Miniaturization, shape of product variation (Adv.Energy Mater., 2011,1 (1):10-33).Together
When solid electrolyte also act the effect of barrier film, therefore simplify the structure of battery, without the need in protection
The encapsulation of battery is carried out under atmosphere, cost of manufacture is reduced.
Development all-solid-state battery, also needs to find ion in addition to the contact problems between interface are solved
The high solid electrolyte of electrical conductivity.NASICON (Na Super Ion Conductors) structure
Na1+xZr2SixP3-xO12(0≤x≤3) are due to its excellent ionic conduction characteristic, stable chemical
Matter, wider electrochemical window are subject to the extensive concern of researcher.As x=2, (i.e.
Na3Zr2Si2PO12) with highest ionic conductivity (Mater.Res.Bull., 1976,11:
203-220), up to 10 under room temperature-4S/cm, however, its ionic conductivity is also well below liquid electricity
Xie Zhi, becomes and limits its big factor applied in all-solid-state battery.
The content of the invention
It is an object of the invention to provide a kind of solid electrolytic composite material based on NASICON structures
And its preparation method and application.The sodion solid electrolytes composite material preparation process is simple, former
Material is cheap and easy to get therefore cheap for manufacturing cost；Excellent heat stability, is a kind of free of contamination inorganic green
Color material, can be used as the critical component-solid electrolyte in sodium ion all-solid-state battery.Using the present invention
Sodion solid electrolytes composite secondary cell, cycle performance is excellent, has a safety feature,
With great practical value.
In a first aspect, the invention provides a kind of sodion solid based on NASICON structures is electrolysed
Composite material, the formula of the composite is：xNa3La(PO4)2/Na3-2xZr2-xSi2P1-2xO12-8x,
Wherein 0 ＜ x≤0.5.
According to the sodion solid electrolytes composite wood based on NASICON structures that the present invention is provided
Material, its ionic conductivity are 0.9 × 10-3～5 × 10-3S/cm。
Second aspect, the invention provides preparing the sodion solid based on NASICON structures
The method of electrolyte composite material, specially solid phase method, the preparation method include：
By the Na of the 110～115wt% of stoichiometry of required sodium2CO3With stoichiometric ZrO2、
La2O3、SiO2And NH4H2PO4Or (NH4)2HPO4It is mixed to form presoma；
The presoma is uniformly mixed to get by precursor powder using the method for ball milling；
By the precursor powder at 750～950 DEG C heat treatment 2～24 hours；
By the precursor powder grinding after heat treatment, tabletting, and 2～24 are sintered at 1050～1200 DEG C
Hour, that is, obtain the sodion solid electrolytes composite based on NASICON structures.Root
According to above-mentioned preparation method, also include：Before presoma is mixed to form, by La2O31000 DEG C with
Upper heat treatment 2h, to remove the CO of absorption2。
The third aspect, present invention also offers another kind of prepare the sodium based on NASICON structures
The method of ion solid electrolyte composite material, specially sol-gel process, the preparation method include：
By tetraethyl orthosilicate (TEOS) and H2O, ethanol are with 1：8～12：18～22 mol ratio is mixed
It is molten, citric acid (citric acid is 1～2 with the mol ratio of cation) is added, and water is stirred at 55～65 DEG C
Solution 0.5～3 hour, then sequentially add the 110～115wt% of stoichiometry of required sodium sodium nitrate or
Sodium acetate and stoichiometric zirconyl nitrate, Lanthanum (III) nitrate or lanthanum acetate, last Deca NH4H2PO4
Or (NH4)2HPO4Aqueous solution, obtain colloidal sol, being warming up to 70～90 DEG C of stirrings makes moisture evaporation, obtains
To Gel Precursor；
The Gel Precursor is dried 3～5 hours at 150～200 DEG C, xerogel is obtained；
By the xerogel at 500～600 DEG C heat treatment 3～6 hours, then at 750～950 DEG C
Presintering 2～24 hours；
Presoma xerogel after presintering is ground, then sintering 2～24 is little at 1050～1200 DEG C
When, obtain the sodion solid electrolytes composite based on NASICON structures.
According to above-mentioned preparation method, wherein, the consumption of the citric acid is preferred with the mol ratio of cation
For 1～2.
According to above-mentioned preparation method, wherein, may be used also for the ease of operation, the sodium nitrate or sodium acetate
To be first dissolved in water, the concentration of sodium nitrate aqueous solution can be 0.05～10.7mol/L, sodium acetate aqueous solution
Concentration can be 0.05～6.6mol/L；The zirconyl nitrate can also be first dissolved in water, its aqueous solution
Concentration can be 0.5～1.5mol/L；The Lanthanum (III) nitrate or lanthanum acetate can also be first dissolved in water, Lanthanum (III) nitrate water
The concentration of solution can be 0.05～4.2mol/L, and the concentration of lanthanum acetate aqueous solution can be 0.05～2.0
mol/L.The NH4H2PO4The concentration of aqueous solution can be 0.05～3.5mol/L, (NH4)2HPO4
The concentration of aqueous solution can be 0.05～4.5mol/L.
The present invention is respectively adopted conventional solid reaction method and sol-gel process synthesized the present invention based on
The solid electrolytic composite material of NASICON structures.The room temperature of the composite solid electrolyte for obtaining from
Electron conductivity up to 3.4 × 10-3S/cm.On the one hand, the introducing of La can capture NASICON principal phases
In Na ions, be formed in situ Na3La(PO4)2, there are Na rooms in second phase in causing principal phase,
So that bulk conductivity rate is improved；On the other hand, the introducing of La substantially increases the consistency of potsherd,
And due to the space charge effect of biphase grain boundaries, cause grain boundary conductivities to improve a quantity
Level.
Fourth aspect, present invention also offers the sodion solid electricity based on NASICON structures
Solution application of the composite material in all-solid sodium ion battery is prepared.
In terms of 5th, the invention provides a kind of all-solid sodium ion battery, the battery includes this
The sodion solid electrolytes composite based on NASICON structures of bright offer.
The sodion solid electrolytes composite based on NASICON structures that the present invention is provided, system
Standby process is simple, raw material are cheap and easy to get therefore cheap for manufacturing cost；Excellent heat stability, is a kind of
Free of contamination inorganic green material, can be used as the critical component-solid state electrolysis in sodium ion all-solid-state battery
Matter.Using the secondary electricity of the sodion solid electrolytes material based on NASICON structures of the present invention
Pond, cycle performance are excellent, have a safety feature, and with very big practical value, can be used for solar energy and send out
Electricity, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station it is extensive
Energy storage device.
Description of the drawings
Hereinafter, with reference to accompanying drawing describing embodiment of the present invention in detail, wherein：
Fig. 1 is that the sodion solid based on NASICON structures prepared by the embodiment of the present invention 1 is electrolysed
Composite material xNa3La(PO4)2/Na3-2xZr2-xSi2P1-2xO12-8x(x=0.05,0.1,0.15,0.2,
0.25th, 0.3,0.35,0.4 and XRD spectrum 0.45)；
Fig. 2 is 0.15Na prepared by the embodiment of the present invention 33La(PO4)2/Na2.7Zr1.85Si2P0.7O10.8It is multiple
Close the transmission electron microscope EDS results of solid electrolyte ceramic piece；
Fig. 3 is xNa prepared by embodiment of the present invention 1-53La(PO4)2/Na3-2xZr2-xSi2P1-2xO12-8x
The impedance spectra of (x=0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4 and 0.45)；
Fig. 4 is sodium ion all-solid-state battery charging and discharging curve figure prepared by the embodiment of the present invention 6；
Fig. 5 is sodium ion all-solid-state battery charging and discharging curve figure prepared by the embodiment of the present invention 7；
Fig. 6 is sodium ion all-solid-state battery charging and discharging curve figure prepared by the embodiment of the present invention 8；
Fig. 7 is Na prepared by comparative example 13Zr2Si2PO12The XRD spectrum of solid electrolyte material；
Fig. 8 is Na prepared by comparative example 13Zr2Si2PO12The impedance spectra of solid electrolyte material.
Specific embodiment
The present invention is further described in detail with reference to specific embodiment, the enforcement for being given
Example only for illustrating the present invention, rather than in order to limit the scope of the present invention.
Embodiment 1
The present embodiment is used for the sodion solid electrolytes based on NASICON structures for illustrating the present invention
Composite, its formula is：xNa3La(PO4)2/Na3-2xZr2-xSi2P1-2xO12-8x, wherein 0 ＜ x≤
0.5。
The X that the sodion solid electrolytes composite of different composite ratio is given in Fig. 1 is penetrated
Line diffraction (X-ray diffraction, XRD) collection of illustrative plates, the diffraction maximum correspondence wherein at black filled circle
Na3La(PO4)2Phase, other diffraction maximum correspondence NASICON phases.
The sodion solid electrolytes composite can be applicable to Na/S batteries, ZEBRA batteries,
Sodium ion all-solid-state battery and sensor etc..
Below by way of the explanation of multiple instantiations using the solid phase described in second aspect in present invention
Sol-gel process described in method and the third aspect prepares the sodion solid based on NASICON structures
The detailed process of electrolyte composite material, and be applied to sodium ion all-solid-state battery method and
Battery performance.
Embodiment 2
The present embodiment is used for explanation and prepares base using the solid phase method described in second aspect in present invention
In the sodion solid electrolytes composite of NASICON structures
0.05Na3La(PO4)2/Na2.9Zr1.95Si2P0.9O11.6。
By the Na of stoichiometry 110wt% of required sodium2CO3、ZrO2、La2O3(before use
More than 1000 DEG C heat treatment 2h, to remove the CO of absorption2)、SiO2、(NH4)2HPO4Match somebody with somebody in proportion
Material, is mixed into presoma；The presoma is uniformly mixed to get by precursor using the method for ball milling
End；The precursor powder is placed in Muffle furnace, in 750 DEG C of air atmosphere, heat treatment 12 is little
When；Precursor powder after pre-burning is ground, tabletting, and in 1100 DEG C of air atmosphere high temperatures
Sintering 6 hours, obtains the potsherd of the sodion solid electrolytes composite.
Its x-ray diffractogram of powder spectrum is (x=0.05) as shown in Figure 1, it will be seen from figure 1 that
The material for arriving is Na3La(PO4)2With the compound phase of NASICON, due to the synthesis of material be according to
Na3+xLaxZr2-xSi2PO12(x=0.05) stoichiometric proportion designing, it is possible thereby to infer
The concrete component of NASICON principal phases is Na2.9Zr1.95Si2P0.9O11.6.Therefore the composite solid electrolyte
Composition can write 0.05Na3La(PO4)2/Na2.9Zr1.95Si2P0.9O11.6。
In the fine and close gold of the above-mentioned potsherd two sides injection last layer for preparing as blocking electrode, adopt
The ionic conductivity of potsherd is tested with AC impedence method.At 25 DEG C, the composite solid electrolyte
Ionic conductivity is 0.96 × 10-3S/cm, its impedance spectra such as Fig. 3 (x=0.05).
Embodiment 3
Prepared using the sol-gel process in present invention described in the third aspect in the present embodiment and be based on
The sodion solid electrolytes composite of NASICON structures
0.15Na3La(PO4)2/Na2.7Zr1.85Si2P0.7O10.8。
By TEOS and H2O, ethanol are with 1:10:20 mol ratios are miscible, add citric acid (citric acid
Mol ratio with cation is 2:1), the stirring hydrolysis 1h at 60 DEG C, is subsequently adding the change of required sodium
Learn sodium nitrate and stoichiometric zirconyl nitrate, the Lanthanum (III) nitrate of metering 115wt%, last Deca
NH4H2PO4, being warming up to 80 DEG C of stirrings makes moisture evaporation, obtains Gel Precursor；By the gel
Presoma is placed in baking oven, dries 3 hours, obtain xerogel at 200 DEG C；Above-mentioned xerogel is existed
550 DEG C of heat treatments 5 hours；Then sinter 12 hours at 850 DEG C；Then by the forerunner after presintering
Body powder is ground, then sinters 4 hours at 1200 DEG C, obtains the white complex solid electrolysis of lamellar
Matter.
Its x-ray diffractogram of powder spectrum is (x=0.15) as shown in Figure 1, it will be seen from figure 1 that
The material for arriving is Na3La(PO4)2With the compound phase of NASICON, due to the synthesis of material be according to
Na3+xLaxZr2-xSi2PO12(x=0.15) stoichiometric proportion designing, it is possible thereby to infer
The concrete component of NASICON principal phases is Na2.7Zr1.85Si2P0.7O10.8.Therefore the complex solid is electrolysed
The composition of matter can write 0.15Na3La(PO4)2/Na2.7Zr1.85Si2P0.7O10.8。
Fig. 2 is 0.15Na3La(PO4)2/Na2.7Zr1.85Si2P0.7O10.8Composite solid electrolyte piece
STEM shape appearance figures, it can be seen that potsherd is clearly present two kinds of different crystal grain of contrast,
EDS results show that the essential element of white portion consists of Na, La, P, O, with reference to XRD
Result, it is known that the composition in the region be Na3La(PO4)2, and gray area group is wanted elementary composition and is
Na, Zr, Si, P, O, can extrapolate the region consist of Na2.7Zr1.85Si2P0.7O10.8。
Further, it is also possible to find out about 200～400 nanometers of grain size inside potsherd, crystal grain with
Contact tight between crystal grain, gap or crackle is not observed, consistency is very high.
In the fine and close gold of the above-mentioned potsherd two sides injection last layer for preparing as blocking electrode, adopt
The ionic conductivity of potsherd is tested with AC impedence method.At 25 DEG C, the composite solid electrolyte
Ionic conductivity is 1.5 × 10-3S/cm, its impedance spectra such as Fig. 3 (x=0.15).
Embodiment 4
The present embodiment is used for explanation using the sol-gel legal system in present invention described in the third aspect
The standby sodion solid electrolytes composite 0.25 based on NASICON structures
Na3La(PO4)2/Na2.25Zr1.75Si2P0.5O8。
By TEOS and H2O, ethanol are with 1：8：18 mol ratio is miscible, adds citric acid (Fructus Citri Limoniae
Acid is 1 with the mol ratio of cation:1), stirring hydrolysis 0.5 hour at 65 DEG C, then sequentially adds
The sodium acetate of stoichiometry 115wt% of required sodium and stoichiometric zirconyl nitrate, Lanthanum (III) nitrate,
Last Deca (NH4)2HPO4Aqueous solution, being warming up to 90 DEG C of stirrings makes moisture evaporation, obtains gel
Presoma；The Gel Precursor is dried 5 hours at 150 DEG C, xerogel is obtained；Will be described
Xerogel heat treatment 3 hours at 600 DEG C, then presintering 2 hours at 950 DEG C；By pre-burning
Presoma xerogel grinding after knot, then sinter 6 hours at 1150 DEG C, obtain described being based on
The sodion solid electrolytes composite of NASICON structures.
Its x-ray diffractogram of powder spectrum is (x=0.25) as shown in Figure 1, it will be seen from figure 1 that
The material for arriving is Na3La(PO4)2With the compound phase of NASICON, due to the synthesis of material be according to
Na3+xLaxZr2-xSi2PO12(x=0.25) stoichiometric proportion designing, it is possible thereby to infer
The concrete component of NASICON principal phases is Na2.5Zr1.75Si2P0.5O10.Therefore the composite solid electrolyte
Composition can write 0.25Na3La(PO4)2/Na2.5Zr1.75Si2P0.5O10。
In the fine and close gold of the above-mentioned potsherd two sides injection last layer for preparing as blocking electrode, adopt
The ionic conductivity of potsherd is tested with AC impedence method.At 25 DEG C, the composite solid electrolyte
Ionic conductivity is 3.2 × 10-3S/cm, its impedance spectra such as Fig. 3 (x=0.25).
Embodiment 5
Prepared using the solid phase method described in present invention second aspect in the present embodiment and be based on
The sodion solid electrolytes composite of NASICON structures
0.35Na3La(PO4)2/Na2.3Zr1.65Si2P0.3O9.2。
By the Na of stoichiometry 110wt% of required sodium2CO3、ZrO2、La2O3(before use
More than 1000 DEG C heat treatment 2h, to remove the CO of absorption2)、SiO2、(NH4)2HPO4Match somebody with somebody in proportion
Material, is mixed into presoma；The presoma is uniformly mixed to get by precursor using the method for ball milling
End；The precursor powder is placed in Muffle furnace, in 750 DEG C of air atmosphere, heat treatment 8 is little
When；Precursor powder after pre-burning is ground, tabletting, and in 1200 DEG C of air atmosphere high temperatures
Sintering 2 hours, obtains the sodion solid electrolytes composite based on NASICON structures.
Its x-ray diffractogram of powder spectrum is (x=0.35) as shown in Figure 1, it will be seen from figure 1 that
The material for arriving is Na3La(PO4)2With the compound phase of NASICON, due to the synthesis of material be according to
Na3+xLaxZr2-xSi2PO12(x=0.35) stoichiometric proportion designing, it is possible thereby to infer
The concrete component of NASICON principal phases is Na2.3Zr1.65Si2P0.3O9.2.Therefore the composite solid electrolyte
Composition can write 0.35Na3La(PO4)2/Na2.3Zr1.65Si2P0.3O9.2。
In the fine and close gold of the above-mentioned potsherd two sides injection last layer for preparing as blocking electrode, adopt
The ionic conductivity of potsherd is tested with AC impedence method.At 25 DEG C, the composite solid electrolyte
Ionic conductivity is 2.0 × 10-3S/cm, its impedance spectra such as Fig. 3 (x=0.35).
Embodiment 6
The present embodiment is entirely solid to prepare sodium ion using the composite solid electrolyte that embodiment 4 is prepared
State battery, and illustrate battery behavior.
The solid electrolytic composite material that embodiment 4 is prepared is used for all-solid sodium ion battery
Prepare.Concretely comprise the following steps：By the composite solid electrolyte grind into powder for preparing, with positive-active
Material Na3V2(PO4)3, white carbon black and binding agent PVDF be according to 30：50：10：10 mass ratio is mixed
Close uniform, add appropriate N-Methyl pyrrolidone (NMP) solution, in the environment of normal temperature drying
Under grind to form slurry, then slurry is coated uniformly on the composite solid electrolyte obtain in embodiment 4
On potsherd, it is dried in being transferred to baking oven, obtains being coated with the potsherd of positive pole.
By the above-mentioned potsherd for being coated with positive pole in vacuum tube furnace heat treatment 2 hours at 700 DEG C,
It is transferred to after lowering the temperature standby in glove box.
Battery be assemblied in glove box in carry out.The potsherd for being coated with positive pole after by above-mentioned heat treatment
The uncoated side stick metal Na pieces, be assembled into battery and seal.
The battery being assembled into is tested at room temperature, test voltage scope be 2.5～3.6V, discharge and recharge
Curve is shown in Fig. 4.Indicate the discharge and recharge song of the 1st week, the 2nd week and the 100th week in Fig. 4 respectively
Line.As can be seen that first week charge specific capacity is up to 117mAh/g, the coulombic efficiency in first week is 90%,
After circulating 100 weeks, reversible specific capacity is still maintained at 105mAh/g.
Embodiment 7
The composite solid electrolyte that the present embodiment is prepared using embodiment 4 prepare all solid state sodium from
Sub- battery, and illustrate battery behavior.
The solid electrolytic composite material that embodiment 4 is prepared is used for all-solid sodium ion battery
Prepare.Concretely comprise the following steps：By the composite solid electrolyte grind into powder for preparing, with positive-active
Material Na3(VOPO4)2F, white carbon black and binding agent PVDF are according to 30：45：15：10 mass ratio
Mix homogeneously, adds appropriate N-Methyl pyrrolidone (NMP) solution, in the ring of normal temperature drying
Slurry is ground to form under border, then slurry is coated uniformly on the complex solid electrolysis obtain in embodiment 4
On matter potsherd, it is dried in being transferred to baking oven, obtains being coated with the potsherd of positive pole.
By the above-mentioned potsherd for being coated with positive pole in vacuum tube furnace heat treatment 2 hours at 450 DEG C,
It is transferred to after lowering the temperature standby in glove box.
Battery be assemblied in glove box in carry out.The potsherd for being coated with positive pole after by above-mentioned heat treatment
The uncoated side stick metal Na pieces, be assembled into battery and seal.
The battery being assembled into is tested at room temperature, test voltage scope be 3～4.2V, discharge and recharge
Curve is shown in Fig. 5.The discharge and recharge behavior of the last fortnight, first week charging and discharging specific capacity are illustrated in Fig. 5
Respectively 140.5mAh/g and 110.2mAh/g, the reversible specific capacity of second week are maintained at 110
mAh/g。
Embodiment 8
The composite solid electrolyte that the present embodiment is prepared using embodiment 4 prepare all solid state sodium from
Sub- battery, and illustrate battery behavior.
The solid electrolytic composite material that embodiment 4 is prepared is used for all-solid sodium ion battery
Prepare.Concretely comprise the following steps：By the composite solid electrolyte grind into powder for preparing, with positive-active
Material NaTi2(PO4)3, white carbon black and binding agent PVDF be according to 35：45：10：10 mass ratio is mixed
Close uniform, add appropriate N-Methyl pyrrolidone (NMP) solution, in the environment of normal temperature drying
Under grind to form slurry, then slurry is coated uniformly on the composite solid electrolyte obtain in embodiment 4
On potsherd, it is dried in being transferred to baking oven, obtains being coated with the potsherd of positive pole.
By the above-mentioned potsherd for being coated with positive pole in vacuum tube furnace heat treatment 2 hours at 600 DEG C,
It is transferred to after lowering the temperature standby in glove box.
Battery be assemblied in glove box in carry out.The potsherd for being coated with positive pole after by above-mentioned heat treatment
The uncoated side stick metal Na pieces, be assembled into battery and seal.
The battery being assembled into is tested at room temperature, test voltage scope be 1.5～2.8V, discharge and recharge
Curve is shown in Fig. 6.The charging and discharging curve of the last fortnight is illustrated in Fig. 6.As can be seen that head Zhou Fang electricity ratios
Capacity and charging capacity are respectively 133mAh/g and 115mAh/g, and the reversible specific capacity of second week is protected
Hold in 114mAh/g.
Comparative example 1
By TEOS and H2O, ethanol are with 1:10:20 mol ratios are miscible, add appropriate citric acid,
The stirring hydrolysis 1h at 60 DEG C, then by the sodium nitrate of stoichiometry 115wt% of required sodium and institute
The aqueous solution of the stoichiometric zirconyl nitrate of need is sequentially added and is hydrolyzed in completely TEOS, last Deca
NH4H2PO4Or (NH4)2HPO4, being warming up to 80 DEG C of stirrings makes moisture evaporation, obtains Gel Precursor；
The Gel Precursor is placed in baking oven, is dried 3 hours at 200 DEG C, is obtained xerogel；Will
Above-mentioned xerogel was in 550 DEG C of heat treatments 5 hours；Then sinter 12 hours at 850 DEG C；Then will be pre-
Precursor powder after sintering is ground, then sinters 4 hours at 1200 DEG C, obtains the white of lamellar
Solid electrolyte Na3Zr2Si2PO12。
Its x-ray diffractogram of powder is composed as shown in fig. 7, from figure 7 it can be seen that the material for obtaining is
Pure phase NASICON, no impurities phase are produced.In the above-mentioned potsherd two sides injection for preparing
One layer of fine and close gold tests the ionic conductivity of potsherd using AC impedence method as blocking electrode.
At 25 DEG C, Na3Zr2Si2PO12Ionic conductivity be 6.6 × 10-4S/cm, its ac impedance spectroscopy
Figure is shown in Fig. 8.
Table 1 lists Na obtained in comparative example 13Zr2Si2PO12And embodiment of the present invention 1-5 is obtained
XNa3La(PO4)2/Na3-2xZr2-xSi2P1-2xO12-8x(x=0.05,0.1,0.15,0.2,0.25,0.3,
0.35th, 0.4 and 0.45) in 25 DEG C of ionic conductivity.
Table 1
| Chemical composition | Ionic conductivity (S/cm) |
| Na3Zr2Si2PO12 | 6.60×10-4 |
| X=0.05 | 9.6×10-4 |
| X=0.1 | 1.3×10-3 |
| X=0.15 | 1.5×10-3 |
| X=0.2 | 1.8×10-3 |
| X=0.25 | 3.2×10-3 |
| X=0.3 | 3.4×10-3 |
| X=0.35 | 2.0×10-3 |
| X=0.4 | 1.3×10-3 |
| X=0.45 | 9.6×10-4 |
Can be seen that by La elements are introduced in NASICON systems by the data in table 1,
La elements are with Na3La(PO4)2In the form of second phase, and principal phase is consisted of
Na3-2xZr2-xSi2P1-2xO12-8x.The potsherd conductivity at room temperature for obtaining reaches as high as 3.4 × 10-3
S/cm.The presence of La elements affects the ionic conductance performance of potsherd in terms of following two：On the one hand,
La's is introduced into the Na ions that can capture in NASICON principal phases, forms Na3La(PO4)2Second phase,
Occur Na rooms in causing principal phase so that bulk conductivity rate is improved；On the other hand, the introducing of La is big
The consistency of potsherd is improve greatly, and due to the space charge effect of biphase grain boundaries, causes crystalline substance
Boundary's electrical conductivity improves an order of magnitude.
Above-described specific embodiment, enters to the purpose of the present invention, technical scheme and beneficial effect
Further description is gone, the be should be understood that specific embodiment party that the foregoing is only the present invention
Formula, the protection domain being not intended to limit the present invention, it is all within the spirit and principles in the present invention,
Any modification, equivalent substitution and improvements done etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of sodion solid electrolytes composite based on NASICON structures, the composite wood
The formula of material is：xNa3La(PO4)2/Na3-2xZr2-xSi2P1-2xO12-8x, wherein 0 ＜ x≤0.5.
2. the sodion solid electrolytes based on NASICON structures according to claim 1 are multiple
Condensation material, wherein, the ionic conductivity of the composite is 0.9 × 10-3～5.0 × 10-3S/cm。
3. sodion solid electrolytes described in claim 1 or 2 based on NASICON structures are combined
The preparation method of material, the method include：
By the Na of the 110～115wt% of stoichiometry of required sodium2CO3With stoichiometric ZrO2、
La2O3、SiO2And NH4H2PO4Or (NH4)2HPO4It is mixed to form presoma；
The presoma is uniformly mixed to get by precursor powder using the method for ball milling；
By the precursor powder at 750～950 DEG C heat treatment 2～24 hours；
By the precursor powder grinding after heat treatment, tabletting, and 2～24 are sintered at 1050～1200 DEG C
Hour, that is, obtain the sodion solid electrolytes composite based on NASICON structures.
4. preparation method according to claim 3, wherein, the preparation method also includes：
Before being mixed to form presoma, by La2O3The heat treatment 2h more than 1000 DEG C, to remove absorption
CO2。
5. sodion solid electrolytes described in claim 1 or 2 based on NASICON structures are combined
The preparation method of material, the method include：
By tetraethyl orthosilicate and H2O, ethanol are with 1：8～12：18～22 mol ratio is miscible, adds
Citric acid, at 55～65 DEG C, stirring hydrolysis 0.5～3 hour, then sequentially adds the chemistry of required sodium
The sodium nitrate of 110～115wt% of metering or sodium acetate and stoichiometric zirconyl nitrate and Lanthanum (III) nitrate
Or lanthanum acetate, last Deca NH4H2PO4Or (NH4)2HPO4Aqueous solution, obtain colloidal sol, heat up
Moisture evaporation is made to 70～90 DEG C of stirrings, Gel Precursor is obtained；
The Gel Precursor is dried 3～5 hours at 150～200 DEG C, xerogel is obtained；
By the xerogel at 500～600 DEG C heat treatment 3～6 hours, then at 750～950 DEG C
Presintering 2～24 hours；
Presoma xerogel after presintering is ground, then sintering 2～24 is little at 1050～1200 DEG C
When, obtain the sodion solid electrolytes composite based on NASICON structures.
6. preparation method according to claim 5, wherein, the citric acid is rubbed with cation
You are than being 1～2.
7. preparation method according to claim 5, wherein, the sodium nitrate, sodium acetate, nitre
Sour oxygen zirconium, Lanthanum (III) nitrate and lanthanum acetate are respective aqueous solution, wherein, the concentration of sodium nitrate aqueous solution
For 0.05～10.7mol/L, the concentration of sodium acetate aqueous solution is 0.05～6.6mol/L, and zirconyl nitrate is water-soluble
The concentration of liquid is 0.5～1.5mol/L, and the concentration of lanthanum nitrate aqueous solution is 0.05～4.2mol/L, acetic acid
The concentration of lanthanum aqueous solution is 0.05～2.0mol/L.
8. preparation method according to claim 5, wherein, the NH4H2PO4Aqueous solution
Concentration is 0.05～3.5mol/L, (NH4)2HPO4The concentration of aqueous solution is 0.05～4.5mol/L.
9. the sodion solid electrolytes based on NASICON structures described in claim 1 or 2 are multiple
Condensation material or according to obtained in method any one of claim 3 to 8 be based on NASICON
Application of the sodion solid electrolytes composite of structure in all-solid sodium ion battery is prepared.
10. a kind of all-solid sodium ion battery, the battery include the base described in claim 1 or 2
In the sodion solid electrolytes composite of NASICON structures or according to claim 3 to 8
Any one of the obtained sodion solid electrolytes composite wood based on NASICON structures of method
Material.
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Cited By (7)
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| CN108695552A (en) * | 2018-07-11 | 2018-10-23 | 中国科学院宁波材料技术与工程研究所 | NASICON structures sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN109818050A (en) * | 2017-11-22 | 2019-05-28 | 中国科学院物理研究所 | NASICON structure sodion solid electrolytes/sodium halide composite material and preparation method and application |
| CN109860700A (en) * | 2019-01-16 | 2019-06-07 | 广东工业大学 | A kind of Nasicon structure sodion solid electrolytes and its preparation method and application |
| CN110280854A (en) * | 2018-03-19 | 2019-09-27 | 天津大学 | The solid state electrolysis processing method and its solid electrolyte and preparation method of a kind of array micro-pit structure |
| CN113073357A (en) * | 2021-03-19 | 2021-07-06 | 西南石油大学 | Electrolytic device based on solid electrolyte diaphragm material and method for preparing sodium by using electrolytic device |
| CN113346127A (en) * | 2021-05-31 | 2021-09-03 | 东风汽车集团股份有限公司 | NASICON type lithium ion solid electrolyte, preparation method and battery |
| CN113675463A (en) * | 2021-08-21 | 2021-11-19 | 西南石油大学 | NASICON type inorganic solid electrolyte material and preparation method and application thereof |
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| CN109818050A (en) * | 2017-11-22 | 2019-05-28 | 中国科学院物理研究所 | NASICON structure sodion solid electrolytes/sodium halide composite material and preparation method and application |
| CN110280854A (en) * | 2018-03-19 | 2019-09-27 | 天津大学 | The solid state electrolysis processing method and its solid electrolyte and preparation method of a kind of array micro-pit structure |
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| CN109860700A (en) * | 2019-01-16 | 2019-06-07 | 广东工业大学 | A kind of Nasicon structure sodion solid electrolytes and its preparation method and application |
| CN113073357A (en) * | 2021-03-19 | 2021-07-06 | 西南石油大学 | Electrolytic device based on solid electrolyte diaphragm material and method for preparing sodium by using electrolytic device |
| CN113346127A (en) * | 2021-05-31 | 2021-09-03 | 东风汽车集团股份有限公司 | NASICON type lithium ion solid electrolyte, preparation method and battery |
| CN113346127B (en) * | 2021-05-31 | 2022-08-30 | 东风汽车集团股份有限公司 | NASICON type lithium ion solid electrolyte, preparation method and battery |
| CN113675463A (en) * | 2021-08-21 | 2021-11-19 | 西南石油大学 | NASICON type inorganic solid electrolyte material and preparation method and application thereof |
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