CN106064821A - A kind of Na3+2xzr2 xmxsi2pO12the preparation method of solid electrolyte powder body material - Google Patents

A kind of Na3+2xzr2 xmxsi2pO12the preparation method of solid electrolyte powder body material Download PDF

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CN106064821A
CN106064821A CN201610393725.0A CN201610393725A CN106064821A CN 106064821 A CN106064821 A CN 106064821A CN 201610393725 A CN201610393725 A CN 201610393725A CN 106064821 A CN106064821 A CN 106064821A
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CN106064821B (en
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刘占国
贺思博
任哲
欧阳家虎
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Heilongjiang Industrial Technology Research Institute Asset Management Co ltd
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Harbin Institute of Technology
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Abstract

A kind of Na3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material.The invention belongs to solid electrolyte material technical field, particularly to the preparation method of a kind of Fast ion conductor powder body material.The present invention seeks to solve the problem that existing high temperature solid-state method reaction temperature is high, electrical conductivity is low and existing sol gel process obtains powder reuniting is serious.Method: one, by NaNO3、ZrO(NO3)2·2H2O、M(NO3)2·nH2O and (NH4)2HPO4Use deionized water dissolving respectively；Two, in dehydrated alcohol, add deionized water and dispersant, TEOS, regulate pH；Three, four kinds of solution that the most dropwise dropping step one obtains in the colloidal sol that step 2 obtains；Four, still aging under sealing and lucifuge, dry, obtain presoma；Five, calcining, grinds, obtains Na3+2xZr2–xMxSi2PO12Powder body.

Description

A kind of Na3+2xZr2-xMxSi2PO12The preparation method of solid electrolyte powder body material
Technical field
The invention belongs to solid electrolyte material technical field, particularly to the system of a kind of Fast ion conductor powder body material Preparation Method.
Background technology
, easily there is the problem such as leakage and electrode corrosion, at height in the most traditional secondary cell many employings liquid electrolyte Blast it is also possible under temperature.By contrast, solid electrolyte have the highest heat stability, reliability, long cycle life and Various geometric configuration.Na+With Li+Having similar embedding and electrical conduction mechanism, and Na element is widely distributed in the earth's crust, it is rich Degree reaches 2.64%, easily obtains, cheap, can be used in fixed sources of energy field of storage.This means sodium ion electrolyte There is good application prospect.Therefore, sodion solid electrolytes is of great interest.
Fast ion conductor, referred to as NASICON, be a kind of typical sodion solid electrolytes.Fast ion conductor Be a kind of electrical conductivity height, stable performance, safe and reliable, prepare simple, cheap and Na+Can isotropism conduction material, Also have do not react with Na, decomposition voltage is higher, sintering temperature is relatively low, to the advantage such as steam is insensitive.Its chemical formula is Na1+xZr2SixP3–xO12, as x=2, i.e. Na3Zr2Si2PO12Ionic conductivity the highest, at room temperature up to 10–4S/cm number Magnitude.
But this material there is problems in that traditional preparation method is mainly high temperature solid-state method, reaction temperature is 1100 DEG C so that the Na element in material and P element volatilization, destroy crystal structure, introduce SiO2And ZrO2Dephasign, reduces material Electrical conductivity.And generally there is more serious reunion in the powder body using existing sol gel process to obtain.Current doping changes Journal of Sex Research is concentrated mainly on the quadrivalent cation doping (Ge of Zr position4+、Sn4+And Ti4+Deng) and trivalent rare earth cation doping (Dy3 +、Yb3+And Er3+Deng).It is true that Ni2+And Zn2+Deng bivalent cation and Zr4+Ionic radius very close to, and equally with Oxygen atom forms octahedral structure, and lower valence state can introduce more gap Na+And reduce Na+Migration resistance.Institute With the M that adulterates in Zr position in theory2+(M=Co, Ni, Zn, Mg) can effectively promote the electrical conductivity of material.
Summary of the invention
The present invention seeks to solve that existing high temperature solid-state method reaction temperature is high, electrical conductivity is low and existing collosol and gel work The problem that powder reuniting that skill obtains is serious, and a kind of Na is provided3+2xZr2–xMxSi2PO12The preparation of solid electrolyte powder body material Method.
A kind of Na of the present invention3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material is entered according to the following steps OK:
One, by NaNO3、ZrO(NO3)2·2H2O、M(NO3)2·nH2O and (NH4)2HPO4Respectively with deionized water dissolving, Obtain the NaNO that concentration is 1.5mol/L～6mol/L3Solution, concentration are the ZrO (NO of 0.25mol/L～1mol/L3)2Solution, Concentration is the M (NO of 0.1mol/L～1mol/L3)2Solution and the (NH that concentration is 0.25mol/L～1mol/L4)2HPO4Solution；Institute M (the NO stated3)2·nH2M=Co in O2+、Ni2+、Zn2+Or Mg2+；
Two, adding deionized water and dispersant in dehydrated alcohol, stirring is completely dissolved to dispersant, obtains dispersant molten Liquid, then adds TEOS in dispersant solution, uses magnetic stirring apparatus under conditions of rotating speed is 15r/min～25r/min Stirring is to mix homogeneously, then drips catalyst regulation pH to 0.5～3.5, then hydrolyzes under conditions of temperature is 40～60 DEG C 1h～5h obtains Sol A；Described deionized water is 1:(300～500 with the volume ratio of dehydrated alcohol)；Described dispersant with The mol ratio of TEOS is 1:(1.8～2.2)；The amount of the material of described dispersant and the volume ratio of dehydrated alcohol be (0.8～ 1.2)mol:100L；
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.5mol/L～6mol/L3Molten Liquid, concentration are the ZrO (NO of 0.25mol/L～1mol/L3)2Solution, concentration are the M (NO of 0.1mol/L～1mol/L3)2Solution With (the NH that concentration is 0.25mol/L～1mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 70～90 DEG C, The volume stirred under conditions of temperature is 70～90 DEG C to sol B becomes the 1/3 of sol B initial volume, obtains colloidal sol C；
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L～1mol/L4)2HPO4NH in solution4 +'s Mol ratio is (0.8～1.2): 2；Described concentration is the NaNO of 1.5mol/L～6mol/L3NaNO in solution3: concentration is ZrO (the NO of 0.25mol/L～1mol/L3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L～1mol/L3)2Solution In M (NO3)2: concentration is the (NH of 0.25mol/L～1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:(2 x):x:1；Wherein 0 ＜ x≤0.3；
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge D puts in baking oven dries 24h under conditions of temperature is 70～90 DEG C and obtains presoma；
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky In steam stove, it is warmed up to 850～950 DEG C with the heating rate of 4 DEG C/min～6 DEG C/min, is then 850～950 DEG C in temperature Under the conditions of calcine 6h～12h, be ground to particle diameter in 0.4 μm～0.6 μm, obtain finely disseminated Na3+2xZr2–xMxSi2PO12Solid Electrolyte powder body material.
Beneficial effects of the present invention:
Present invention sol-gal process, by control catalyst type, calcining heat, calcination time, dispersant with And NaNO3(NH4)2HPO4Consumption, the Na that prepared composition is uniformly, good dispersion, reactivity are high3+2xZr2–xMxSi2PO12(M =Co2+,Ni2+,Zn2+,Mg2+) pure phase powder body, diameter of particle is 0.4 μm～0.6 μm, and the method for the present invention reduces block materials Sintering temperature, the beneficially lifting of electrical conductivity, and operational approach is simple, reproducible, can realize producing in enormous quantities.The present invention Concrete advantage as follows:
(1) use sol-gal process to make raw material reach the other uniform mixing of molecular level, be particularly advantageous in doped chemical and melt Entering in crystal structure, the product component finally obtained is uniform.
(2) sol-gal process can reduce reaction temperature, not only energy-and time-economizing, it is also possible to reduces because of Na element and P element The SiO that volatilization produces2And ZrO2Dephasign.
(3) by controlling catalyst type, calcining heat, calcination time, dispersant and NaNO3(NH4)2HPO4Consumption, effectively reduce diameter of particle and also promote its dispersibility, efficiently avoid the powder body that sol-gal process often occurs Agglomeration, is conducive to promoting the consistency of ceramic block.
(4) dehydrated alcohol has simultaneously worked as effect the most molten, that dilute and inhibit.
(5) acid catalyzed reaction condition accelerates the hydrolytic process of TEOS and suppresses the polycondensation process of product, in dropping electrolysis Being difficult to coagulation during matter solution, controllability is good.
(6) operation is simple for the present invention, with short production cycle, can apply in large-scale commercial production.
Accompanying drawing explanation
Fig. 1 is test Na prepared by3.4Zr1.8Zn0.2Si2PO12Powder body and Na3Zr2Si2PO12The XRD comparison diagram of powder body Spectrum；Wherein 1 Na prepared by test one3.4Zr1.8Zn0.2Si2PO12Powder body, 2 is Na3Zr2Si2PO12Powder body；
Fig. 2 is test Na prepared by3.4Zr1.8Zn0.2Si2PO12The SEM photograph of powder body；
Fig. 3 is test Na prepared by two3.2Zr1.9Ni0.1Si2PO12Powder body and Na3Zr2Si2PO12The XRD comparison diagram of powder body Spectrum；Wherein 1 Na prepared by test two3.2Zr1.9Ni0.1Si2PO12Powder body, 2 is Na3Zr2Si2PO12Powder body；
Fig. 4 is test Na prepared by two3.2Zr1.9Ni0.1Si2PO12The SEM photograph of powder body.
Detailed description of the invention
Detailed description of the invention one: a kind of Na of present embodiment3+2xZr2–xMxSi2PO12The system of solid electrolyte powder body material Preparation Method sequentially includes the following steps:
One, by NaNO3、ZrO(NO3)2·2H2O、M(NO3)2·nH2O and (NH4)2HPO4Respectively with deionized water dissolving, Obtain the NaNO that concentration is 1.5mol/L～6mol/L3Solution, concentration are the ZrO (NO of 0.25mol/L～1mol/L3)2Solution, Concentration is the M (NO of 0.1mol/L～1mol/L3)2Solution and the (NH that concentration is 0.25mol/L～1mol/L4)2HPO4Solution；Institute M (the NO stated3)2·nH2M=Co in O2+、Ni2+、Zn2+Or Mg2+；
Two, adding deionized water and dispersant in dehydrated alcohol, stirring is completely dissolved to dispersant, obtains dispersant molten Liquid, then adds TEOS in dispersant solution, uses magnetic stirring apparatus under conditions of rotating speed is 15r/min～25r/min Stirring is to mix homogeneously, then drips catalyst regulation pH to 0.5～3.5, then hydrolyzes under conditions of temperature is 40～60 DEG C 1h～5h obtains Sol A；Described deionized water is 1:(300～500 with the volume ratio of dehydrated alcohol)；Described dispersant with The mol ratio of TEOS is 1:(1.8～2.2)；The amount of the material of described dispersant and the volume ratio of dehydrated alcohol be (0.8～ 1.2)mol:100L；
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.5mol/L～6mol/L3Molten Liquid, concentration are the ZrO (NO of 0.25mol/L～1mol/L3)2Solution, concentration are the M (NO of 0.1mol/L～1mol/L3)2Solution With (the NH that concentration is 0.25mol/L～1mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 70～90 DEG C, The volume stirred under conditions of temperature is 70～90 DEG C to sol B becomes the 1/3 of sol B initial volume, obtains colloidal sol C；
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L～1mol/L4)2HPO4NH in solution4 +'s Mol ratio is (0.8～1.2): 2；Described concentration is the NaNO of 1.5mol/L～6mol/L3NaNO in solution3: concentration is ZrO (the NO of 0.25mol/L～1mol/L3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L～1mol/L3)2Solution In M (NO3)2: concentration is the (NH of 0.25mol/L～1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:(2 x):x:1；Wherein 0 ＜ x≤0.3；
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge D puts in baking oven dries 24h under conditions of temperature is 70～90 DEG C and obtains presoma；
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky In steam stove, it is warmed up to 850～950 DEG C with the heating rate of 4 DEG C/min～6 DEG C/min, is then 850～950 DEG C in temperature Under the conditions of calcine 6h～12h, be ground to particle diameter in 0.4 μm～0.6 μm, obtain finely disseminated Na3+2xZr2–xMxSi2PO12Solid Electrolyte powder body material.
Present embodiment sol-gal process, by controlling catalyst type, calcining heat, calcination time, dispersant kind Class and NaNO3(NH4)2HPO4Consumption, the Na that prepared composition is uniformly, good dispersion, reactivity are high3+2xZr2– xMxSi2PO12(M=Co2+,Ni2+,Zn2+,Mg2+) pure phase powder body, diameter of particle is 0.4 μm～0.6 μm, the side of present embodiment Method reduces the lifting of the sintering temperature of block materials, beneficially electrical conductivity, and operational approach is simple, reproducible, can realize Produce in enormous quantities.Particularly advantage of the invention is as follows:
(1) use sol-gal process to make raw material reach the other uniform mixing of molecular level, be particularly advantageous in doped chemical and melt Entering in crystal structure, the product component finally obtained is uniform.
(2) sol-gal process can reduce reaction temperature, not only energy-and time-economizing, it is also possible to reduces because of Na element and P element The SiO that volatilization produces2And ZrO2Dephasign.
(3) by controlling catalyst type, calcining heat, calcination time, dispersant and NaNO3(NH4)2HPO4Consumption, effectively reduce diameter of particle and also promote its dispersibility, effectively evaded the powder body that sol-gal process often occurs Agglomeration, is conducive to promoting the consistency of ceramic block.
(4) dehydrated alcohol has simultaneously worked as effect the most molten, that dilute and inhibit.
(5) acid catalyzed reaction condition accelerates the hydrolytic process of TEOS and suppresses the polycondensation process of product, in dropping electrolysis Being difficult to coagulation during matter solution, controllability is good.
(6) operation is simple for present embodiment, with short production cycle, can apply in large-scale commercial production.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: the dispersion described in step 2 Agent is citric acid, PEG1000 or CTAB.Other steps and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: described in step 2 Catalyst is concentrated nitric acid, oxalic acid or acetic acid.Other steps and parameter are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: institute in step 2 The deionized water stated is 1:400 with the volume ratio of dehydrated alcohol.Other steps and one of parameter and detailed description of the invention one to three Identical.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: institute in step 2 The dispersant stated is 1:2 with the mol ratio of TEOS.Other steps and parameter are identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: institute in step 2 The amount of the material of the dispersant stated and the volume ratio of dehydrated alcohol are 1mol:100L.Other steps and parameter and specific embodiment party One of formula one to five is identical.
Detailed description of the invention seven: present embodiment is unlike one of detailed description of the invention one to six: in step 2 to Adding deionized water and dispersant in dehydrated alcohol, stirring is completely dissolved to dispersant, obtains dispersant solution, then to dispersion Agent solution adds TEOS, stirs to mix homogeneously under conditions of rotating speed is 20r/min, then drip catalyst regulation pH to 2, Then under conditions of temperature is 50 DEG C, hydrolyzes 1h obtains Sol A.Other steps and parameter and detailed description of the invention one to six it One is identical.
Detailed description of the invention eight: present embodiment is unlike one of detailed description of the invention one to seven: institute in step 3 Dispersant in the Sol A stated and concentration are the (NH of 0.25mol/L～1mol/L4)2HPO4NH in solution4 +Mol ratio be 1: 2.Other steps and parameter are identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention one to eight: institute in step 3 The concentration stated is the NaNO of 1.5mol/L～6mol/L3NaNO in solution3: concentration is the ZrO of 0.25mol/L～1mol/L (NO3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L～1mol/L3)2M (NO in solution3)2: concentration is (the NH of 0.25mol/L～1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:1.8:0.2:1:2.Other steps And parameter is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention one to nine: institute in step 3 The concentration stated is the NaNO of 1.5mol/L～6mol/L3NaNO in solution3: concentration is the ZrO of 0.25mol/L～1mol/L (NO3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L～1mol/L3)2M (NO in solution3)2: concentration is (the NH of 0.25mol/L～1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:1.9:0.1:1:2.Other steps And parameter is identical with one of detailed description of the invention one to nine.
Detailed description of the invention 11: present embodiment is unlike one of detailed description of the invention one to ten: in step 3 Being heated to temperature is 80 DEG C, and the volume stirred under conditions of temperature is 80 DEG C to sol B becomes the 1/3 of sol B initial volume, Obtain colloidal sol C.Other steps and parameter are identical with one of detailed description of the invention one to ten.
Detailed description of the invention 12: present embodiment is unlike one of detailed description of the invention one to ten one: step 4 Middle colloidal sol C step 3 obtained is sealing and is obtaining gel D after still aging 24h under the conditions of lucifuge, and gel D is put into baking oven In under conditions of temperature is 80 DEG C dry 24h obtain presoma.Other steps and parameter and detailed description of the invention one to ten one One of identical.
Detailed description of the invention 13: present embodiment is unlike one of detailed description of the invention one to ten two: step 5 In be warmed up to 900 DEG C with the heating rate of 5 DEG C/min, then under conditions of temperature is 900 DEG C calcine 9h, being ground to particle diameter is 0.5 μm, obtains finely disseminated Na3+2xZr2–xMxSi2PO12Solid electrolyte powder body material.Other steps and parameter are real with concrete Execute one of mode one to ten two identical.
By following verification experimental verification beneficial effects of the present invention:
Test one: a kind of Na of this test3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material is by following Step is carried out:
One, by the NaNO of 2.89g3, the ZrO (NO of 5.08g3)2·2H2Zn (the NO of O, 0.60g3)2·2H2O's and 1.32g (NH4)2HPO4Respectively with deionized water dissolving, obtain the NaNO that concentration is 1.7mol/L3Solution, concentration are 0.45mol/L's ZrO(NO3)2Solution, concentration are the Zn (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution；
The concentration obtained is the NaNO of 1.7mol/L3The volume of solution is 20mL；Concentration is the ZrO (NO of 0.45mol/L3)2 The volume of solution is 40mL；Concentration is the Zn (NO of 0.2mol/L3)2The volume of solution is 5mL；Concentration is 0.25mol/L's (NH4)2HPO4The volume of solution is 40mL；
Two, add 2.5mL deionized water and 4.20g citric acid to 1L dehydrated alcohol, stir and be completely dissolved to dispersant, obtain To dispersant solution, then adding 4.5mLTEOS in dispersant solution, using magnetic stirring apparatus is 20r/min's at rotating speed Under the conditions of stir to mix homogeneously, then drip concentrated nitric acid regulation pH to 2, then under conditions of temperature is 50 DEG C hydrolyze 1h obtain Sol A；
Described dispersant is 1:2 with the mol ratio of TEOS；The amount of the material of described dispersant and the body of dehydrated alcohol Long-pending ratio is 1mol:100L；
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.7mol/L3Solution, concentration are ZrO (the NO of 0.45mol/L3)2Solution, concentration are the Zn (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 80 DEG C, stirs the volume to sol B under conditions of temperature is 80 DEG C Become the 1/3 of sol B initial volume, obtain colloidal sol C；
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L4)2HPO4NH in solution4 +Mol ratio be 1:2；Described concentration is the NaNO of 1.7mol/L3NaNO in solution3: concentration is the ZrO (NO of 0.45mol/L3)2In solution ZrO(NO3)2: concentration is the Zn (NO of 0.2mol/L3)2Zn (NO in solution3)2: concentration is the (NH of 0.25mol/L4)2HPO4Molten (NH in liquid4)2HPO4Mol ratio be 3:1.8:0.2:1:2；
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge D puts in baking oven dries 24h under conditions of temperature is 80 DEG C and obtains presoma；
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky In steam stove, it is warmed up to 900 DEG C with the heating rate of 5 DEG C/min, under conditions of temperature is 900 DEG C, then calcines 9h, is ground to Particle diameter is 0.5 μm, obtains finely disseminated Na3.4Zr1.8Zn0.2Si2PO12Solid electrolyte powder body material.
(1) X-ray diffractometer analysis test Na obtained by is utilized3.4Zr1.8Zn0.2Si2PO12Powder body and Na3Zr2Si2PO12The thing phase composition of powder body, obtains the Na obtained by test one as shown in Figure 13.4Zr1.8Zn0.2Si2PO12Powder body And Na3Zr2Si2PO12The XRD figure spectrum of powder body.
Contrast Na3Zr2Si2PO12And Na3.4Zr1.8Zn0.2Si2PO12XRD figure spectrum understand, Na3.4Zr1.8Zn0.2Si2PO12's Diffraction maximum entirety offsets to the right, does not has miscellaneous peak to occur, illustrates that thing is correct mutually, Zn2+Successfully replace Zr4+Enter in lattice.
(2) utilize scanning electron microscope to Na3.4Zr1.8Zn0.2Si2PO12The tissue topography of powder body characterizes, and obtains The Na obtained by test one as shown in Figure 23.4Zr1.8Zn0.2Si2PO12The SEM photograph of powder body.
Result shows, the Na prepared by the inventive method3.4Zr1.8Zn0.2Si2PO12Powder body hard aggregation-free, good dispersion, removes Individual particles particle diameter is about 1 μm, and the particle diameter of most granules is between 0.2 μm～0.5 μm.
Test two: a kind of Na of this test3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material is by following Step is carried out:
One, by the NaNO of 5.43g3, the ZrO (NO of 10.16g3)2·2H2Ni (the NO of O, 0.58g3)2·2H2O and 2.64g (NH4)2HPO4Respectively with deionized water dissolving, obtain the NaNO that concentration is 1.6mol/L3Solution, concentration are 0.475mol/L ZrO (NO3)2Solution, concentration are the Ni (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution；
The concentration obtained is the NaNO of 1.6mol/L3The volume of solution is 40mL；Concentration is the ZrO of 0.475mol/L (NO3)2The volume of solution is 80mL；Concentration is the Ni (NO of 0.2mol/L3)2The volume of solution is 10mL；Concentration is 0.25mol/ (the NH of L4)2HPO4The volume of solution is 80mL；
Two, adding 5mL deionized water and 8.40g citric acid to 2L dehydrated alcohol, stirring is completely dissolved to dispersant, obtains Dispersant solution, then adds 9mLTEOS in dispersant solution, and using magnetic stirring apparatus is the condition of 20r/min at rotating speed Lower stirring is to mix homogeneously, then drips concentrated nitric acid regulation pH to 2, then hydrolyzes 1h under conditions of temperature is 50 DEG C and obtains colloidal sol A；
Described dispersant is 1:2 with the mol ratio of TEOS；The amount of the material of described dispersant and the body of dehydrated alcohol Long-pending ratio is 1mol:100L；
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.6mol/L3Solution, concentration are ZrO (the NO of 0.475mol/L3)2Solution, concentration are the Ni (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 80 DEG C, stirs the volume to sol B under conditions of temperature is 80 DEG C Become the 1/3 of sol B initial volume, obtain colloidal sol C；
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L4)2HPO4NH in solution4 +Mol ratio be 1:2；Described concentration is the NaNO of 1.6mol/L3NaNO in solution3: concentration is the ZrO (NO of 0.475mol/L3)2In solution ZrO(NO3)2: concentration is the Ni (NO of 0.2mol/L3)2Ni (NO in solution3)2: concentration is the (NH of 0.25mol/L4)2HPO4Molten (NH in liquid4)2HPO4Mol ratio be 3:1.9:0.1:1:2；
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge D puts in baking oven dries 24h under conditions of temperature is 80 DEG C and obtains presoma；
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky In steam stove, it is warmed up to 900 DEG C with the heating rate of 5 DEG C/min, under conditions of temperature is 900 DEG C, then calcines 9h, is ground to Particle diameter is 0.5 μm, obtains finely disseminated Na3.2Zr1.9Ni0.1Si2PO12Solid electrolyte powder body material.
(3) Na obtained by X-ray diffractometer analysis test two is utilized3.2Zr1.9Ni0.1Si2PO12Powder body and Na3Zr2Si2PO12The thing phase composition of powder body, obtains Na obtained by test two as shown in Figure 33.2Zr1.9Ni0.1Si2PO12Powder body and Na3Zr2Si2PO12The XRD figure spectrum of powder body.
Contrast Na3Zr2Si2PO12And Na3.2Zr1.9Ni0.1Si2PO12XRD figure spectrum understand Na3.2Zr1.9Ni0.1Si2PO12's Diffraction maximum entirety offsets to the right, does not has miscellaneous peak to occur, illustrates that thing is correct mutually, Ni2+Successfully replace Zr4+Enter in lattice.
(4) utilize scanning electron microscope to Na3.2Zr1.9Ni0.1Si2PO12The tissue topography of powder body characterizes, and obtains Na obtained by test two as shown in Figure 43.2Zr1.9Ni0.1Si2PO12The SEM photograph of powder body.
Result shows, Na prepared by the inventive method3.2Zr1.9Ni0.1Si2PO12Powder body is without substantially reunion, good dispersion, grain Footpath is substantially between 0.2 μm～0.5 μm, and only individual particles particle diameter is about 1 μm.

Claims (10)

1. a Na3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, it is characterised in that the method is by following Step is carried out:
One, by NaNO3、ZrO(NO3)2·2H2O、M(NO3)2·nH2O and (NH4)2HPO4Respectively with deionized water dissolving, obtain dense Degree is the NaNO of 1.5mol/L～6mol/L3Solution, concentration are the ZrO (NO of 0.25mol/L～1mol/L3)2Solution, concentration are M (the NO of 0.1mol/L～1mol/L3)2Solution and the (NH that concentration is 0.25mol/L～1mol/L4)2HPO4Solution；Described M (NO3)2·nH2M=Co in O2+、Ni2+、Zn2+Or Mg2+；
Two, adding deionized water and dispersant in dehydrated alcohol, stirring is completely dissolved to dispersant, obtains dispersant solution, Then in dispersant solution add TEOS, use magnetic stirring apparatus stir under conditions of rotating speed 15r/min～25r/min to Mix homogeneously, then drip catalyst regulation pH to 0.5～3.5, under conditions of temperature is 40～60 DEG C, then hydrolyze 1h～5h Obtain Sol A；Described deionized water is 1:(300～500 with the volume ratio of dehydrated alcohol)；Described dispersant is with TEOS's Mol ratio is 1:(1.8～2.2)；The amount of the material of described dispersant and the volume ratio of dehydrated alcohol are (0.8～1.2) mol: 100L；
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.5mol/L～6mol/L3Solution, concentration ZrO (NO for 0.25mol/L～1mol/L3)2Solution, concentration are the M (NO of 0.1mol/L～1mol/L3)2Solution and concentration are (the NH of 0.25mol/L～1mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 70～90 DEG C, in temperature is The volume stirred under conditions of 70～90 DEG C to sol B becomes the 1/3 of sol B initial volume, obtains colloidal sol C；
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L～1mol/L4)2HPO4NH in solution4 +Mole Than being (0.8～1.2): 2；Described concentration is the NaNO of 1.5mol/L～6mol/L3NaNO in solution3: concentration is ZrO (the NO of 0.25mol/L～1mol/L3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L～1mol/L3)2Solution In M (NO3)2: concentration is the (NH of 0.25mol/L～1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:(2 x):x:1；Wherein 0 ＜ x≤0.3；
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D after still aging 24h under the conditions of lucifuge, is put by gel D Enter baking oven is dried under conditions of temperature is 70～90 DEG C 24h and obtain presoma；
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into air furnace In, it is warmed up to 850～950 DEG C with the heating rate of 4 DEG C/min～6 DEG C/min, then in the condition that temperature is 850～950 DEG C Lower calcining 6h～12h, is ground to particle diameter in 0.4 μm～0.6 μm, obtains finely disseminated Na3+2xZr2–xMxSi2PO12Solid electrolytic Matter powder body material.
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by that the dispersant described in step 2 is citric acid, PEG1000 or CTAB.
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by that the catalyst described in step 2 is concentrated nitric acid, oxalic acid or acetic acid.
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by that the deionized water described in step 2 is 1:400 with the volume ratio of dehydrated alcohol.
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by that the dispersant described in step 2 is 1:2 with the mol ratio of TEOS.
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by that the amount of material of the dispersant described in step 2 and the volume ratio of dehydrated alcohol are 1mol:100L.
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its The dispersant being characterised by the Sol A described in step 3 and concentration are the (NH of 0.25mol/L～1mol/L4)2HPO4Solution Middle NH4 +Mol ratio be 1:2.
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by the NaNO that the concentration described in step 3 is 1.5mol/L～6mol/L3NaNO in solution3: concentration is ZrO (the NO of 0.25mol/L～1mol/L3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L～1mol/L3)2Solution In M (NO3)2: concentration is the (NH of 0.25mol/L～1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3: 1.8:0.2:1:2。
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by the NaNO that the concentration described in step 3 is 1.5mol/L～6mol/L3NaNO in solution3: concentration is ZrO (the NO of 0.25mol/L～1mol/L3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L～1mol/L3)2Solution In M (NO3)2: concentration is the (NH of 0.25mol/L～1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3: 1.9:0.1:1:2。
A kind of Na the most according to claim 13+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material, its It is characterised by step 5 being warmed up to the heating rate of 5 DEG C/min 900 DEG C, then calcines under conditions of temperature is 900 DEG C 9h, is ground to particle diameter in 0.5 μm, obtains finely disseminated Na3+2xZr2–xMxSi2PO12Solid electrolyte powder body material.
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CN110581312A (en) * 2019-08-07 2019-12-17 广东工业大学 High-ionic-conductivity solid electrolyte with NASICON structure, and preparation and application thereof
CN112952189A (en) * 2021-04-25 2021-06-11 西南石油大学 Sodium super-ion conductor NASICON type structure sodium ion solid electrolyte material and preparation method and application thereof
CN114171787A (en) * 2021-12-07 2022-03-11 四川大学 Mg2+Doped and modified NASCION type sodium ion solid electrolyte and preparation method thereof

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CN105609871A (en) * 2016-01-22 2016-05-25 昆明理工大学 Preparation method of sodium-ion solid electrolyte with NASICON structure
CN105609881A (en) * 2015-12-18 2016-05-25 中国科学院青岛生物能源与过程研究所 Inorganic solid-state electrolyte material and preparation method therefor

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CN105609881A (en) * 2015-12-18 2016-05-25 中国科学院青岛生物能源与过程研究所 Inorganic solid-state electrolyte material and preparation method therefor
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Publication number Priority date Publication date Assignee Title
CN110581312A (en) * 2019-08-07 2019-12-17 广东工业大学 High-ionic-conductivity solid electrolyte with NASICON structure, and preparation and application thereof
CN110581312B (en) * 2019-08-07 2022-08-12 广东工业大学 High-ionic-conductivity solid electrolyte with NASICON structure, and preparation and application thereof
CN112952189A (en) * 2021-04-25 2021-06-11 西南石油大学 Sodium super-ion conductor NASICON type structure sodium ion solid electrolyte material and preparation method and application thereof
CN114171787A (en) * 2021-12-07 2022-03-11 四川大学 Mg2+Doped and modified NASCION type sodium ion solid electrolyte and preparation method thereof
CN114171787B (en) * 2021-12-07 2024-04-16 四川大学 Mg (magnesium) 2+ Doped modified NASCION sodium ion solid electrolyte and preparation method thereof

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