CN113675463A - NASICON type inorganic solid electrolyte material and preparation method and application thereof - Google Patents
NASICON type inorganic solid electrolyte material and preparation method and application thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000002228 NASICON Substances 0.000 title claims abstract description 40
- 229910003480 inorganic solid Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 17
- 239000002001 electrolyte material Substances 0.000 claims abstract description 13
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 43
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 claims 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a NASICON type inorganic solid electrolyte material, a preparation method and application thereof, wherein the general formula of the NASICON type inorganic solid electrolyte material is Na1+4a+2b+c‑e+fZr2‑a‑b‑c‑d‑eVaWb ⅡXc ⅢYd ⅣZe ⅤSifP3‑ fO12Wherein V is a vacancy for introducing Zr site; wⅡ、XⅢ、YⅣ、ZⅤRespectively are two, three, four and five valent metal elements for doping substitution of Zr site; a, b, c, d, e and f are respectively the mol percentage of the corresponding elements, wherein 0<a<2，2.2<f is less than or equal to 3, b, c, d and e are all between 0 and 0.5 and are not 0 at the same time. The electrolyte material can be synthesized by a solution-assisted solid phase method and a solid phase reaction method, the preparation process is simple and easy, the cost is low, and the NASICON type solid electrolyte material provided by the invention has higher ionic conductivity at room temperature.
Description
Technical Field
The invention relates to the technical field of solid electrolyte materials, in particular to a NASICON type inorganic solid electrolyte material and a preparation method and application thereof.
Background
Even when the technology is so rapidly developed, the traditional fossil energy sources such as oil, coal and natural gas play an indispensable and important role in the past, but the energy sources are essentially non-renewable primary energy sources, and the energy crisis is also aggravated by the large amount of exploitation and use of the energy sources. Due to the fact that the emerging green clean energy sources such as wind energy and solar energy are intermittent and are limited by factors such as geographical environment, energy loss is easily caused in the production process of the green clean energy sources, and therefore an energy storage device matched with the green clean energy sources is needed to carry out effective storage and utilization.
Electrochemical energy storage is energy storage by interconversion between chemical and electrical energy. Electrochemical energy storage technology as an efficient and low-cost energy storage technology occupies a considerable proportion of the global energy system. Common electrochemical energy storage devices include lead-acid batteries, nickel-metal hydride batteries, lithium ion batteries and the like, wherein the lithium ion batteries are widely applied to a plurality of digital products such as mobile phones, computers, cameras and the like due to the advantages of high energy density, long cycle life, rapid charge and discharge, convenience in use, high technical maturity and the like. Lithium ion batteries have been successful not only in the 3C field but also in the electric vehicle field in recent years. However, the other end of the lithium ion battery with unlimited wind and light faces the embarrassment of lithium resource scarcity, according to the report of 2018 of the U.S. geological survey bureau, the globally proven lithium resource reserve is about 5300 ten thousand tons, the lithium resource is mainly distributed in regions of south america and the like, the lithium resource in China seriously depends on import, along with the introduction of technology upgrading, the demand of various industries of the society on the lithium ion battery is also increased year by year, and the supply of the global lithium resource is expected to have a tension trend in the near future. Compared with the shortage of lithium resources, the reserve of sodium resources in the crust reaches 2.68%, and besides the advantages of high reserve and low cost, the lithium ion battery and the sodium ion battery have similar working principles because the lithium and the sodium belong to the same main group and the physical and chemical properties of the lithium and the sodium are similar. The sodium ion battery realizes energy storage through reversible insertion and extraction of sodium ions between positive and negative electrode materials along with conduction of external circuit electrons. During charging, sodium ions are extracted from the positive electrode and are embedded into the negative electrode through the electrolyte; the opposite is true when discharging. These advantages make sodium ion batteries very attractiveAn energy storage device with potential. However, the liquid organic electrolyte currently used in the conventional sodium ion battery is very easy to generate risks such as combustion and explosion, and has low safety coefficient, so that it has great strategic significance to develop a solid electrolyte material with high safety and excellent conductivity. The NASICON type inorganic solid electrolyte material has the advantages of stable chemical property, wide electrochemical window, low electronic conductivity and the like, is considered to be one of the most promising solid electrolyte materials for commercialization in all-solid sodium ion batteries, but the main reason for the low room-temperature ionic conductivity (10) is not applied in large scale-4Scm-1) Therefore, improvement of the ion conductivity of the NASICON-type inorganic solid electrolyte material at room temperature will help accelerate the commercialization process of the all-solid sodium ion battery.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an NASICON-type inorganic solid electrolyte material with high ionic conductivity, and therefore the present invention provides an NASICON-type inorganic solid electrolyte material, and a preparation method and an application thereof.
An NASICON type inorganic solid electrolyte material, the general structural formula of the solid electrolyte material is Na1+4a+2b+c-e+fZr2-a-b-c-d-eVaWb ⅡXc ⅢYd ⅣZe ⅤSifP3-fO12Wherein V is a vacancy introduced at the Zr site; w isⅡIs a divalent metal element for doping and replacing Zr site; said XⅢTrivalent metal elements for doping substitution of Zr sites; said YⅣIs tetravalent metal element for doping and replacing Zr site; z isⅤIs a pentavalent metal element for doping and replacing Zr site. A, b, c, d, e and f are respectively the mol percentage of the corresponding elements, wherein 0<a<2，0≤b≤0.5，0≤c≤0.5，0≤d≤0.5，0≤e≤0.5，2.2<f is less than or equal to 3, and b, c, d and e are not 0 at the same time. W isⅡOne or more selected from Zn, Mg, Ca, Cu, Mn, Ni, Ba, Co, Cd, Sr and Pb; the above-mentionedX of (2)ⅢOne or more selected from Al, Sc, Fe, Y, La, Bi, In, Ga, Lu, Mo, Er, Pr, Dy and Yb; said YⅣOne or more selected from Ti, Hf, Ce, Sn and Ge; z isⅤOne or more selected from Nb, V, Ta and Sb.
The invention also provides the NASICON type inorganic solid electrolyte material and a preparation method thereof, wherein the preparation method comprises a solution-assisted solid phase reaction method and a solid phase reaction method.
Preferably, the solution-assisted solid phase reaction method is carried out according to the following steps:
firstly, mixing a sodium source, a zirconium source and other metal salts, stirring to obtain a clear solution, and then adding hydrolyzed Si (OCH)2CH3)4Finally, adding a phosphorus source, and stirring to obtain a gel solution. Drying the gel solution at 60-130 ℃ to obtain dry gel, and then carrying out heat treatment at 600-1000 ℃ in an air atmosphere to obtain precursor powder particles; and respectively carrying out ball milling, drying and tabletting on the obtained precursor powder particles, and finally calcining at 900-1500 ℃ in an air atmosphere to obtain the NASICON type inorganic solid electrolyte material.
Preferably, the solid phase reaction method is carried out according to the following steps:
firstly, mixing a sodium source, a zirconium source, a silicon source, a phosphorus source and other metal oxides, and then carrying out heat treatment at 600-1000 ℃ in an air atmosphere to obtain precursor powder particles; and respectively carrying out ball milling, drying and tabletting on the obtained precursor powder particles, and finally calcining at 900-1500 ℃ in an air atmosphere to obtain the NASICON type inorganic solid electrolyte material.
The NASICON type inorganic solid electrolyte material is applied to preparing a sodium battery containing a solid electrolyte.
The invention has the beneficial effects that:
the NASICON type inorganic solid electrolyte material and the preparation method thereof adopt a solution-assisted solid phase reaction method and a solid phase reaction method, have simple synthesis process and low manufacturing cost, and cause Zr vacancy by doping Zr in the NASICON type solid electrolyte material, and the element-doped NASICON type solid electrolyte material can cause charge imbalance in crystals.
The invention can obtain a NASICON type inorganic solid electrolyte material and a preparation method and application thereof.
Drawings
FIG. 1 is an AC impedance spectrum of a NASICON type solid electrolyte material prepared in example 1 of the present invention;
FIG. 2 is an AC impedance spectrum of a NASICON type solid electrolyte material prepared in example 2 of the present invention;
FIG. 3 is an AC impedance spectrum of a NASICON type solid electrolyte material prepared in example 3 of the present invention;
FIG. 4 is an AC impedance spectrum of a NASICON type solid electrolyte material prepared in example 4 of the present invention;
Detailed Description
The first embodiment is as follows: in this embodiment, the general structural formula of the NASICON-type inorganic solid electrolyte material is Na1+4a+2b+c-e+fZr2-a-b-c-d-eVaWb ⅡXc ⅢYd ⅣZe ⅤSifP3-fO12Wherein V is a vacancy for introducing Zr site; w isⅡIs a divalent metal element for doping and replacing Zr site; said XⅢTrivalent metal elements for doping substitution of Zr sites; said YⅣIs tetravalent metal element for doping and replacing Zr site; z isⅤIs a pentavalent metal element for doping and replacing Zr site.
The second embodiment is as follows: the true bookThe difference between the embodiment and the specific embodiment is as follows: the solid electrolyte material Na1+4a+2b+c-e+fZr2-a-b-c-d-eVaWb ⅡXc ⅢYd ⅣZe ⅤSifP3-fO12Wherein a, b, c, d, e and f are respectively the mole percentage of the corresponding elements, wherein 0<a<2，0≤b≤0.5，0≤c≤0.5，0≤d≤0.5，0≤e≤0.5，2.2<f is less than or equal to 3, and b, c, d and e are not 0 at the same time.
Other steps are the same as those in the first embodiment.
The third concrete implementation mode: the second embodiment differs from the first embodiment in that: the solid electrolyte material Na1+4a+2b+c-e+fZr2-a-b-c-d-eVaWb ⅡXc ⅢYd ⅣZe ⅤSifP3-fO12In (1), the WⅡOne or more selected from Zn, Mg, Ca, Cu, Mn, Ni, Ba, Co, Cd, Sr and Pb; said XⅢOne or more selected from Al, Sc, Fe, Y, La, Bi, In, Ga, Lu, Mo, Er, Pr, Dy and Yb; said YⅣOne or more selected from Ti, Hf, Ce, Sn and Ge; z isⅤOne or more selected from Nb, V, Ta and Sb.
The other steps are the same as those in the second embodiment.
The fourth concrete implementation mode: the present embodiment relates to a NASICON-type inorganic solid electrolyte material and a method for producing the same, and the method for producing the same includes a solution-assisted solid-phase reaction method and a solid-phase reaction method.
The fifth concrete implementation mode: preferably, the solution-assisted solid phase reaction method is carried out according to the following steps:
firstly, mixing a sodium source, a zirconium source and other metal salts, stirring to obtain a clear solution, and then adding hydrolyzed Si (OCH)2CH3)4Finally, adding a phosphorus source, and stirring to obtain a gel solution. Drying the gel-like solution at 60-130 ℃ to obtain dry gel, and then drying the dry gel in airCarrying out heat treatment at 600-1000 ℃ in a gas atmosphere to obtain precursor powder particles; and respectively carrying out ball milling, drying and tabletting on the obtained precursor powder particles, and finally calcining at 900-1500 ℃ in an air atmosphere to obtain the NASICON type inorganic solid electrolyte material.
The sixth specific implementation mode: preferably, the solid phase reaction method is carried out according to the following steps:
firstly, mixing a sodium source, a zirconium source, a silicon source, a phosphorus source and other metal oxides, and then carrying out heat treatment at 600-1000 ℃ in an air atmosphere to obtain precursor powder particles; and respectively carrying out ball milling, drying and tabletting on the obtained precursor powder particles, and finally calcining at 900-1500 ℃ in an air atmosphere to obtain the NASICON type inorganic solid electrolyte material.
The beneficial results of the embodiment are as follows:
the NASICON type inorganic solid electrolyte material and the preparation method thereof adopt a solution-assisted solid phase reaction method and a solid phase reaction method, have simple synthesis process and low manufacturing cost, and cause Zr vacancy by doping Zr in the NASICON type solid electrolyte material, and the element-doped NASICON type solid electrolyte material can cause charge imbalance in crystals.
The seventh embodiment: the present embodiment differs from the first to sixth embodiments in that: the sodium source in the fifth step is selected from NaNO3、Na2CO3、Na2C2O4One or more of the above; the zirconium source is selected from Zr (NO)3)2And Zr (NO)3)4·5H2One or two of O; the phosphorus source is selected from NH4H2PO4、(NH4)3PO4、Na3PO4One or more of the above; the sodium source, the zirconium source, the vacancy, other metal salt and Si (OCH)2CH3)4And the molar ratio of the phosphorus source is 3.1-3.5: 1.5-1.98: 0.01-0.5: 0.01-0.5: 2.3-2.9: 0.1 to 0.7.
The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from the first to seventh embodiments in that: the sodium source in the sixth step is selected from NaNO3、Na2CO3、NaHCO3、Na2C2O4One or more of the above; the source of zirconium is ZrO2(ii) a The silicon source is SiO2(ii) a The phosphorus source is selected from P2O5、H3PO4、NH4H2PO4、(NH4)3PO4、(NH4)2HPO4、Na3PO4One or more of the above; the sodium source, the zirconium source, the vacancy, other metal oxides and Si (OCH)2CH3)4And the molar ratio of the phosphorus source is 3.1-3.5: 1.5-1.98: 0.01-0.5: 0.01-0.5: 2.3-2.9: 0.1 to 0.7.
The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the embodiment provides a NASICON type inorganic solid electrolyte material, a preparation method and application thereof, and the solid electrolyte material can be used for preparing all-solid-state sodium batteries.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of an NASICON type inorganic solid electrolyte material comprises the following steps:
first, Na is added2C2O4、Zr(NO3)2And C10H5NbO20Mixing, stirring to obtain clear solution, adding hydrolyzed Si (OCH)2CH3)4Finally adding Na3PO4Stirring to obtain gel solutionAnd (4) liquid. Drying the gel solution at 90 ℃ to obtain dried gel, and then carrying out heat treatment at 800 ℃ in air atmosphere to obtain precursor powder particles; ball-milling, drying and tabletting the obtained precursor powder particles respectively, and finally calcining at 1300 ℃ in air atmosphere to obtain Na3.25Zr1.95Nb0.05Si2.3P0.7O12Solid state electrolyte material, said Na2C2O4、Zr(NO3)2、C10H5NbO20、Si(OCH2CH3)4With Na3PO4Is 3.25: 1.95: 0.05: 2.3: 0.7. the ionic conductivity of the nano-particles at room temperature is 3.61mS cm-1。
Example 2: a preparation method of an NASICON type inorganic solid electrolyte material comprises the following steps:
first, Na is added2C2O4、Zr(NO3)2And C10H5NbO20Mixing, stirring to obtain clear solution, adding hydrolyzed Si (OCH)2CH3)4Finally adding Na3PO4And stirred to obtain a gel solution. Drying the gel solution at 90 ℃ to obtain dried gel, and then carrying out heat treatment at 800 ℃ in air atmosphere to obtain precursor powder particles; ball-milling, drying and tabletting the obtained precursor powder particles respectively, and finally calcining at 1300 ℃ in air atmosphere to obtain Na3.29Zr1.94V0.01Nb0.05Si2. 3P0.7O12Solid state electrolyte material, said Na2C2O4、Zr(NO3)2Vacancy, C10H5NbO20、Si(OCH2CH3)4With Na3PO4Is 3.29: 1.94: 0.01: 0.05: 2.3: 0.7. the ionic conductivity of the nano-particles at room temperature is 4.04mS cm-1。
Example 3: a preparation method of an NASICON type inorganic solid electrolyte material comprises the following steps:
first, Na is added2C2O4、ZrO2、SiO2、P2O5And Nb2O5Mixing, and then carrying out heat treatment at 700 ℃ in air atmosphere to obtain precursor powder particles; ball-milling, drying and tabletting the obtained precursor powder particles respectively, and finally calcining at 1300 ℃ in air atmosphere to obtain Na3.33Zr1.93V0.02Nb0.05Si2.3P0.7O12Solid state electrolyte material, said Na2C2O4、ZrO2Vacancy, Nb2O5、SiO2And P2O5Is 3.33: 1.93: 0.02: 0.05: 2.3: 0.7. the ionic conductivity of the nano-particles at room temperature is 4.57mS cm-1。
Example 4: a preparation method of an NASICON type inorganic solid electrolyte material comprises the following steps:
first, Na is added2C2O4、Zr(NO3)2And C10H5NbO20Mixing, stirring to obtain clear solution, adding hydrolyzed Si (OCH)2CH3)4Finally adding Na3PO4And stirred to obtain a gel solution. Drying the gel solution at 90 ℃ to obtain dried gel, and then carrying out heat treatment at 800 ℃ in air atmosphere to obtain precursor powder particles; ball-milling, drying and tabletting the obtained precursor powder particles respectively, and finally calcining at 1300 ℃ in air atmosphere to obtain Na3.33Zr1.93V0.02Nb0.05Si2. 3P0.7O12Solid state electrolyte material, said Na2C2O4、Zr(NO3)2Vacancy, C10H5NbO20、Si(OCH2CH3)4With Na3PO4Is 3.33: 1.93: 0.02: 0.05: 2.3: 0.7. the ionic conductivity of the solution at room temperature is 5.0mS cm-1。
The NASICON type inorganic solid electrolyte material provided by the invention has higher ionic conductivity at room temperature; in addition, the preparation method provided by the invention is simple to operate, short in synthesis step and low in manufacturing cost. The NASICON-type inorganic solid electrolyte material of the present invention can be used for assembling a sodium battery containing a solid electrolyte.
Claims (9)
1. An NASICON type inorganic solid electrolyte material, a preparation method and an application thereof, which are characterized in that the general structural formula of the solid electrolyte material is Na1+4a+2b+c-e+fZr2-a-b-c-d-eVaWb ⅡXc ⅢYd ⅣZe ⅤSifP3-fO12Wherein V is a vacancy for introducing Zr site; w isⅡIs a divalent metal element for doping and replacing Zr site; said XⅢTrivalent metal elements for doping substitution of Zr sites; said YⅣIs tetravalent metal element for doping and replacing Zr site; z isⅤIs a pentavalent metal element for doping and replacing Zr site.
2. The NASICON type inorganic solid state electrolyte material of claim 1, wherein the solid state electrolyte material is Na1+4a+2b+c-e+fZr2-a-b-c-d-eVaWb ⅡXc ⅢYd ⅣZe ⅤSifP3-fO12Wherein a, b, c, d, e and f are respectively the mole percentage of the corresponding elements, wherein 0<a<2，0≤b≤0.5，0≤c≤0.5，0≤d≤0.5，0≤e≤0.5，2.2<f is less than or equal to 3, and b, c, d and e are not 0 at the same time.
3. The NASICON type inorganic solid state electrolyte material of claim 1, wherein W is selected from the group consisting ofⅡOne or more selected from Zn, Mg, Ca, Cu, Mn, Ni, Ba, Co, Cd, Sr and Pb; said XⅢSelected from Al, Sc, Fe,One or more of Y, La, Bi, In, Ga, Lu, Mo, Er, Pr, Dy and Yb; said YⅣOne or more selected from Ti, Hf, Ce, Sn and Ge; z isⅤOne or more selected from Nb, V, Ta and Sb.
4. The method for preparing the NASICON type inorganic solid state electrolyte material according to claim 1, wherein the method is a solution-assisted solid phase reaction method or a solid phase reaction method.
5. The method according to claim 4, wherein the solution-assisted solid phase reaction method comprises the steps of:
firstly, mixing a sodium source, a zirconium source and other metal salts, stirring to obtain a clear solution, and then adding hydrolyzed Si (OCH)2CH3)4Finally, adding a phosphorus source, and stirring to obtain a gel solution; drying the gel solution at 60-130 ℃ to obtain dry gel, and then carrying out heat treatment at 600-1000 ℃ in an air atmosphere to obtain precursor powder particles; and respectively carrying out ball milling, drying and tabletting on the obtained precursor powder particles, and finally calcining at 900-1500 ℃ in an air atmosphere to obtain the NASICON type inorganic solid electrolyte material.
6. The NASICON type inorganic solid state electrolyte material of claim 1, wherein the sodium source of claim 5 is selected from NaNO3、Na2CO3、Na2C2O4One or more of the above; the zirconium source is selected from Zr (NO)3)2And Zr (NO)3)4·5H2One or two of O; the phosphorus source is selected from NH4H2PO4、(NH4)3PO4、Na3PO4One or more of the above; the sodium source, the zirconium source, the vacancy, other metal salt and Si (OCH)2CH3)4And the molar ratio of the phosphorus source is 3.1-3.5: 1.5-1.98: 0.01-0.5: 0.01-0.5: 2.3-2.9: 0.1 to 0.7.
7. The method according to claim 4, wherein the solid phase reaction method comprises the steps of:
firstly, mixing a sodium source, a zirconium source, a silicon source, a phosphorus source and other metal oxides, and then carrying out heat treatment at 600-1000 ℃ in an air atmosphere to obtain precursor powder particles; and respectively carrying out ball milling, drying and tabletting on the obtained precursor powder particles, and finally calcining at 900-1500 ℃ in an air atmosphere to obtain the NASICON type inorganic solid electrolyte material.
8. The NASICON type inorganic solid state electrolyte material of claim 1, wherein the sodium source of claim 7 is selected from NaNO3、Na2CO3、NaHCO3、Na2C2O4One or more of the above; the source of zirconium is ZrO2(ii) a The silicon source is SiO2(ii) a The phosphorus source is selected from P2O5、H3PO4、NH4H2PO4、(NH4)3PO4、(NH4)2HPO4、Na3PO4One or more of the above; the sodium source, the zirconium source, the vacancy, other metal oxides and Si (OCH)2CH3)4And the molar ratio of the phosphorus source is 3.1-3.5: 1.5-1.98: 0.01-0.5: 0.01-0.5: 2.3-2.9: 0.1 to 0.7.
9. Use of the NASICON type inorganic solid state electrolyte material according to claims 1-3, wherein the solid state electrolyte material is used for preparing sodium batteries containing solid state electrolytes.
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