CN114349494A - Modified NASICON type structure sodium ion solid electrolyte ceramic material and preparation method and application thereof - Google Patents
Modified NASICON type structure sodium ion solid electrolyte ceramic material and preparation method and application thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 47
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 40
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 33
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002228 NASICON Substances 0.000 title claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 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 abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 102
- 238000000227 grinding Methods 0.000 claims description 66
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 37
- 238000000498 ball milling Methods 0.000 claims description 35
- 238000005245 sintering Methods 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 238000007873 sieving Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 150000002500 ions Chemical group 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention provides a modified NASICON type structure sodium ion solid electrolyte ceramic material, wherein the chemical general formula of the ceramic material is Na3+x+yZr2‑xScxSi2+yP1‑yO12X is more than 0 and less than or equal to 0.3, y is more than 0 and less than or equal to 0.2, and the electrical conductivity of the ceramic material is 0.7 multiplied by 10‑3S/cm～1.6×10‑3S/cm, the ceramic material has a C2/2 monoclinic phase structure, the diversification of sodium ion transmission channels is kept, and the sodium ion transmission capacity is higher. The invention also provides a preparation method of the ceramic material andand the application of the ceramic material in preparing all-solid-state sodium batteries.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a modified NASICON type structure sodium ion solid electrolyte ceramic material and a preparation method and application thereof.
Background
In the last century, the science and technology of human society have been developed at a high speed, along with the continuous aggravation of energy shortage and environmental pollution, the large-scale application of renewable energy sources is realized, the realization of 2030C peak reaching is accelerated, and the prospect planning of 2060C neutralization has become industry consensus. In the energy storage equipment matched with the lithium ion battery, the lithium ion battery has the characteristics of higher energy density, excellent cycle performance, rate capability and the like, so that the lithium ion battery becomes a research hotspot in the field of energy storage devices at present. With the development and maturity of the lithium ion battery, the lithium ion battery also helps the industrial revolution in the field of new energy automobiles, so that the new energy automobiles gradually get rid of the anxiety of endurance mileage, and the popularization and application of the new energy automobiles are greatly promoted.
Along with the application and development of lithium ion batteries, the demand of lithium resources is greatly increased worldwide, and the price of lithium battery raw materials is continuously increased. By 9 months 2021, the price of lithium carbonate has drifted to 170000 yuan/ton. Meanwhile, China has found that the reserve of lithium resources only accounts for about 13% of the world, and more novel energy storage devices besides lithium ion batteries are required to guarantee the national energy security bureau. Sodium ion batteries are now a new choice. Sodium carbonate used as a raw material of a sodium battery is abundant in reserves on the earth and lower in price, and sodium and lithium are the same elements of the first main group and have similar electrochemical properties.
Meanwhile, the traditional lithium ion battery adopts organic liquid electrolyte, when the battery is in severe conditions such as collision and puncture in the using process, the liquid electrolyte may leak, and meanwhile, the high temperature generated by the short circuit of the battery can induce the electrolyte to burn, so that the battery burns and even explodes, which also becomes the largest potential safety hazard of the lithium ion battery. Therefore, the research on a safe, green and effective solid electrolyte becomes a solution to solve the big problem, and the sodium ion battery is a preferable mode, but the conductivity of the electrolyte material of the sodium ion battery in the prior art is lower.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a modified NASICON type structure sodium ion solid electrolyte ceramic material, which solves the problem of low conductivity of the sodium ion battery electrolyte material in the prior art.
According to the embodiment of the invention, the chemical general formula of the modified NASICON structure sodium ion solid electrolyte ceramic material is Na3+x+yZr2-xScxSi2+yP1-yO12X is more than 0 and less than or equal to 0.3, and y is more than 0 and less than or equal to 0.2.
The ceramic material has an electrical conductivity of 0.7 × 10-3S/cm～1.6×10-3S/cm, the ceramic material has a C2/2 monoclinic phase structure, the diversification of sodium ion transmission channels is kept, and the sodium ion transmission capacity is higher.
This example is achieved by regulating Na3Zr2Si2PO12Based on the components of the NASICON type solid electrolyte ceramic material of the sodium fast ion conductor, ion substitution (Sc) is added3+；Si4+) The effective regulation and control of the size of a sodium ion transmission channel in the crystal form on the atomic scale are successfully realized by carrying out equal charge doping, the fact that the size of the sodium ion transmission channel is closely related to the ion conductivity sigma of the sodium ion solid electrolyte is found in the regulation and control process of the size of the channel, the prepared sodium ion solid electrolyte ceramic material has a monoclinic phase lattice structure, and the ion conductivity can reach 1.6 multiplied by 10-3S/cm。
In sodium ion solid electrolyte, Na having three-dimensional spatial structure3Zr2Si2PO12The solid electrolyte has the advantages of safety, easy preparation, high ionic conductivity, wide electrochemical window, excellent chemical and electrochemical stability and the like;
Na3Zr2Si2PO12in the structure of tetrahedron PO4And octahedral ZrO6Form a network structure together, generate a hole on the structure and can be filled with coordination to allow sodium ions to pass through, and Na3Zr2Si2PO12Based on the system, by regulatingThe components are used for realizing the evolution of lattice parameters, improving the content of sodium ions in a system, enhancing the transmission capability of the sodium ions and finally obtaining the novel sodium ion solid electrolyte with high ionic conductivity.
The invention also provides a preparation method of the ceramic material, which comprises the following steps:
mixing Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3Preparing the components according to the chemical general formula to form a mixture, mixing the mixture for the first time, then pre-burning, mixing for the second time, and then sintering to obtain the material.
Further, the first mixing and the second mixing are ball milling mixing, wherein, during the first mixing,
adding a grinding ball of zirconium dioxide and alcohol into the mixture, wherein the mixture comprises: grinding ball with zirconium dioxide: the mass ratio of the alcohol is 1 (5-7) to 2-4, the primary ball grinding material is obtained after ball milling for 8-10 hours,
drying the primary ball grinding material, and then sieving the dried primary ball grinding material with a 100-mesh sieve to obtain dried powder, wherein the dried powder is used for presintering to obtain a base material;
during the second ball milling, according to the base material: grinding ball with zirconium dioxide: the mass ratio of the alcohol is 1 (3-5) to (1-2), ball milling is carried out for 4-8 hours to obtain secondary ball grinding material,
and drying the secondary ball grinding material, and then sieving the dried secondary ball grinding material with a 100-mesh sieve to obtain pre-sintered powder, carrying out dry pressing on the pre-sintered powder to obtain a green body, and sintering the green body to obtain the ceramic material.
Furthermore, the pre-sintering is carried out by adopting an alumina crucible and is carried out for 6-8 hours at the temperature of 700-900 ℃.
Furthermore, a sintering furnace is adopted for sintering, the temperature is increased at the temperature increase rate of 4-6 ℃/min, and the sintering is carried out for 10-16 h at the temperature of 1100-1300 ℃.
Further, the ball milling and mixing adopts a sand milling type ball mill.
The invention also provides application of the ceramic material in preparing an all-solid-state sodium battery, and the cycle of the obtained all-solid-state sodium battery is more than 600 h.
Compared with the prior art, the invention has the following beneficial effects:
1) the contents of Na, Zr, Si, P and Sc ions are controlled by comprehensively regulating and controlling the values of x and y so as to achieve the purposes of comprehensively regulating and controlling the lattice constant and improving the ionic conductivity, thereby ensuring that the prepared ceramic material has high compactness in microscopic appearance, no pores and no microcracks, has a monoclinic phase structure, widens the channel for transmitting sodium ions in the lattice due to the existence of Sc ions, and introduces more sodium ions, so that the ionic conductivity of the sodium ion solid electrolyte material is greatly improved and can reach 1.6 multiplied by 10-3S/cm, and stable performance, and can meet the application requirement of all-solid-state sodium batteries;
2) the raw materials for preparing the sodium ion solid electrolyte material are sufficiently supplied at home and have relatively low price, so the method has important industrial application value; the sintering temperature of the solid electrolyte ceramic material is 1100-1300 ℃, the sintering temperature range is wide, and the solid electrolyte ceramic material has good process adaptability;
3) the invention adopts a secondary ball milling process to realize the particle size control of the material;
4) the all-solid-state sodium battery prepared from the ceramic material can stably circulate for more than 600h under the current density of 0.1mA/cm 2.
Drawings
Fig. 1 is a result of XRD analysis of the solid electrolyte sheet prepared in example 1 of the present invention.
Fig. 2 is a result of XRD analysis of the solid electrolyte sheet prepared in example 2 of the present invention.
Fig. 3 is a XRD analysis result of the solid electrolyte sheet prepared in example 3 of the present invention.
Fig. 4 is a SEM image of a solid electrolyte sheet prepared in example 1 of the present invention.
Fig. 5 is a SEM image of a solid electrolyte sheet prepared in example 4 of the present invention.
Fig. 6 is a SEM image of a solid electrolyte sheet prepared in example 5 of the present invention.
Fig. 7 is an EIS diagram of a solid electrolyte sheet prepared in example 2 of the present invention.
Fig. 8 is an EIS diagram of a solid electrolyte sheet prepared in example 4 of the present invention.
Fig. 9 is an EIS diagram of a solid electrolyte sheet prepared in example 5 of the present invention.
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
Table 1 mass percentage of each raw material in each example
| Examples | Chemical formula (II) | Na2CO3 | ZrO2 | SiO2 | NH4H2PO4 | Sc2O3 |
| 1 | Na3.04Zr1.98Sc0.02Si2.02P0.98O12 | 25.15 | 38.09 | 18.95 | 17.60 | 0.22 |
| 2 | Na3.12Zr1.94Sc0.06Si2.06P0.94O12 | 25.82 | 37.33 | 19.33 | 16.88 | 0.65 |
| 3 | Na3.18Zr1.92Sc0.08Si2.10P0.90O12 | 26.32 | 36.95 | 19.70 | 16.17 | 0.86 |
| 4 | Na3.20Zr1.90Sc0.10Si2.10P0.90O12 | 26.49 | 36.56 | 19.71 | 16.17 | 1.08 |
| 5 | Na3.14Zr1.88Sc0.12Si2.02P0.98O12 | 25.98 | 36.17 | 18.95 | 17.60 | 1.29 |
| 6 | Na3.22Zr1.86Sc0.14Si2.08P0.92O12 | 26.65 | 35.79 | 19.52 | 16.53 | 1.51 |
| 7 | Na3.32Zr1.82Sc0.18Si2.14P0.86O12 | 27.49 | 35.03 | 20.09 | 15.45 | 1.94 |
| 8 | Na3.40Zr1.80Sc0.20Si2.20P0.80O12 | 28.15 | 34.66 | 20.65 | 14.38 | 2.15 |
Example 1:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3Respectively mixing the raw materials according to the mass ratio of 25.15%, 38.09%, 18.95%, 17.60% and 0.22% to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding the alcohol for 8 hours at a mass ratio of 1:5:2 to obtain a uniformly mixed primary ball grinding material;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 6 hours at 800 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding for 4 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the alcohol is 1:3: 1;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green buried device obtained in the step (7) in a sintering furnace, heating at the heating rate of 4 ℃/min, and sintering at 1100 ℃ for 16h to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
Example 2:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3Respectively mixing the raw materials according to the mass ratio of 25.82%, 37.33%, 19.33%, 16.88% and 0.65% to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding the alcohol for 9 hours at a mass ratio of 1:5:3 to obtain a uniformly mixed primary ball grinding material;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 6 hours at the temperature of 750 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding for 6 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the alcohol is 1:3: 1;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green body burying device obtained in the step (7) in a sintering furnace, heating at the heating rate of 4 ℃/min, and sintering at 1120 ℃ for 15h to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
Example 3:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3The materials are respectively prepared according to the mass ratio of 26.32%, 36.95%, 19.70%, 16.17% and 0.86% to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding for 10 hours to obtain a uniformly mixed primary ball grinding material, wherein the mass ratio of the alcohol is 1:6: 2;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 7 hours at the temperature of 750 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding the alcohol for 8 hours at a mass ratio of 1:3:2 to obtain a uniformly mixed secondary ball grinding material;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green body burying device obtained in the step (7) in a sintering furnace, heating at the heating rate of 4 ℃/min, and sintering at 1160 ℃ for 15h to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
Example 4:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3The components are respectively proportioned according to the mass ratio of 26.49%, 36.56%, 19.71%, 16.17% and 1.08% to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding the alcohol for 9 hours at a mass ratio of 1:7:3 to obtain a uniformly mixed primary ball grinding material;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 8 hours at 850 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding for 7 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the alcohol is 1:4: 2;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green burying device obtained in the step (7) in a sintering furnace, heating at the heating rate of 5 ℃/min, and sintering at 1210 ℃ for 12h to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
Example 5:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3Respectively mixing the raw materials according to the mass ratio of 25.98%, 36.17%, 18.95%, 17.60% and 1.29% to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding for 10 hours to obtain a uniformly mixed primary ball grinding material, wherein the mass ratio of the alcohol is 1:7: 4;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 8 hours at the temperature of 750 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding for 5 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the alcohol is 1:4: 2;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green body burying device obtained in the step (7) into a sintering furnace, heating at the heating rate of 5 ℃/min, and sintering at 1230 ℃ for 10 hours to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
Example 6:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O326.65%, 35.79%, 19.52%, 16.53% and 1.51% of the substance, respectivelyProportioning according to the amount ratio to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding the alcohol for 8 hours at a mass ratio of 1:5:4 to obtain a uniformly mixed primary ball grinding material;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 8 hours at 900 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding for 4 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the alcohol is 1:4: 1;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green body burying device obtained in the step (7) in a sintering furnace, heating at the heating rate of 6 ℃/min, and sintering at 1200 ℃ for 11h to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
Example 7:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3Respectively mixing according to the mass ratio of 27.49%, 35.03%, 20.09%, 15.45% and 1.94% to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding the alcohol for 9 hours at a mass ratio of 1:6:3 to obtain a uniformly mixed primary ball grinding material;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 6 hours at 850 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding for 6 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the alcohol is 1:3: 2;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green body burying device obtained in the step (7) in a sintering furnace, heating at the heating rate of 4 ℃/min, and sintering at 1270 ℃ for 10 hours to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
Example 8:
step 1: the raw material comprises Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3Respectively mixing the components according to the mass ratio of 28.15%, 34.66%, 20.65%, 14.38% and 2.15% to form a mixture;
step 2: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: grinding for 10 hours to obtain a uniformly mixed primary ball grinding material, wherein the mass ratio of the alcohol is 1:5: 4;
and step 3: drying the primary ball-milled material obtained in the step 2 and sieving the dried material by a 100-mesh sieve to obtain dried powder;
and 4, step 4: placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 8 hours at 700 ℃ to obtain a base material;
and 5: and (4) carrying out secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as a ball milling medium, and mixing the base material: grinding balls: grinding for 6 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the alcohol is 1:3: 2;
step 6: drying the secondary ball-milled material obtained in the step 5 and sieving the dried material by a 100-mesh sieve to obtain pre-sintered powder;
and 7: putting the pre-sintered powder obtained in the step 6 into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) placing the green buried device obtained in the step (7) into a sintering furnace, heating at the heating rate of 5 ℃/min, and sintering at 1140 ℃ for 14h to obtain the final solid electrolyte ceramic material (namely the solid electrolyte sheet).
In examples 1 to 8, the ball mill mixing was performed by a sand mill.
TABLE 2 Processes and Properties used in the examples
All the ceramic materials obtained in the embodiments 1 to 8 can be used for preparing all-solid-state sodium-sodium batteries, and the obtained all-solid-state sodium-sodium batteries can stably circulate for more than 600 hours under the current density of 0.1mA/cm 2;
finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A modified NASICON type structure sodium ion solid electrolyte ceramic material is characterized in that the chemical general formula of the ceramic material is Na3+x+yZr2-xScxSi2+yP1-yO12X is more than 0 and less than or equal to 0.3, and y is more than 0 and less than or equal to 0.2.
2. The modified NASICON-type structural sodium ion solid electrolyte ceramic material of claim 1, wherein the ceramic material has an ionic conductivity of 0.7 x 10-3S/cm～1.6×10-3S/cm。
3. The modified NASICON-type structural sodium ion solid electrolyte ceramic material of claim 1, wherein the ceramic material has a C2/2 monoclinic phase structure.
4. A preparation method of the modified NASICON-type structural sodium ion solid electrolyte ceramic material according to any one of claims 1 to 3, which comprises the following steps:
mixing Na2CO3，ZrO2，SiO2，NH4H2PO4And Sc2O3Preparing the components according to the chemical general formula to form a mixture, mixing the mixture for the first time, then pre-burning, mixing for the second time, and then sintering to obtain the material.
5. The method of claim 4, wherein the first mixing and the second mixing are ball milling, and wherein during the first mixing,
adding a grinding ball of zirconium dioxide and alcohol into the mixture, wherein the mixture comprises: grinding ball with zirconium dioxide: the mass ratio of the alcohol is 1 (5-7) to 2-4, the primary ball grinding material is obtained after ball milling for 8-10 hours,
drying the primary ball grinding material, and then sieving the dried primary ball grinding material with a 100-mesh sieve to obtain dried powder, wherein the dried powder is used for presintering to obtain a base material;
during the second ball milling, according to the base material: grinding ball with zirconium dioxide: the mass ratio of the alcohol is 1 (3-5) to (1-2), ball milling is carried out for 4-8 hours to obtain secondary ball grinding material,
and drying the secondary ball grinding material, and then sieving the dried secondary ball grinding material with a 100-mesh sieve to obtain pre-sintered powder, carrying out dry pressing on the pre-sintered powder to obtain a green body, and sintering the green body to obtain the ceramic material.
6. The preparation method according to claim 4 or 5, wherein the pre-sintering is performed by using an alumina crucible and is performed at 700 to 900 ℃ for 6 to 8 hours.
7. The preparation method according to claim 4 or 5, wherein the sintering is carried out in a sintering furnace, and the temperature is raised at a temperature raising rate of 4-6 ℃/min and sintered at 1100-1300 ℃ for 10-16 h.
8. The method of claim 5, wherein the ball milling and mixing is performed using a sand mill.
9. The application of the modified NASICON-type structural sodium ion solid electrolyte ceramic material is characterized by being used for preparing all-solid-state sodium-electrolyte batteries.
10. The use of claim 9, wherein the cycle of an all-solid-state to sodium battery is greater than 600 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| US20210107835A1 (en) * | 2019-10-10 | 2021-04-15 | International Business Machines Corporation | Facile synthesis of solid sodium ion-conductive electrolytes |
-
2021
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| US20210107835A1 (en) * | 2019-10-10 | 2021-04-15 | International Business Machines Corporation | Facile synthesis of solid sodium ion-conductive electrolytes |
Non-Patent Citations (3)
| Title |
|---|
| 吴其胜等: "《材料物理性能》", 31 December 2018, 华东理工大学出版社 * |
| 强亮生等, 哈尔滨工业大学出版社 * |
| 曹万强等: "《材料物理专业实验教程》", 29 February 2016, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117174996A (en) * | 2023-11-02 | 2023-12-05 | 合肥国轩高科动力能源有限公司 | Modified titanium aluminum lithium phosphate, preparation method thereof and lithium ion solid-state battery |
| CN117174996B (en) * | 2023-11-02 | 2024-03-05 | 合肥国轩高科动力能源有限公司 | Modified titanium aluminum lithium phosphate, preparation method thereof and lithium ion solid-state battery |
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