CN109244549B - Method for preparing garnet electrolyte sheet with high density and high conductivity by guiding crystal growth - Google Patents
Method for preparing garnet electrolyte sheet with high density and high conductivity by guiding crystal growth Download PDFInfo
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
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- 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
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- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
- H01M6/186—Only oxysalts-containing solid electrolytes
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- H—ELECTRICITY
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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Abstract
The invention provides a method for preparing a high-density and high-conductivity electrolyte sheet by guiding crystal growth, which comprises the following steps: fully ball-milling and roasting the raw materials for synthesizing the solid electrolyte powder, fully ball-milling and drying again, and then pressing into tablets by isostatic pressing and roasting at the temperature of 1000-; grinding the roasted electrolyte sheet to obtain electrolyte particles with a certain particle size, adding the electrolyte particles into solid electrolyte powder, uniformly mixing and grinding the electrolyte particles, performing isostatic pressing again to obtain the compact high-conductivity solid electrolyte sheet, and roasting the compact high-conductivity solid electrolyte sheet. The invention induces the formation and growth of crystal grains in the solid electrolyte by introducing the solid electrolyte crystal seeds, reduces the energy required by nucleation and crystal nucleus growth of the material, and reduces the temperature required by the densification of the solid electrolyte sheet. The low-temperature densification effectively inhibits the volatilization of lithium element in the solid electrolyte, the composition of the synthesized solid electrolyte is accurately controlled, and the solid electrolyte sheet with low impedance and high conductivity is prepared.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a solid electrolyte with high density and high conductivity.
Background
Having a high conductivity (10)-4S/cm) of Li7La3Zr2O12The garnet solid electrolyte and metal Li have relatively stable interfaces, good chemical stability in air and good application prospect in the research and development of all-solid-state batteries with high energy density and good safety. Li7La3Zr2O12The existence of tetragonal phase and cubic phase, and research shows that the cubic phase with high conductivity is easily synthesized at high temperatureHowever, a certain amount of tetragonal phase appears during the cooling process. To stabilize Li7La3Zr2O12Phase of Al3+、B3+、Ga3+、Ta5+Doping with equal elements, comparing the research results, Ta5+The doping of the ions is beneficial to improving the conductivity of the solid electrolyte while stabilizing the structure of the object phase. The research finds that: the low density and the presence of a large number of grain boundaries in the solid electrolyte sheet produce a high grain boundary resistance for the electrolyte sheet. In order to improve the compactness of the solid electrolyte sheet and reduce the grain boundary, optimization of the preparation process (such as hot-pressing sintering, SPS sintering, cold isostatic pressing and high-temperature sintering) and low-melting-point components (such as LiBO) are often adopted3LiF) is introduced. The optimized preparation process adopts high temperature and high pressure, which is not beneficial to the mass production of the solid electrolyte sheet; and after the low-melting-point component is introduced, a high-impedance phase is generated on the local part of the solid electrolyte sheet, so that the bulk impedance of the solid electrolyte is influenced to a certain extent.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing a pure-phase, high-density and high-conductivity solid electrolyte sheet at low temperature. The method induces the formation and growth of crystal grains in the solid electrolyte by introducing the solid electrolyte crystal seeds, thereby reducing the energy required by material nucleation and crystal nucleus growth and reducing the required temperature for the densification of the solid electrolyte sheet; meanwhile, the volatilization of lithium in the solid electrolyte is effectively inhibited, the composition of the synthesized solid electrolyte is accurately controlled, the solid electrolyte with low impedance and high conductivity is prepared, and a good foundation is provided for the preparation of the all-solid-state battery.
The embodiment of the invention provides a method for preparing a pure-phase, high-density and high-conductivity solid electrolyte sheet at low temperature, which is characterized by comprising the following steps of:
(1) weighing the required raw materials according to the stoichiometric ratio of garnet solid electrolyte powder, adding the raw materials into a ball milling tank, adding a proper amount of grinding aid, carrying out ball milling for 6-15h, and drying for 12h at 50-95 ℃.
(2) The dried powder is roasted for 6-20h at the temperature of 800-950 ℃.
(3) Adding grinding aid into the burnt powder again, ball-milling for 5-10h, drying at 50-95 ℃, and pressing into round pieces by isostatic pressing at 50-400 Mpa.
(4) And (3) placing the solid electrolyte sheet on the high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1000-1100 ℃ at the speed of 2-10 ℃/min, and preserving heat for 6-15 hours to obtain the garnet-type solid electrolyte sheet.
(5) And (4) grinding the solid electrolyte sheet in the step (4) to obtain solid electrolyte particles with the particle size of 10-80 mu m.
(6) Screening electrolyte particles with different particle sizes, adding the solid electrolyte powder obtained in the step (2), adding a grinding aid, performing ball milling for 5-10h, drying at 50-95 ℃, and pressing into a wafer by isostatic pressing at 50-400 Mpa.
(7) And (3) placing the solid electrolyte sheet on the high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1100-fold sand-doped ceramic 1200 ℃ at the speed of 4-10 ℃/min, preserving heat for 2-5h, cooling to 1000-fold sand-doped ceramic 1100, and preserving heat for 4-9h to obtain the compact and high-conductivity garnet-type solid electrolyte sheet.
The garnet-type solid electrolyte in step 1 of the present invention is Li5+xLa5-y-z-z’ZryTazMz’O12，0<x≤2，0<y + z + z' is less than or equal to 4.5, wherein M can be independently selected from one or more of Nb, W, Ti, Hf, Ru, Mo, Nd, Ba, Ga, In, Ge, Sn, Sb and Se.
In the step 1 of the invention, when solid electrolyte powder is synthesized, lithium hydroxide, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium borate, lithium niobate and lithium dihydrogen phosphate are selected as lithium sources; lanthanum source is selected from lanthanum hydroxide, lanthanum carbonate, lanthanum sulfate, lanthanum nitrate, lanthanum oxide, lanthanum chloride and lanthanum nitrate; the tantalum source is selected from tantalum pentoxide and tantalum pentachloride.
The grinding aid in the step 1 is ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
The invention has the advantages that: (1) by introducing the solid electrolyte seed crystal, the formation and growth of crystal grains in the solid electrolyte are induced, the energy required by material nucleation and crystal nucleus growth is reduced, and the required temperature for densification of the solid electrolyte sheet is reduced. (2) The low-temperature densification effectively inhibits the volatilization of lithium element in the solid electrolyte, accurately controls the composition of the synthesized solid electrolyte and prepares the solid electrolyte with low impedance and high conductivity.
Drawings
Fig. 1 is a phase diagram of a solid electrolyte sheet synthesized at different temperatures.
FIG. 2 is a phase diagram of the Ta and Nb doped solid electrolyte powder.
Figure 3 is a cross-sectional topography of a solid electrolyte sheet after seeding.
Fig. 4 is a bottom topography of a solid electrolyte sheet after seeding, in which the scratches are sand burnish marks.
Fig. 5 impedance profiles of differently doped solid electrolyte sheets obtained by pre-seeding.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but are not limited to the following examples. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
(1) Garnet solid electrolyte powder Li6.4La3Zr1.4Ta0.6O12The raw materials are weighed according to the stoichiometric proportion of the components, added into a ball milling tank, added with a proper amount of isopropanol, ball milled for 8 hours, and dried for 12 hours at 75 ℃.
(2) The powder obtained after drying is roasted for 10h at 850 ℃.
(3) Adding isopropanol into the burnt powder again, ball-milling for 5h, drying at 75 ℃, and pressing into a wafer by isostatic pressing at 100 Mpa.
(4) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 10 hours to obtain the garnet-type solid electrolyte sheet.
(5) Grinding the solid electrolyte sheet in the step (4) to obtain a particle size D 50Is 60 mu m solid electrolyte particles.
(6) And (3) adding the electrolyte particles in the step (5) into the solid electrolyte powder obtained in the step (2), adding isopropanol, ball-milling for 6h, drying at 75 ℃, and pressing into a wafer by isostatic pressing at 200 Mpa.
(7) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1200 ℃ at a speed of 5 ℃/min, preserving heat for 2h, cooling to 1000 ℃, and preserving heat for 4h to obtain the compact and high-conductivity garnet type solid electrolyte sheet.
Example 2
(1) Garnet solid electrolyte powder Li6.4La3Zr1.4Ta0.3Nb0.3O12Weighing the required raw materials according to the stoichiometric ratio of the components, adding the raw materials into a ball milling tank, adding a proper amount of grinding aid n-butyl alcohol, carrying out ball milling for 10 hours, and drying for 10 hours at 80 ℃.
(2) The powder obtained after drying is roasted for 10h at 900 ℃.
(3) Adding n-butanol into the burnt powder again, ball-milling for 6h, drying at 80 ℃, and pressing into a wafer by isostatic pressing at 100 Mpa.
(4) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1000 ℃ at a speed of 3 ℃/min, and preserving heat for 10 hours to obtain the garnet type solid electrolyte sheet.
(5) Grinding the solid electrolyte sheet in the step (4) to obtain a particle size D50Is 60 mu m solid electrolyte particles.
(6) Screening electrolyte particles with different particle sizes, adding the solid electrolyte powder obtained in the step (2), adding n-butyl alcohol, ball-milling for 12h, drying at 80 ℃, and pressing into a wafer by isostatic pressing at 300 Mpa.
(7) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1200 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, cooling to 1000 ℃, and preserving heat for 6 hours to obtain the compact and high-conductivity garnet type solid electrolyte sheet.
Example 3
(1) Garnet solid electrolyte powder Li6.8La3Zr1.4Ta0.2Ge0.4O12Weighing the required raw materials according to the stoichiometric ratio of the components, adding the raw materials into a ball milling tank, adding a proper amount of grinding aid ethanol, carrying out ball milling for 12 hours, and drying for 8 hours at 60 ℃.
(2) The powder obtained after drying is roasted for 12h at 900 ℃.
(3) Adding the ethanol into the burnt powder again, ball-milling for 6h, drying at 60 ℃, and pressing into a wafer by isostatic pressing at 100 Mpa.
(4) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1200 ℃ at a speed of 5 ℃/min, preserving heat for 2h, rapidly cooling to 1050 ℃, and preserving heat for 10h to obtain the garnet type solid electrolyte sheet.
(5) Grinding the solid electrolyte sheet in the step (4) to obtain a particle size D50Is 40 mu m solid electrolyte particles.
(6) Adding the electrolyte particles into the solid electrolyte powder obtained in the step (2), adding ethanol, ball-milling for 12h, drying at 60 ℃, and pressing into a wafer by isostatic pressing at 300 Mpa.
(7) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1100 ℃ at the speed of 5 ℃/min, and preserving heat for 10 hours to obtain the compact and high-conductivity garnet type solid electrolyte sheet.
Example 4
(1) Push buttonGarnet solid electrolyte powder Li6.5La3Zr1.4Ta0.2Ge0.1Nb0.3O12Weighing the required raw materials according to the stoichiometric ratio of the components, adding the raw materials into a ball milling tank, adding a proper amount of isobutanol, carrying out ball milling for 12 hours, and drying at 80 ℃ for 10 hours.
(2) The powder obtained after drying is roasted for 10h at 850 ℃.
(3) Adding isobutanol into the burnt powder again, ball-milling for 8 hours, drying at 60 ℃, and pressing into a wafer by isostatic pressing at 200 Mpa.
(4) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1150 ℃ at a speed of 5 ℃/min, preserving heat for 2h, rapidly cooling to 1050 ℃, and preserving heat for 10h to obtain the solid electrolyte sheet.
(5) Grinding the solid electrolyte sheet in the step (4) to obtain a particle size D50Is 40 mu m solid electrolyte particles.
(6) Adding the electrolyte particles into the solid electrolyte powder obtained in the step (2), adding isobutanol, ball-milling for 12h, drying at 60 ℃, and pressing into a wafer by isostatic pressing at 300 MPa.
(7) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1050 ℃ at the speed of 5 ℃/min, and preserving heat for 10 hours to obtain the compact and high-conductivity garnet type solid electrolyte sheet.
Example 5
(1) Garnet solid electrolyte powder Li6.4La3Zr1.4Ta0.3W0.3O12The raw materials are weighed according to the stoichiometric proportion of the components, added into a ball milling tank, added with a proper amount of isopropanol, ball milled for 12 hours, and dried for 10 hours at 80 ℃.
(2) The powder obtained after drying is roasted for 15h at 900 ℃.
(3) Adding isopropanol into the burnt powder again, ball-milling for 8h, drying at 80 ℃, and pressing into a wafer by isostatic pressing at 300 MPa.
(4) And (3) placing the solid electrolyte sheet on the high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1200 ℃ at the speed of 5 ℃/min, preserving heat for 1h, rapidly cooling to 1050 ℃, and preserving heat for 10h to obtain the solid electrolyte sheet.
(5) Grinding the solid electrolyte sheet in the step (4) to obtain a particle size D50Is 10 mu m solid electrolyte particles.
(6) Adding the electrolyte particles into the solid electrolyte powder obtained in the step (2), adding isopropanol, ball-milling for 15h, drying at 60 ℃, and pressing into a wafer by isostatic pressing at 200 MPa.
(7) And (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the electrolyte powder, heating to 1050 ℃ at the speed of 5 ℃/min, and preserving heat for 6 hours to obtain the compact and high-conductivity garnet type solid electrolyte sheet.
Claims (4)
1. A method for preparing a garnet type electrolyte sheet with high density and high conductivity by guiding crystal growth is characterized by comprising the following steps:
(1) weighing required raw materials according to the stoichiometric ratio of garnet type solid electrolyte powder, adding the raw materials into a ball milling tank, adding a grinding aid, carrying out ball milling for 6-15h, and drying at 50-95 ℃ for 12 h;
(2) roasting the dried powder at the temperature of 800-950 ℃ for 6-20 h;
(3) adding grinding aid into the burnt powder again, ball-milling for 5-10h, drying at 50-95 ℃, and pressing into a wafer by isostatic pressing at 50-400 Mpa;
(4) Placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the solid electrolyte powder synthesized in the step (2), heating to 1000-1200 ℃ at the speed of 2-10 ℃/min, and preserving heat for 6-15h to obtain a garnet type solid electrolyte wafer;
(5) grinding the solid electrolyte seed crystal sheet in the step (4) to obtain solid electrolyte seed crystal particles with the particle size of 10-80 mu m;
(6) adding the solid electrolyte seed crystal particles into the solid electrolyte powder obtained in the step (2), adding a grinding aid, performing ball milling for 5-10h, drying at 50-95 ℃, and pressing into a wafer by isostatic pressing at 50-400 Mpa;
(7) and (3) placing the solid electrolyte sheet on a high-purity corundum ceramic plate paved with the solid electrolyte powder synthesized in the step (2), burying the solid electrolyte sheet by adopting the solid electrolyte powder synthesized in the step (2), heating to 1000-fold-type ceramic 1200 ℃ at the speed of 4-10 ℃/min, preserving heat for 2-3h, cooling to 1000-fold-type ceramic 1100 ℃, and preserving heat for 4-6h to obtain the compact and high-conductivity garnet-type solid electrolyte sheet.
2. The method according to claim 1, wherein the garnet-type solid electrolyte powder in the step 1 is composed of Li 5+xLa5-y-z-z’ZryTazMz’O12，0<x≤2，0<y+z+z’Less than or equal to 4.5, wherein M is independently selected from one or more of Nb, W, Ti, Hf, Ru, Mo, Nd, Ba, Ga, In, Ge, Sn, Sb and Se.
3. The method according to claim 1, wherein in step 1, when the required raw materials are weighed in a stoichiometric ratio of the composition of the garnet-type solid electrolyte powder, the lithium source is selected from one or more of lithium hydroxide, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium borate, lithium niobate, and lithium dihydrogen phosphate; the lanthanum source is selected from one or more of lanthanum hydroxide, lanthanum carbonate, lanthanum sulfate, lanthanum nitrate, lanthanum oxide, lanthanum chloride and lanthanum nitrate; the tantalum source is one or more selected from tantalum pentoxide and tantalum pentachloride.
4. The method as claimed in claim 1, wherein the grinding aid in step 1 is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.
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| CN110137567A (en) * | 2019-06-03 | 2019-08-16 | 哈尔滨工业大学 | The preparation method and applications of high-compactness carbuncle type all solid state electrolyte under a kind of low temperature |
| CN110311172B (en) * | 2019-06-04 | 2022-10-14 | 上海应用技术大学 | Preparation method and application of LiCuLaZrO solid electrolyte |
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| CN103113107A (en) * | 2013-02-28 | 2013-05-22 | 中国科学院上海硅酸盐研究所 | Method for preparing ceramic solid electrolyte |
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| CN104124467B (en) * | 2014-07-22 | 2016-06-01 | 武汉理工大学 | A kind of method utilizing lithium lanthanum zirconium oxygen presoma coated powder to prepare solid electrolyte |
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| CN103113107A (en) * | 2013-02-28 | 2013-05-22 | 中国科学院上海硅酸盐研究所 | Method for preparing ceramic solid electrolyte |
| CN103746111A (en) * | 2014-01-28 | 2014-04-23 | 天津先众科技有限公司 | Monocrystal Ni-Co-Mn battery positive pole material and preparing method thereof |
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