CN114243004A - Garnet type solid electrolyte capable of effectively inhibiting lithium dendrites and preparation method thereof - Google Patents
Garnet type solid electrolyte capable of effectively inhibiting lithium dendrites and preparation method thereof Download PDFInfo
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- CN114243004A CN114243004A CN202111520167.7A CN202111520167A CN114243004A CN 114243004 A CN114243004 A CN 114243004A CN 202111520167 A CN202111520167 A CN 202111520167A CN 114243004 A CN114243004 A CN 114243004A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 13
- 239000002223 garnet Substances 0.000 title description 8
- 239000000843 powder Substances 0.000 claims abstract description 73
- 235000015895 biscuits Nutrition 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 47
- 239000013078 crystal Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- OSYUGTCJVMTNTO-UHFFFAOYSA-D oxalate;tantalum(5+) Chemical compound [Ta+5].[Ta+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OSYUGTCJVMTNTO-UHFFFAOYSA-D 0.000 claims description 6
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 claims description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 3
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- ZIRLXLUNCURZTP-UHFFFAOYSA-I tantalum(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Ta+5] ZIRLXLUNCURZTP-UHFFFAOYSA-I 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 239000004570 mortar (masonry) Substances 0.000 description 15
- 229910012463 LiTaO3 Inorganic materials 0.000 description 14
- 238000005303 weighing Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 229910003327 LiNbO3 Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910010142 Li2MnSiO4 Inorganic materials 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- 241000219991 Lythraceae Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000014360 Punica granatum Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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Images
Classifications
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- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a garnet-type solid electrolyte for effectively inhibiting lithium dendrites and a preparation method thereof, wherein the garnet-type solid electrolyte comprises the following steps: according to the formula Li7La3Zr1.5Ta0.5O12-xM, ball milling a lithium source, a lanthanum source, a zirconium source and a tantalum source to obtain raw powder; x is more than or equal to 2.5 percent and less than or equal to 25 percent; pre-burning the raw powder to obtain a primary-burned powder body; adding a low-electron conductivity substance M into the primary sintered powder, and grinding uniformly to obtain mother powder; pressing the mother powder into a biscuit sheet; and sintering the biscuit to obtain the garnet-type solid electrolyte capable of effectively inhibiting the lithium dendrites. The invention adopts the traditional simple solid-phase sintering preparation process and is completed by a two-step sintering method, and the invention has the advantages of simple process, easy operation, high repeatability, low production cost and the like, and is suitable for practical application and large-scale production.
Description
Technical Field
The invention belongs to the technical field of oxide solid electrolyte preparation, and particularly relates to a garnet type solid electrolyte capable of effectively inhibiting lithium dendrites and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) have the advantages of higher energy density, environmental friendliness, and the like, and have been widely used in higher-power mobile electronic devices, electric vehicles, and power grid-scale energy storage devices. However, most of the current commercial LIBs adopt organic liquid electrolytes, and due to the defects of flammability, fluidity, toxicity, volatility and the like, the safety of the lithium ion batteries is concerned. Therefore, the replacement of conventional liquid electrolytes with nonflammable and stable Solid Electrolytes (SEs) is considered the best strategy to overcome the safety challenges of lithium ion batteries. In addition, the energy density of the battery can be greatly improved by using metallic lithium as a negative electrode. Therefore, a solid-state battery using a solid electrolyte is considered as the method that best solves the safety problem of a large energy density energy storage device, and has attracted a great deal of attention in recent years.
Inorganic electrolyte cubic phase garnet type solid electrolyte Li7La3Zr2O12(LLZO) is one of the most promising electrolytes. Its advantage is high ionic conductivity up to 10 at room temp-4S cm-1And the lithium metal contact shows excellent chemical/electrochemical stability and higher shear modulus (55 GPa). Initially, the higher shear modulus of garnet-type solid electrolytes was thought to be effective in inhibiting the growth of lithium dendrites. However, in subsequent researches, it is found that the garnet solid electrolyte cannot effectively inhibit the growth of lithium dendrites in the application process, and the lithium dendrites penetrate and spread to the whole solid electrolyte, so that the short circuit phenomenon is finally caused. Currently, researchers believe that there are two main causes of lithium dendrite growth in garnet-type solid electrolytes: firstly, the electronic conductivity of garnet-type solid electrolyte is high, and Li+The combination with electrons is the main reason of the formation of lithium dendrites, the electron conduction in the electrolyte induces the formation of dendrites, and the lithium dendrites can be directly deposited in the electrolyte to cause a short circuit phenomenon; secondly, pre-existing defects, such as cracks, in the electrolyte surface and bulk are considered to be an important cause of lithium dendrite growth, because dendrites will grow and accumulate more easily in the defects or cracks, and the resulting stress can propagate the cracks, further exacerbating the propagation of lithium dendrites.
Disclosure of Invention
The garnet-type solid electrolyte effectively improves the internal defects of the garnet-type solid electrolyte, reduces the electronic conductivity of the material, has a remarkable effect of inhibiting lithium dendrites, and has good stability on lithium metal. The method has the advantages of simple preparation, low cost and large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of garnet-type solid electrolyte for effectively inhibiting lithium dendrites comprises the following steps:
(1) according to the formula Li7La3Zr1.5Ta0.5O12-xM, ball milling a lithium source, a lanthanum source, a zirconium source and a tantalum source to obtain raw powder; x is more than or equal to 2.5 percent and less than or equal to 25 percent;
(2) pre-burning the raw powder to obtain a primary-burned powder body;
(3) adding a low-electron conductivity substance M into the primary sintered powder, and grinding uniformly to obtain mother powder; pressing the mother powder into a biscuit sheet;
(4) and sintering the biscuit to obtain the garnet-type solid electrolyte capable of effectively inhibiting the lithium dendrites.
Further, the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
Further, the lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
Further, the zirconium source is one of zirconium oxide, zirconium hydroxide and zirconium nitrate.
Further, the tantalum source is one of tantalum pentoxide, tantalum oxalate and tantalum hydroxide.
Further, the low electron conductivity substance M is one of lithium tantalate, lithium niobate, lithium manganese phosphate and lithium manganese silicate.
Further, adding the lithium source in an excessive amount, wherein the added mass is 10-15% of the mass of the lithium source calculated according to the chemical formula; the pre-sintering temperature is 750-900 ℃, and the time is 8-10 h.
Further, the pressure for pressing the mother powder into the biscuit blank sheet is 350-450 MPa; the sintering temperature is 950-1250 ℃, and the sintering time is 30 mins-2 h.
Furthermore, x is more than or equal to 2.5 percent and less than or equal to 15 percent.
An effective inhibitor prepared by the above methodA garnet-type solid electrolyte for making lithium dendrites, characterized in that the crystal structure of the electrolyte is a cubic structure and the electronic conductivity at 25 ℃ is 10-8S cm-1。
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the low-electron-conductivity substance M is added into the garnet-type solid electrolyte, so that the internal defects of the garnet-type solid electrolyte body material are improved, meanwhile, the electron concentration at the grain boundary of the material is reduced, and the electronic conductivity is greatly reduced, so that the combination of lithium ions and electrons in the garnet-type solid electrolyte is reduced, the deposition of lithium metal in the material is reduced, the formation of lithium dendrites is greatly inhibited, the working stability of the garnet-type solid electrolyte under high current density is improved, the service life is prolonged, and a new idea is provided for inhibiting the growth of the lithium dendrites in the garnet-type solid electrolyte. The invention adopts the traditional simple solid-phase sintering preparation process and is completed by a two-step sintering method, and the method is simple and easy to operate, has lower cost and can be used for large-scale production. Compared with the non-modified garnet-type solid electrolyte material, the modified garnet-type LLZTO-xM solid electrolyte can obviously improve the stability of the garnet-type LLZTO-xM solid electrolyte to a lithium metal negative electrode, and improves the performance of a solid battery. The invention adopts the traditional simple solid-phase sintering preparation process and is completed by a two-step sintering method, and the invention has the advantages of simple process, easy operation, high repeatability, low production cost and the like, and is suitable for practical application and large-scale production.
Furthermore, the raw powder is pre-sintered for 8-10 hours at 750-900 ℃, so that the raw powder can be converted into a cubic phase from a tetragonal phase through a chemical reaction.
Further, the biscuit piece is sintered for 30 mins-2 hours at 950-1250 ℃ so that crystal grains grow and a compact ceramic piece body can be formed. Too low a temperature can lead to a very brittle material without porcelain formation, and too high a temperature can lead to severe lithium volatilization and over-sintering of the material.
The garnet-type solid electrolyte LLZTO-xM prepared by the invention can effectively improve the internal defects of the garnet-type solid electrolyte body material, meanwhile, the electronic conductivity of the LLZTO-xM electrolyte is greatly reduced by about 20-30 times, the combination of lithium ions and internal electrons thereof is reduced, the formation of lithium dendrites is inhibited, the working stability of the garnet-type solid electrolyte under high current density is improved, and the service life is prolonged.
Drawings
FIG. 1 is an SEM image of a garnet-type solid electrolyte prepared in comparative example 1 of the present invention to which no third component was added;
FIG. 2 is a diagram of LLZTO-10% LiTaO prepared in example 2 of the present invention3SEM image of solid electrolyte;
FIG. 3 is a constant potential test curve at 25 ℃ of an unmodified garnet-type solid electrolyte prepared in comparative example 1 of the present invention;
FIG. 4 is a diagram of LLZTO-5% LiNbO prepared in example 1 of the present invention3A constant potential test curve of the solid electrolyte at 25 ℃;
FIG. 5 is a diagram of LLZTO-10% LiTaO prepared in example 2 of the present invention3A constant potential test curve of the solid electrolyte at 25 ℃;
FIG. 6 shows LLZTO-10% LiTaO prepared in example 2 of the present invention3Solid electrolyte assembled medium Li | Au/LLZTO-10% LiTaO3Cycling performance of/Au | Li symmetric cells;
FIG. 7 shows LLZTO-10% LiTaO prepared in example 2 of the present invention3Solid electrolyte assembled Li | LLZTO-10% LiTaO3|LiFePO4Cycling performance of quasi-solid state batteries.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments, and the embodiments of the present invention are not limited thereto. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The invention relates to a preparation method of garnet type solid electrolyte for inhibiting lithium dendrite, and the structural expression is Li7La3Zr1.5Ta0.5O12-xM (LLZTO-xM), 2.5% ≦ x ≦ 25%, preferably, 2.5% ≦ x ≦ 15%, and by adding a third component composition having low electron conductivity, and by changing the content of x, it is possible to significantly reduce the electron conductivity of the garnet solid electrolyte, improve its lithium dendrite suppression capability and thus improve the cycle stability of the lithium metal battery.
A method for preparing a garnet-type solid electrolyte having low electronic conductivity at room temperature, which effectively suppresses lithium dendrites, comprising the steps of:
(1) according to the formula Li7La3Zr1.5Ta0.5O12-xM (LLZTO-xM) by ball milling powders of a lithium source, a lanthanum source, a zirconium source and a tantalum source to obtain raw powders; the lithium source needs to be added excessively; the excessive mass is 10-15% of the mass of the lithium source calculated according to the chemical formula; preferably, x is more than or equal to 2.5% and less than or equal to 15%.
(2) Pre-sintering the raw powder at 750-900 ℃ for 8-10 h to obtain a primary sintered powder body; after the step of low-temperature presintering at 750-900 ℃, the raw powder undergoes a chemical reaction to convert from a tetragonal phase to a cubic phase.
(3) Weighing a certain mass of primary sintering powder, adding a low-electron conductivity substance M with low electron conductivity and mass fraction of x, and grinding uniformly to obtain mother powder; pressing the mother powder into a circular biscuit sheet under the pressure of 350-450 MPa;
(4) sintering the biscuit blank sheet at 950-1250 ℃ for 30 mins-2 h to obtain modified Li7La3Zr1.5Ta0.5O12-an xM garnet-type solid electrolyte. Wherein, only when the sintering crystal grain grows at 950-1250 ℃, the compact ceramic sheet body can be formed. Too low a temperature can lead to a very brittle material without porcelain formation, and too high a temperature can lead to severe lithium volatilization and over-sintering of the material. Therefore, sintering is selected at 950-1250 ℃.
Wherein the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
The lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
The zirconium source is one of zirconium oxide, zirconium hydroxide and zirconium nitrate.
The tantalum source is one of tantalum pentoxide, tantalum oxalate and tantalum hydroxide.
The third component compound having low electronic conductivity is one of lithium tantalate, lithium niobate, lithium manganese phosphate and lithium manganese silicate.
The lithium source needs to be excessive, and the mass of the excessive lithium source is 10-15% of the mass of the lithium source calculated according to the chemical formula.
Modified Li prepared according to the above process7La3Zr1.5Ta0.5O12The crystal structure of the-xM garnet-type solid electrolyte is a cubic structure, the electronic conductivity is low, and the electronic conductivity at 25 ℃ is 10 to below zero-8S cm-1The electron conductivity can be reduced by 20 to 30 times.
Comparative example 1 is unmodified Li7La3Zr1.5Ta0.5O12Preparation of solid electrolyte:
comparative example 1
According to Li7La3Zr1.5Ta0.5O12Weighing 0.15mol of La2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2O is in excess of 10% of the total mass. The raw materials are mixed and ball-milled in isopropanol ball-milling media at the rotating speed of 400r/min for 20 hours and then dried in an oven at the temperature of 80 ℃ for 24 hours. Grinding the obtained powder uniformly by using a mortar, calcining at 900 ℃ for 9h to obtain a presintering product, weighing a certain mass of mother powder, placing the mother powder into a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying the pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 1200 ℃ for 2h, naturally cooling to room temperature, and sintering to obtain unmodified Li7La3Zr1.5Ta0.5O12A solid electrolyte.
The following examples are pomegranate effective in suppressing lithium dendritesSolid-state-of-stone electrolyte Li7La3Zr1.5Ta0.5O12Preparation of-xM (LLZTO-xM).
Example 1
According to Li7La3Zr1.5Ta0.5O12-xLiNbO3Stoichiometric ratio of (x ═ 5%) 0.15mol of La was weighed out2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, the raw material (La)2O3、LiOH·H2O、ZrO2And Ta2O5) LiOH. H in (1)2The O excess is 10% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling media at the rotating speed of 450r/min for 20 hours, and then dried in an oven at the temperature of 80 ℃ for 24 hours to obtain powder. The obtained powder is ground to be uniform by a mortar, and the master batch can be obtained after the powder is calcined for 9 hours at 900 ℃. Weighing a certain mass of mother powder and LiNbO with the mass fraction of 5 percent of the weighed mother powder3And putting the biscuit into a mortar, uniformly grinding, putting the mould on a workbench of a tabletting machine in a mould with the diameter of 15mm, applying the pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit to form a complete biscuit sheet. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 1200 deg.C for 2 hr, and naturally cooling to room temperature to obtain LLZTO-5% LiNbO3A solid electrolyte.
Example 2
According to Li7La3Zr1.5Ta0.5O12-10％LiTaO3Weighing 0.15mol of La2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 15% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 400r/min for 20h, and then dried in an oven at the temperature of 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined for 8.5 hours at 900 ℃ to obtain a master batch. Weighing a fixed massThe mother powder and the LiTaO with the mass fraction of 10 percent of the weighed mother powder3The biscuit is placed in a mortar and ground uniformly, the mold is placed on a workbench of a tabletting machine in a mold with the diameter of 15mm, the pressure of 450MPa is applied, the pressure is maintained for 5min, and the biscuit is demoulded and taken out to be molded completely. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 1250 deg.C for 50min, and naturally cooling to room temperature to obtain LLZTO-10% LiTaO3A solid electrolyte.
Example 3
According to Li7La3Zr1.5Ta0.5O12-12％LiTaO3Weighing 0.15mol of La2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 15% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 350r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and a master batch can be obtained after the powder is calcined for 10 hours at 750 ℃. Weighing a certain mass of mother powder and LiTaO with the mass fraction of 12 percent of the weighed mother powder3The biscuit is placed in a mortar and ground uniformly, the mold is placed on a workbench of a tabletting machine in a mold with the diameter of 15mm, the pressure of 450MPa is applied, the pressure is maintained for 5min, and the biscuit is demoulded and taken out to be molded completely. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 1100 deg.C for 1.5h, and naturally cooling to room temperature to obtain LLZTO-12% LiTaO3A solid electrolyte.
Example 4
According to Li7La3Zr1.5Ta0.5O12-xLiMnPO4Stoichiometric ratio of (x ═ 5%) 0.15mol of La was weighed out2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 10% by mass calculated on the stoichiometric ratio. Will be provided withThe raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 350r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and a master batch can be obtained after calcination is carried out for 9h at 825 ℃. Weighing a certain mass of mother powder and LiMnPO with the mass fraction of 5 percent of the weighed mother powder4And putting the biscuit into a mortar, uniformly grinding, putting the mould on a workbench of a tabletting machine in a mould with the diameter of 15mm, applying the pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit to form a complete biscuit sheet. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 950 deg.C for 1.75h, and naturally cooling to room temperature to obtain LLZTO-5% LiMnPO4A solid electrolyte.
Example 5
According to Li7La3Zr1.5Ta0.5O12-xLi2MnSiO4Stoichiometric ratio of (x ═ 7.5%) 0.15mol of La was weighed out2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess was 12.5% by mass calculated as the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 400r/min for 20h, and then dried in an oven at the temperature of 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and a master batch can be obtained after calcination is carried out for 9h at 825 ℃. Weighing a certain mass of mother powder and 7.5 mass percent of Li in the weighed mother powder2MnSiO4And putting the biscuit into a mortar, uniformly grinding, putting the mould on a workbench of a tabletting machine in a mould with the diameter of 15mm, applying the pressure of 350MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit to form a complete biscuit sheet. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 925 deg.C for 1.5 hr, and naturally cooling to room temperature to obtain LLZTO-7.5% Li2MnSiO4A solid electrolyte.
Example 6
The same as in example 1, except that x is 10%.
Example 7
The same as example 1, except that the final firing temperature and time of the biscuit sheet were 1180 ℃ and sintering time was 1.6 hours.
Example 8
The same as example 4, except that x is 7.5%.
Example 9
The same as example 4, except that the final firing temperature and time of the biscuit piece were 975 ℃ for 1.5 hours.
Example 10
The same as example 5, except that x is 15%.
Example 11
According to Li7La3Zr1.5Ta0.5O12-xLiNbO3Stoichiometric ratio of (x ═ 25%) 0.15mol of La was weighed out2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, the raw material (La)2O3、LiOH·H2O、ZrO2And Ta2O5) LiOH. H in (1)2The O excess is 10% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 450r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and the master batch can be obtained after the powder is calcined for 9 hours at 800 ℃. Weighing a certain mass of mother powder and LiNbO with the mass fraction of 25 percent of the weighed mother powder3The biscuit is placed in a mortar and ground uniformly, the mold is placed on a workbench of a tabletting machine in a mold with the diameter of 15mm, the pressure of 370MPa is applied, the pressure is maintained for 5min, and the biscuit is demoulded and taken out to be molded completely. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 1000 deg.C for 1 hr, and naturally cooling to room temperature to obtain LLZTO-25% LiNbO3A solid electrolyte.
Example 12
According to Li7La3Zr1.5Ta0.5O12-xLiNbO3Stoichiometric ratio of (x ═ 20%) 0.15mol of La was weighed out2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, the raw material (La)2O3、LiOH·H2O、ZrO2And Ta2O5) LiOH. H in (1)2The O excess is 10% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 450r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and the master batch can be obtained after the powder is calcined for 9 hours at 860 ℃. Weighing a certain mass of mother powder and LiNbO with the mass fraction of 20 percent of the weighed mother powder3And putting the biscuit into a mortar, uniformly grinding, putting the mould on a workbench of a tabletting machine in a mould with the diameter of 15mm, applying the pressure of 420MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit to form a complete biscuit sheet. Placing the biscuit in an alumina crucible, embedding with mother powder, sintering in a muffle furnace at 1250 deg.C for 0.5h, and naturally cooling to room temperature to obtain LLZTO-2% LiNbO3A solid electrolyte.
Example 13
The difference from example 12 is that the lithium source is lithium carbonate.
Example 14
The difference from example 12 is that the lithium source is lithium acetate.
Example 15
The difference from example 12 is that the lithium source is lithium nitrate.
Example 16
The difference from example 12 is that the lanthanum source is lanthanum hydroxide.
Example 17
The difference from example 12 is that the lanthanum source is lanthanum nitrate.
Example 18
The difference from example 12 is that the zirconium source is tantalum oxalate.
Example 19
The difference from example 12 is that the zirconium source is zirconium nitrate.
Example 20
The difference from example 12 is that the tantalum source is tantalum oxalate.
Example 21
The difference from example 12 is that the tantalum source is tantalum oxalate.
The preparation process of the anode for the quasi-solid battery is the same as that of the common anode material, and the anode material adopts LiFePO4According to LiFePO4:LLZTO-10％LiTaO3Preparing composite anode slurry by using PVDF and SuperP in a mass ratio of 70:10:10:10, and then preparing the anode piece. Then the solid-state battery Li | LLZTO-10% LiTaO is assembled in a glove box filled with argon3|LiFePO4And testing the charge and discharge performance. To verify LLZTO-10% LiTaO3Stability of electrolyte material to lithium metal, assembling Li | Au/LLZTO-10% LiTaO3Au | Li symmetric cells were tested for stability to lithium metal.
Microstructure analysis of the prepared solid electrolyte sample was performed using a TM 3000 Scanning Electron Microscope (SEM) as shown in fig. 1 and 2. FIG. 1 is comparative example 1, i.e. unmodified Li7La3Zr1.5Ta0.5O12The microstructure of the solid electrolyte, as can be seen from fig. 1, has many irregular and very distinct pores between the electrolyte grains, indicating that the bulk of the material has many defects. FIG. 2 is the LLZTO-10% LiTaO prepared in example 23SEM image of solid electrolyte, as is apparent from FIG. 2, LiTaO3Distributed among the crystal grains, so that the crystal grains are tightly connected and the holes are obviously reduced, which indicates that the LiTaO3The introduction of (b) reduces defects in the bulk of the material.
The electrolyte materials prepared in comparative example 1, example 1 and example 2 were subjected to a potentiostatic test of 5V at 25 ℃ by a Princeton electrochemical workstation to analyze the electronic conductivity of the materials. Potentiostatic testing of comparative example 1 As shown in FIG. 3, the current index after stabilization of the current response was 4.61X 10-2And mA. FIGS. 4 and 5 are potentiostatic test charts of examples 1 and 2, the current indexes being 1.60X 10, respectively-3mA and 2.20X 10-3And mA. It was found by calculation that the electronic conductivities of the electrolytes prepared in comparative example 1, example 1 and example 2 were respectively 9.23 × 10-7,3.21×10-8And 4.42X 10-8S cm-1. By comparisonIt can be seen that, after the third component (i.e., the low electron conductivity substance M) is added, the polarization current of the garnet-type solid electrolyte is reduced by one order of magnitude, and the electron conductivity is reduced by about 20 to 30 times. The method is shown to be effective in reducing the electron conductivity of garnet solid electrolytes.
In addition, the lithium symmetric battery was assembled to verify the lithium dendrite suppression ability of the modified solid electrolyte.
FIG. 6 is the solid electrolyte LLZTO-10% LiTaO prepared in example 23Assembled symmetrical cell Li | Au/LLZTO-10% LiTaO3Cycling Performance of/Au | Li at room temperature, 0.3mA cm-2At a current density of (A), a solid electrolyte LLZTO-10% LiTaO3The assembled lithium symmetrical battery can be stably cycled for 300h without obvious potential fluctuation and short circuit, which shows that the electrolyte has good stability to lithium metal and can effectively inhibit the growth of lithium dendrites.
FIG. 7 is the solid electrolyte LLZTO-10% LiTaO prepared in example 23Assembled quasi-solid state battery Li | LLZTO-10% LiTaO3|LiFePO4The cycle performance of the battery is that the first discharge specific capacity reaches 150mAh g when the battery is charged and discharged under the current of 0.4C-1。
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily understand that the features of the present invention should be included in the scope of the present invention by any modifications, variations, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention, and therefore the scope of the present invention is subject to the protection scope of the following claims.
Claims (10)
1. A preparation method of garnet-type solid electrolyte for effectively inhibiting lithium dendrites is characterized by comprising the following steps:
(1) according to the formula Li7La3Zr1.5Ta0.5O12-xM, ball milling a lithium source, a lanthanum source, a zirconium source and a tantalum source to obtain raw powder; x is more than or equal to 2.5 percent and less than or equal to 25 percent;
(2) pre-burning the raw powder to obtain a primary-burned powder body;
(3) adding a low-electron conductivity substance M into the primary sintered powder, and grinding uniformly to obtain mother powder; pressing the mother powder into a biscuit sheet;
(4) and sintering the biscuit to obtain the garnet-type solid electrolyte capable of effectively inhibiting the lithium dendrites.
2. The method of claim 1, wherein the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
3. The method of claim 1, wherein the lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
4. The method of claim 1, wherein the zirconium source is one of zirconia, zirconium hydroxide and zirconium nitrate.
5. The method of claim 1, wherein the tantalum source is one of tantalum pentoxide, tantalum oxalate and tantalum hydroxide.
6. The method of claim 1, wherein the low electron conductivity material M is one of lithium tantalate, lithium niobate, lithium manganese phosphate and lithium manganese silicate.
7. The method of claim 1, wherein the lithium source is added in an excess amount of 10 to 15% by mass based on the mass of the lithium source calculated by the formula; the pre-sintering temperature is 750-900 ℃, and the time is 8-10 h.
8. The method for preparing a garnet-type solid electrolyte capable of effectively suppressing lithium dendrites as claimed in claim 1, wherein the pressure for pressing the mother powder into the biscuit sheet is 350-450 MPa; the sintering temperature is 950-1250 ℃, and the sintering time is 30 mins-2 h.
9. The method of claim 1, wherein x is 2.5% to 15%.
10. A garnet-type solid electrolyte effective in suppressing lithium dendrites prepared according to any one of claims 1 to 9, wherein the crystal structure of the electrolyte is a cubic structure and the electronic conductivity at 25 ℃ is 10-8S cm-1。
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