CN113964390A - Halogen ion doped LLZO solid electrolyte and preparation method thereof - Google Patents
Halogen ion doped LLZO solid electrolyte and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 30
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- 235000015895 biscuits Nutrition 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 halogen ion Chemical class 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 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 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 3
- 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 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 239000002001 electrolyte material Substances 0.000 description 5
- 239000002223 garnet Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052788 barium Inorganic materials 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
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical group 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 238000012360 testing method Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- H01M10/058—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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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 halogen ion doped LLZO solid electrolyte and a preparation method thereof, according to the chemical formula Li7La3Zr2O12‑xXxPerforming ball milling on a lithium source, a lanthanum source, a zirconium source and halide powder to obtain raw powder; wherein x is more than 0.0 and less than or equal to 2.5 mol; pre-sintering the raw powder at 800-950 ℃ for 7-10 h, and then pressing into a circular biscuit sheet; sintering the biscuit sheet to obtain the halogen ion doped LLZO solid electrolyte. According to the invention, by adopting anions to regulate and control the lithium content, the nucleation of crystals can be obviously promoted, the crystal grains can be refined, the crystal boundary can be reduced, and the density can be improved, so that the ionic conductivity of LLZO can be improved, and Li with good stability to lithium metal can be obtained7La3Zr2O12‑xXxThe solid electrolyte 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 halogen ion doped LLZO solid electrolyte and a preparation method thereof.
Background
The power performance and cruising range of the electric automobile depend on a power supply, and the high specific energy of the lithium battery makes the electric automobile a powerful competitor. Safety is an essential element of electric vehicles, and since the frequent occurrence of spontaneous combustion events in electric vehicles, higher requirements have been placed on the safety of electric vehicles. The electrolyte is one of important components of the lithium battery, and the research and development of the solid electrolyte to replace flammable and explosive organic liquid electrolyte has the possibility of solving the safety problems, so that the electrolyte has extremely high research and commercial values.
At present, although the electrolytes of lithium ion batteries are various, such as organic liquid electrolytes, room temperature ionic liquid electrolytes, gel electrolytes, crystalline and amorphous inorganic solid electrolytes, and the like, and are used in next generation of novel lithium ion batteries, the electrolytes still have the defect of being difficult to avoid. Among the numerous electrolytes, Li having a cubic phase garnet structure7La3Zr2O12The (LLZO) solid electrolyte has the following advantages: (1) the ionic conductivity can reach 10 at room temperature-4S cm-1(2) the thermal stability is good, and the device can work in a wide temperature range; (3) the electrochemical window is wide and can reach 6V (vs. Li)+The electrochemical stability window of/Li) ensures that the electrolyte does not generate obvious side reaction at two electrodes, and the unicity of electrode reaction in the electrochemical process is met; (4) the material can replace a diaphragm, and has good mechanical property and processability; (5) the safety is good and the fuel is not burnt.
Known as LLZO (Li)7La3Zr2O12) Two phases are present at room temperature, each with an ionic conductivity of only 10-6S cm-1Has a tetragonal phase and a conductivity which is two orders of magnitude to 10 higher-4S cm-1The cubic phase of (c). In cubic phase LLZO, [ La ] is present3Zr2O12]7-Constituting the structural skeleton, lithium ions occupy 24d tetrahedral voids and 96h octahedral voids, Li+Where the transmission takes place. However, during the preparation of cubic phase LLZO, tetragonal phase is easily generated, thereby reducing the conductivity of the material, which is only 10-5S cm-1Therefore, the cubic phase of the LLZO is stabilized under the room temperature condition by a doping method, thereby achieving the purpose of improving the conductivity of the LLZO.
In the prior method, the sintering is carried out for 36 hours at the sintering temperature of 1230 ℃, the energy consumption is high, and the ionic conductivity is only 5 multiplied by 10-5S cm-1。
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a halogen ion doped LLZO solid electrolyte and a preparation method thereof, wherein the garnet-structured lithium ion solid electrolyte Li7La3Zr2O12-xXxThe lithium metal negative electrode is stable, the introduction of anions can obviously reduce the sintering temperature and the sintering time, the density of the material is improved, the preparation method is simple, and the lithium metal negative electrode can be produced in a large scale.
The invention solves the technical problem by the following technical scheme:
the preparation method of the halogen ion doped LLZO solid electrolyte comprises the following steps:
(1) according to the formula Li7La3Zr2O12-xXxPerforming ball milling on a lithium source, a lanthanum source, a zirconium source and halide powder to obtain raw powder; wherein x is more than 0.0 and less than or equal to 2.5 mol;
(2) pre-sintering the raw powder at 800-950 ℃ for 7-10 h to obtain a primary sintered powder;
(3) pressing the primary sintering powder into a circular biscuit sheet under the pressure of 300-500 MPa;
(4) sintering the biscuit piece at 1120-1250 ℃ for 2-16 h to obtain the halogen ion doped LLZO solid electrolyte.
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 halide is metal halide MX, M is alkali metal or alkaline earth metal or high valence metal, and X ═ F, Cl, Br or I.
Further, the alkali metal is Li, Na or K.
Further, the alkaline earth metal is Mg, Ca, Sr or Ba.
Further, the high valence metal is Al, Sn, Fe, Ti or La.
Furthermore, x is more than 0.5 and less than or equal to 2.5 mol; the lithium source is added in an excessive amount, and the excessive mass is 5-15% of the mass of the lithium source calculated according to the chemical formula.
A halogen ion-doped LLZO solid electrolyte prepared according to the above method, the crystal structure of the halogen ion-doped LLZO solid electrolyte is cubic, and the lithium ion conductivity at 25 ℃ is 4.11 x 10-4S cm-1～7.62×10-4S cm-1。
Compared with the prior art, the invention has the following beneficial technical effects:
the invention takes halogen as doping element, reduces the concentration of lithium ion, promotes the nucleation speed of crystal, refines primary crystal grains and reduces the crystal boundary in the crystal, thereby improving the density of the material, greatly improving the ionic conductivity of electrolyte and providing a new idea for anion modification of LLZO. 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 and can be used for large-scale production. Compared with the unmodified LLZO material, the introduction of the anions can obviously reduce the sintering temperature and the sintering time, has good stability to the lithium metal cathode, and greatly reduces the energy consumption on the premise of obtaining high lithium ion conductivity and high compactness.
The halogen ion doped LLZO solid electrolyte prepared by the invention has the advantages that the phases of samples obtained within 0.5-2.5 mol of anion doped substances are cubic phases, and the lithium ion conductivity is 4.11 multiplied by 10 at 25 DEG C-4S cm-1～7.62×10-4S cm-1。
Drawings
FIG. 1 is an XRD diffraction pattern of LLZO of an electrolyte prepared by comparative example 1 of the present invention after being subjected to final firing at 1200 ℃ for 24 hours;
FIG. 2 is an XRD diffraction pattern of anion modified electrolytes prepared in examples 1-3 under different sintering conditions;
FIG. 3 is a graph showing LLZO and Li prepared in comparative example 1 and examples 4-8 of the present invention7La3Zr2O12-xBrxElectrochemistry of electrolyte material at 25 DEG CAn impedance spectrum;
FIG. 4 is a graph showing LLZO and Li prepared in comparative example 1 and examples 4-8 of the present invention7La3Zr2O12-xBrxE of the electrolyte materialaComparing the images;
FIG. 5 shows Li prepared in example 6 of the present invention7La3Zr2O11.85Br0.15SEM images of the electrolyte material;
FIG. 6 shows Li | Li in example 6 of the present invention7La3Zr2O11.85Br0.15|LiFePO4The cycling performance of the battery;
FIG. 7 shows Li | Au/Li in example 6 of the present invention7La3Zr2O11.85 Br0.15/Au | Li symmetric cell performance.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto.
Halogen ion (X) of the invention-) Doped garnet-type LLZO (Li)7La3Zr2O12) A solid electrolyte having a structural expression of Li7La3Zr2O12-xXxX is more than 0.0 and less than or equal to 2.5mol, and halogen ions (X) are added-) Substituted O2-And by changing X-The content of (a) can remarkably improve the density and ionic conductivity of the garnet solid electrolyte and improve the cycling stability of the garnet solid electrolyte to lithium metal. The preparation method of the solid electrolyte material comprises the following steps:
(1) according to the formula Li7La3Zr2O12-xXxPerforming ball milling on lithium source, lanthanum source, zirconium source and halide powder for 20 hours at the rotating speed of 300-600 r/min to prepare mixed slurry, and drying the mixed slurry for 10-24 hours at the temperature of 50-100 ℃ to obtain raw powder, wherein the lithium source needs to be excessive in order to prevent the volatilization of lithium element;
wherein the lithium source is one of lithium carbonate, lithium hydroxide (with or without crystal water), 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 halide is metal halide (alkali metal such as MX, M ═ Li, Na, K and the like, alkaline earth metal such as M ═ Mg, Ca, Sr, Ba and the like, or high valence state type such as M ═ Al, Sn, Fe, Ti, La and the like, X ═ F, Cl, Br, I), and the addition amount is X, wherein X is more than 0.0 and less than or equal to 2.5 mol. Preferably, x is more than 0.5 and less than or equal to 2.5 mol;
the lithium source is added in an excessive amount, and the excessive amount is 5-15% of the mass of the lithium source calculated according to the chemical formula.
(2) Pre-burning the dried raw powder at 800-950 ℃ for 7-10 h, naturally cooling, and grinding to obtain primary-burned powder;
(3) continuously ball-milling and drying the primary sintering powder, and pressing the primary sintering powder into a biscuit blank sheet with the diameter of 15mm in a uniaxial pressure mode under the pressure of 300-500 MPa;
(4) sintering the thin sheet in the step (3) for 2-24 hours at 1000-1200 ℃, and then grinding and polishing the electrolyte sheet on 200-3000-mesh sand paper to obtain Li7La3Zr2O12-xXxA solid electrolyte.
The crystal structures of the garnet solid electrolyte obtained by the preparation method are all cubic structures, and the ionic conductivity is more than 10 at room temperature-4S cm-1Electron conductivity of less than 10-7S cm-1And the electrolyte prepared by this method can significantly enhance the interfacial stability to lithium metal.
Comparative example 1 is unmodified Li7La3Zr2O12Preparation of (LLZO) solid electrolyte:
comparative example 1
According to Li7La3Zr2O12Weighing 0.15mol of La2O3，LiOH·H2O,ZrO2In 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 with mortar to uniform, calcining at 900 deg.C for 10 hr to obtain mother powder of pre-sintered product, weighing the mother powder, and placing in 15mm moldAnd placing the die on a workbench of a tabletting machine, applying pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit sheet which is completely molded. And (3) placing the biscuit in an alumina crucible, embedding the biscuit by using mother powder, sintering the biscuit in a muffle furnace at 1200 ℃ for 24h, and naturally cooling to room temperature to obtain a sintered LLZO ceramic electrolyte blank.
Comparative example 1 the unmodified LLZO solid electrolyte prepared in comparative example 1 was subjected to phase analysis using Bruker D8 ADVANCE powder X-ray diffractometer, and XRD is shown in fig. 1. It can be seen that the electrolyte has no impure phase and is a uniform cubic phase after being sintered at 1200 ℃ for 24 hours. Comparative example 1 gave an ionic conductivity of only 1.80X 10 at room temperature- 4S cm-1。
The following examples are anionically modified Li7La3Zr2O12-xXxPreparing an electrolyte:
example 1
According to Li7La3Zr2O11.95I0.05Weighing 0.15mol of La2O3，LiOH·H2O，ZrO2And 0.05mol of LiI, LiOH. H in the raw material in order to compensate for volatilization of Li element at high temperature in the crystal structure2The 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 calcined at 900 ℃ for 9 hours to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a 15mm mould, placing the mould on a workbench of a tabletting machine, applying pressure of 450MPa, 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 1180 ℃ for 4h, and naturally cooling to room temperature to obtain Li7La3Zr2O11.95I0.05A ceramic electrolyte green body.
Example 2
According to Li7La3Zr2O11.90F0.10Transformation ofWeighing 0.15mol of La according to the stoichiometric ratio2O3,LiOH·H2O,ZrO2And 0.10mol LiF, LiOH. H in the raw material in order to compensate for the volatilization of Li element at high temperature in the crystal structure2The 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 calcined for 10 hours at 850 ℃ to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a 15mm mould, placing the mould on a workbench of a tabletting machine, applying pressure of 450MPa, 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 1150 ℃ for 6h, and naturally cooling to room temperature to obtain sintered Li7La3Zr2O11.90F0.10A ceramic electrolyte green body.
Example 3
According to Li7La3Zr2O11.85Cl0.15Weighing 0.15mol of La2O3,LiOH·H2O,ZrO2And 0.15mol LiCl, LiOH. H in the raw material in order to compensate for the volatilization of Li element at high temperature in the crystal structure2The 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 calcined for 8.5 hours at 950 ℃ to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a 15mm mould, placing the mould on a workbench of a tabletting machine, applying pressure of 450MPa, 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 1160 deg.C for 2.5h, and naturally cooling to room temperature to obtain sintered Li7La3Zr2O11.85Cl0.15A ceramic electrolyte green body.
Example 4
According to Li7La3Zr2O12-xBrxStoichiometric ratio of (x ═ 0.05) 0.15mol of La was weighed2O3,LiOH·H2O,ZrO2And LiBr to compensate for volatilization of Li element at high temperature in crystal structure, LiOH. H in raw material2The 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 calcined at 900 ℃ for 9 hours to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a 15mm mould, placing the mould on a workbench of a tabletting machine, applying pressure of 450MPa, 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 1160 deg.C for 4h, and naturally cooling to room temperature to obtain Li7La3Zr2O121.95Br0.05A ceramic electrolyte green body.
Example 5
The same as example 4, except that x is 0.10.
Example 6
The same as example 4, except that x is 0.15.
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:Li7La3Zr2O11.85Br0.15Preparing composite anode slurry by using PVDF and SuperP in a mass ratio of 70:10:10:10, and then preparing the anode piece. The solid-state cell Li was then assembled in an argon filled glove box7La3Zr2O11.85Br0.15|LiFePO4And testing the charge and discharge performance. To verify Li7La3Zr2O11.85Br0.15Stability of electrolyte material to lithium metal, assembling Li | Au/Li7La3Zr2O11.85Br0.15Au | Li symmetric cells were tested for stability to lithium metal.
Example 7
The same as example 4, except that x is 0.20.
Example 8
The same as example 4, except that x is 0.25
Example 9
According to Li7La3Zr2O11.75F0.25Weighing 0.15mol of La according to stoichiometric ratio2O3,LiOH·H2O,ZrO2And 0.125mol MgF2In 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. 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. Grinding the obtained powder uniformly by using a mortar, calcining at 850 ℃ for 10h to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder in a 15mm mould, placing the mould on a workbench of a tabletting machine, applying pressure of 450MPa, 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 1180 ℃ for 4h, and naturally cooling to room temperature to obtain sintered Li7La3Zr2O11.75F0.25A ceramic electrolyte green body.
Example 10
According to Li7La3Zr2O11.90Br0.10Weighing 0.15mol of La according to stoichiometric ratio2O3,LiOH·H2O,ZrO2And 0.05mol of BaBr2In 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. 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. Grinding the obtained powder uniformly by using a mortar, calcining for 8h at 950 ℃ to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder in a 15mm mould, placing the mould on a workbench of a tabletting machine, applying pressure of 450MPa, 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, and sintering at 1050 deg.C in a muffle furnaceNaturally cooling to room temperature after 10h to obtain sintered Li7La3Zr2O11.90Br0.10A ceramic electrolyte green body.
Example 11
According to Li7La3Zr2O11.80Cl0.20Weighing 0.15mol of La according to stoichiometric ratio2O3,LiOH·H2O,ZrO2And 0.10mol of MgCl2In 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. 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. Grinding the obtained powder uniformly by using a mortar, calcining at 880 ℃ for 9.5h to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder in a 15mm mould, placing the mould on a workbench of a tabletting machine, applying pressure of 450MPa, 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 1050 ℃ for 6h, and naturally cooling to room temperature to obtain sintered Li7La3Zr2O11.80Cl0.20A ceramic electrolyte green body.
In comparison with comparative example 1, it can be seen from examples 1 to 11 above that the sintering temperature for preparing the electrolyte is lowered and the time required for sintering is greatly shortened by anion-doping the modified electrolyte. The XRD patterns of examples 1-3, as shown in fig. 2, allow the preparation of cubic phase garnet electrolytes by anion doping.
Li prepared in examples 4 to 8 by electrochemical workstation7La3Zr2O12-xBrxThe electrolyte material was subjected to an ion conductivity analysis test at 25 ℃ and its ac impedance spectrum is shown in fig. 2, and it can be seen that all the samples prepared showed a clear semicircular shape in the high frequency region and a tail in the low frequency region, and the material was an ionic conductor. It was found by calculation that the ionic conductivities of the electrolytes prepared in examples 4 to 8 were respectively 4.11X 10-4,5.68×10-4,7.62×10-4,6.68×10-4And 3.56X 10-4S cm-1。
In addition, Li7La3Zr2O12-xBrxActivation energy of electrolyte (E)a) Is calculated from 25-65 ℃ according to the Arrhenius law, and E of different electrolytesaFor an example as shown in FIG. 3, it can be seen that Li in example 67La3Zr2O11.85Br0.15E of (A)aMinimum, 0.286eV, so Li7La3Zr2O11.85Br0.15Has higher ion migration capability.
FIG. 5 shows Li | Li in example 67La3Zr2O11.85Br0.15|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 0.3C-1The first coulombic efficiency reaches 89.41%. After circulating for 50 circles, the specific capacity still remains 137mAh g-1。
FIG. 6 is a diagram of Li/Au/Li in example 67La3Zr2O11.85Br0.15Au/Li symmetrical cell, indicating Li produced7La3Zr2O11.85Br0.15The solid electrolyte has excellent stability to lithium metal.
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. The preparation method of the halogen ion doped LLZO solid electrolyte is characterized by comprising the following steps:
(1) according to the formula Li7La3Zr2O12-xXxAdding lithiumPerforming ball milling on the source, the lanthanum source, the zirconium source and halide powder to obtain raw powder; wherein x is more than 0.0 and less than or equal to 2.5 mol;
(2) pre-sintering the raw powder at 800-950 ℃ for 7-10 h to obtain a primary sintered powder;
(3) pressing the primary sintering powder into a circular biscuit sheet under the pressure of 300-500 MPa;
(4) sintering the biscuit piece at 1120-1250 ℃ for 2-16 h to obtain the halogen ion doped LLZO solid electrolyte.
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 halide is MX, M is an alkali metal or alkaline earth metal or a higher valence metal, and X ═ F, Cl, Br, or I.
6. The method of claim 5, wherein the alkali metal is Li, Na or K.
7. The method of claim 5, wherein the alkaline earth metal is Mg, Ca, Sr, or Ba.
8. The method of claim 5, wherein the metal in the high valence state is Al, Sn, Fe, Ti or La.
9. The method of claim 1, wherein 0.5 < x.ltoreq.2.5 mol; the lithium source is added in an excessive amount, and the excessive mass is 5-15% of the mass of the lithium source calculated according to the chemical formula.
10. A halogen ion doped LLZO solid electrolyte prepared according to any of the methods of claims 1-9, wherein the halogen ion doped LLZO solid electrolyte has a cubic crystal structure and a lithium ion conductivity of 4.11 x 10 at 25 ℃-4S cm-1～7.62×10-4S cm-1。
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