CN114421002A - Garnet oxide/coordination boron nitrogen hydride composite solid electrolyte and preparation method and application thereof - Google Patents
Garnet oxide/coordination boron nitrogen hydride composite solid electrolyte and preparation method and application thereof Download PDFInfo
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- 239000002223 garnet Substances 0.000 title claims abstract description 106
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 16
- -1 boron nitrogen hydride compound Chemical class 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 229910052582 BN Inorganic materials 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910000668 LiMnPO4 Inorganic materials 0.000 claims description 2
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 claims description 2
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 claims description 2
- 229910003092 TiS2 Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 2
- 238000003701 mechanical milling Methods 0.000 claims 1
- 229910052961 molybdenite Inorganic materials 0.000 claims 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 description 50
- 239000002001 electrolyte material Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 229910013698 LiNH2 Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012448 Lithium borohydride Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 101710184444 Complexin Proteins 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M10/056—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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
Abstract
The invention discloses a preparation method of garnet oxide/coordination boron nitrogen hydride composite solid electrolyte, which comprises the following steps: under inert gas, mixing garnet oxide and boron nitrogen hydride according to the mass ratio of 80-99:1, and mechanically or manually grinding at normal temperature to obtain the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte, wherein the grinding time is 5min-10h, and the grinding speed is 60-300 rpm. The method can prepare the garnet oxide/coordination boron nitrogen hydride compound solid electrolyte at room temperature, and the prepared garnet oxide/coordination boron nitrogen hydride compound solid electrolyte has higher conductivity and stability. The invention also provides a garnet oxide/coordination boron nitrogen hydride composite solid electrolyte and application thereof in an all-solid-state lithium ion battery.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a garnet oxide/coordination boron nitrogen hydride composite solid electrolyte and a preparation method and application thereof.
Background
The all-solid-state lithium ion battery has the advantages of high energy density, safety, nonflammability, capability of being directly matched with a lithium metal cathode and a high-voltage anode, simpler packaging and the like, and has wide application in real life. The solid electrolyte material is used as one of important components of the all-solid-state lithium ion battery, and has great influence on the battery performance; the garnet electrolyte material has the advantages of high ionic conductivity, environmental friendliness, high safety performance and the like, and is an all-solid-state lithium ion battery electrolyte material with great development potential.
Publication number CN108832173A discloses a garnet-type lithium ion solid electrolyte co-doped with gallium and molybdenum and a preparation method thereof, wherein the garnet-type lithium ion solid electrolyte has a general formula: li6.55-2xGa0.15La3Zr2-xMoxO12Wherein x is more than or equal to 0.05 and less than or equal to 0.25; the preparation method comprises the following steps: s1, weighing Li in stoichiometric ratio according to the general formula2CO3Powder of ZrO2Powder of Ga2O3Powder, La2O3Powder and MoO3Powder; s2, mixing all the powder together and grinding to form a first material to be molded; s3, pressing and forming the first material to be molded, and then calcining to obtain a precursor compound; s4, grinding the precursor compound to form a second material to be molded; and S5, pressing and forming the second material to be molded, and then sintering to obtain the gallium and molybdenum co-doped garnet type lithium ion solid electrolyte.
The publication No. CN110474098A discloses a garnet-type solid electrolyte material, a preparation method and an application thereof, wherein the garnet-type solid electrolyte material is a core-shell structure with a shell layer coating an inner core, and the shell layer is a garnet-type solid electrolyte material Li7-2xMgxLa3-4/3yTiyZr2O12Wherein x is 0.05-0.1, and y is 0.1-0.3; the inner core is made of high nickel material; the preparation method comprises the following steps: 1) according to the formula Li7-2xMgxLa3-4/3yTiyZr2O12Weighing a lithium source, a magnesium source, a lanthanum source, a titanium source and a zirconium source according to a molar ratio, adding deionized water, uniformly stirring to obtain a solution I,wherein x is 0.05-0.1, and y is 0.1-0.3; 2) spray drying the solution I to obtain a material II; 3) roasting the material II in an air atmosphere to obtain a material III; 4) sanding the material III and the dispersing agent together in a sand mill to obtain slurry IV; 5) spray drying the slurry IV to obtain a material V; 6) and roasting the material V in an air atmosphere to obtain the garnet type solid electrolyte material.
The preparation method of the garnet-type solid electrolyte material has certain limitations. For example, the electrolyte material is prepared by prefabricating the electrolyte material into a ceramic material. However, the preparation of ceramic materials requires a long time sintering at over 1000 ℃, which not only consumes a lot of energy, but also greatly increases the brittleness of the electrolyte sheet, resulting in difficult processing, serious interface problems, and the ionic conductivity at room temperature is also much different from that of liquid electrolytes, thus being difficult to be applied in large-scale practice. In addition, the preparation process of the ceramic material is complex, the problems of uneven temperature distribution of a sintering equipment cavity and the like exist, the preparation method is not suitable for preparing large-size ceramic solid electrolyte materials, and the obtained garnet solid electrolyte materials are low in conductivity and stability.
Disclosure of Invention
The invention provides a preparation method of a garnet oxide/coordination boron nitrogen hydride compounded solid electrolyte, which can prepare the garnet oxide/coordination boron nitrogen hydride compounded solid electrolyte at room temperature, and the prepared garnet oxide/coordination boron nitrogen hydride compounded solid electrolyte has higher conductivity and stability.
A method for preparing a garnet oxide/complex boron nitrogen hydride solid electrolyte comprises the following steps:
under inert gas, garnet oxide and boron nitrogen hydride are mixed according to the mass ratio of 80-99:1-20, and then mechanically or manually ground at normal temperature to obtain the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte, wherein the grinding time is 5min-15h, and the grinding speed is 45-300 rpm.
The invention is characterized in that the grinding is carried out manually or mechanically at normal temperature and at a lower rotating speedCoating soft coordination boron nitrogen hydride on the surface of garnet oxide to cover the uneven part of the garnet oxide surface, improving the compactness and reducing Li+Barrier to migration processes, thereby increasing Li+Electrical conductivity and allows the coordinated borohydrides to react with the garnet oxide with less evolution of the oxide, avoiding loss of conductivity of the garnet oxide.
The addition amount of boron-nitrogen hydride is too small, and the amount of boron-nitrogen hydride filling the garnet oxide pores is insufficient, so that the formed garnet oxide/coordination boron-nitrogen hydride composite solid electrolyte has high porosity and more cracks, the lithium ion conduction is influenced, and the ion conductivity is low; boron nitrogen hydride is added in an excessive amount, in which case Li+Conductivity dependent on Li of boron-nitrogen hydride+Transport rate, and Li of boron-nitrogen hydride at room temperature+The conductivity is lower and is 10-5～10-6S cm-1And further, the overall ionic conductivity is lowered.
The inert gas is argon, nitrogen or helium.
Further, the grinding time is 5min-10 h.
Because the energy of the contact process of the garnet oxide and the coordination boron nitrogen hydride in the mixing process is very low, the influence of chemical reaction on the coordination boron nitrogen hydride is reduced. Under proper grinding time, the coordination boron-nitrogen hydride has stable chemical property, does not generate phenomena of phase change, hydrogen release and the like, and can reduce the reaction of the boron-nitrogen hydride and a garnet oxide matrix as much as possible, thereby obtaining a purer boron-nitrogen hydride layer and leading the ion conductivity of the final product to be higher.
The mechanical grinding is mechanical ball milling, the rotating speed of the mechanical ball milling is 60-300rpm, and the mechanical ball milling time is 5min-10 h.
The garnet oxide/coordination boron nitrogen hydride compound solid electrolyte is prepared by adopting the preparation method of the garnet oxide/coordination boron nitrogen hydride compound solid electrolyte.
The garnet oxide/coordination boron nitrogen hydride composite solid electrolyte comprises a garnet oxide matrix and a coordination boron nitrogen hydride layer coated on the surface of the garnet oxide matrix.
The garnet oxide material is in a garnet cubic phase structure.
The molecular formula of the garnet oxide matrix is LiαGα’La3-βMβZr2-γRγO12Wherein G is any one of Al, Fe, Ga or Ge; m is Sr or Rb; r is any one of Ta, Nb, Sb and Mo, wherein alpha is 3-7, alpha' is 0-0.8, beta is 0-0.8 and gamma is 0-0.8.
The coordination boron nitrogen hydride layer is Li (BH)3)(NH2)、Li(BH4)(NH3)、Li2(BH4)(NH2)、Li3(BH4)(NH2)2、Li4(BH4)(NH2)3、(LiBH4)mNH3Or (LiBH)4)nNH3BH3Wherein m is greater than or equal to 1/3 and less than or equal to 10, and n is greater than or equal to 1 and less than or equal to 10.
In the previous research, boron-nitrogen hydride is mostly used in the field of hydrogen storage materials, but no report is made that boron-nitrogen hydride can be coated on garnet oxide to achieve better ionic conductivity, so the invention overcomes the technical prejudice, as the material of the boron nitrogen hydrogen system has higher ionic conductivity at room temperature and excellent softness and formability, can be better filled into the pores among garnet oxides, so that the porosity of the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte is greatly reduced, the structure is very compact, further promotes the transmission of ions in the electrolyte, provides a foundation for high ionic conductivity, and has good stability to lithium due to the boron-nitrogen hydride coating layer, therefore, the obtained garnet oxide/complex boron nitrogen hydride solid electrolyte has ultra-long cycle stability.
In the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte, the mass fraction of the coordination boron nitrogen hydride coated on the surface is 1-20 wt%. When the mass fraction of the boron nitride is higher than 20 wt%, the effect of the ionic conductivity is not obviously changed, and when the mass fraction of the boron nitride is too low, the garnet oxide/coordinated boron-nitrogen hydride composite solid electrolyte formed by the garnet oxide/coordinated boron-nitrogen hydride composite solid electrolyte has high porosity and more cracks due to insufficient boron-nitrogen hydride filling in the gaps of the garnet oxide, so that the lithium ion conduction is influenced, and the ionic conductivity is low.
The coordination boron nitrogen hydride used in the garnet oxide/coordination boron nitrogen hydride composite electrolyte material provided by the invention has a wide range, different garnet-type oxides can be modified by adopting a method of compounding with the coordination boron nitrogen hydride, and the prepared garnet oxide/coordination boron nitrogen hydride composite solid electrolyte material has the advantages of high lithium ion conductivity, high voltage window, good cycle stability and the like, and has great competitiveness in industrial production and application.
The invention also provides an application of the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte in an all-solid-state lithium ion battery, which comprises the following steps:
pressing the garnet oxide/coordinated boron nitrogen hydride compounded solid electrolyte at the pressure of 100-500MPa to obtain a flaky garnet oxide/coordinated boron nitrogen hydride compounded solid electrolyte, and mixing the flaky garnet oxide/coordinated boron nitrogen hydride compounded solid electrolyte with LiCoO2、LiFePO4、LiMnxFe1-xPO4(0＜x＜1)、LiMnPO4、TiS2Or matching the S positive electrode with the lithium metal negative electrode to obtain the all-solid-state lithium ion battery.
As the surface of the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte is soft coordination boron nitrogen hydride, cracks appearing on the surface of the garnet oxide can be covered by the coordination boron nitrogen hydride in the process of changing the pressing process into a sheet, so that the surface is still compact, and the purpose of good conductivity is achieved.
Compared with the prior art, the invention has the beneficial effects that:
(1) said garnet oxide/coordinated boron nitrogen hydride complexIn the preparation method of the solid electrolyte, the coordination boron nitrogen hydride is prevented from reacting with the garnet by uniform mixing, so that the composite electrolyte material has a layer of amorphous flexible coating layer, the compactness of the garnet oxide/coordination boron nitrogen hydride composite electrolyte material is improved, and Li is reduced+Barrier during migration, thereby further increasing Li+The electric conductivity, because the garnet type oxide matrix crystal structure is stable, the garnet oxide/coordination boron nitrogen hydride composite electrolyte material can still keep stable under higher voltage, and has higher voltage window. The preparation method of the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte provided by the invention has the advantages of mild conditions, short time consumption, low energy consumption, simple process, high safety and low cost, and is suitable for industrial production.
(2) Compared with the traditional garnet type electrolyte material, the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte material provided by the invention does not need to be sintered at high temperature in the application process, so that the energy consumption is greatly reduced, and meanwhile, the requirement on equipment is low because the temperature uniformity in the sintering process does not need to be controlled, and the preparation of a large-size solid electrolyte material is facilitated.
(3) The garnet oxide/coordination boron nitrogen hydride composite solid electrolyte material provided by the invention has the ion conductivity of 10 at room temperature-4S cm-1The grade has important significance for the development of all-solid-state lithium ion batteries.
Drawings
FIG. 1 shows a garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material (LLZTO-Li) prepared in example 14(BH4)(NH2)3) Scanning electron microscope images of the LLZTO primary sample, wherein FIG. 1a shows LLZTO particles; FIG. 1b is LLZTO + 5% Li4(BH4)(NH2)3And (3) granules.
FIG. 2 shows a garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material (LLZTO-Li) prepared in example 14(BH4)(NH2)3) Tabletting with LLZTO original sample under 300MPaWherein, fig. 2a is the LLZTO after tabletting; FIG. 2b is a graph of LLZTO + 5% Li after tabletting4(BH4)(NH2)3。
Fig. 3 is an XRD pattern of the garnet oxide/coordinated boron nitride hydride compounded solid electrolyte and the original garnet-type oxide prepared in example 1.
Fig. 4 is an Electrochemical Impedance Spectroscopy (EIS) of the garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material prepared in example 1 and the original LLZTO.
Fig. 5 is a direct current polarization (DC) graph of the garnet oxide/complex boron nitride hydride solid electrolyte material prepared in example 1.
Fig. 6 is a constant current cycle profile of the garnet oxide/complex boron nitrogen hydride solid state electrolyte material prepared in example 1.
FIG. 7 shows a garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material (LLZTO-Li) prepared in example 22(BH4)(NH2) And XRD patterns of the original garnet-type oxide.
Fig. 8 is an Electrochemical Impedance Spectroscopy (EIS) of the garnet oxide/complex boron nitride hydride solid electrolyte material prepared in example 2.
Fig. 9 is a direct current polarization (DC) graph of the garnet oxide/complex boron nitride hydride solid electrolyte material prepared in example 2.
FIG. 10 shows a garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material (LLZTO-Li) prepared in example 33(BH4)(NH2)2) Electrochemical Impedance Spectroscopy (EIS).
Detailed Description
The present invention is further illustrated, but not limited, by the following examples, which are all commercially available materials.
Example 1
In a glove box under argon atmosphere, 120mg of LiBH is weighed4And 380mg of LiNH2(wherein, LiBH4And LiNH2The molar ratio is 1: 3) sequentially loading into a ball milling tank, wherein the ball material ratio is 120:1, and ball milling beads are made of stainless steel; ball-milling the mixture in a planetary ball mill at the rotating speed of 500rpm for 24 hours, taking out the obtained ball-milled product in an argon atmosphere glove box, wherein the ball-milled product is Li4(BH4)(NH2)3。
Mixing LLZTO-LiBH4With Li4(BH4)(NH2)3A total of 500mg, was hand milled in a mortar for 15 minutes at a mass ratio of 95:5 to obtain a blend of Li4(BH4)(NH2)3Coated garnet oxide/coordination boron nitrogen hydride composite solid electrolyte material LLZTO-Li4(BH4)(NH2)3And carrying out subsequent electrochemical performance tests.
As shown in FIG. 1a, the surface of the solid electrolyte material without the coordination boron nitrogen hydride coating has cracks and a large number of voids, which destroy the integral bulk phase structure of the original LLZTO, and the cracks and the voids restrict Li+The garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material LLZTO-Li prepared in example 1 is shown in FIG. 1b4(BH4)(NH2)3Has a coating structure, the inner core is black compact garnet type oxide, and the outer layer is amorphous Li4(BH4)(NH2)3The flexible amorphous layer ensures the integrity of the LLZTO in the pressurizing process, fills gaps, improves the compactness of the garnet composite electrolyte material and reduces Li+Barrier during migration, thereby increasing Li+Electrical conductivity.
As shown in FIG. 2, the prepared garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material LLZTO-Li4(BH4)(NH2)3And the original LLZTO sample has a larger difference in surface after being pressed into tablets at 300 MPa. As shown in FIG. 2a, the original LLZTO sample had more large voids and large cracks on the surface, as shown in FIG. 2b, passing through Li4(BH4)(NH2)3Coated LLZTO-Li4(BH4)(NH2) The sample voids are significantly reduced, andflexible Li4(BH4)(NH2)3The layer serves as a buffer and protection, reduces the occurrence of electrolyte microcracks upon pressurization, and maintains its structural integrity, while the integrity of the LLZTO particles is critical for interfacial transport of lithium ions.
As shown in a of FIG. 3, the prepared garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte material LLZTO-Li4(BH4)(NH2)3An XRD pattern of (a); as shown in b of fig. 3, is an XRD pattern of garnet-type oxide LLZTO raw material; FIG. 3 c shows the PDF cards 01-080 and 6143 of LLZTO. The composite electrolyte material LLZTO + Li can be known from the figure4(BH4)(NH2)3With primary Li6.4La3Zr1.4Ta0.6O12Compared with the method without generating new crystalline phase, the matrix structure of the electrolyte material is not changed.
As shown in FIG. 4, the impedance curve of the garnet oxide/complex boron nitrogen hydride electrolyte is a diagonal line in the low frequency region, reflecting the ion blocking phenomenon, and it can be known from the curve that LLZTO-Li is at 30 deg.C4(BH4)(NH2)3The resistance R of (1) was 312 Ω, the electrolyte sheet thickness d was 0.05cm, and the cross-sectional area S was 0.785cm2According to the formula σLi +Calculated as d/SR, Li+The conductivity can reach 2.04X 10-4S/cm; and Li6.4La3Zr1.4Ta0.6O12The impedance of the original sample is as high as 30.5M omega, the thickness d of the electrolyte sheet is 0.080cm, and Li is calculated+The conductivity is only 3.34 multiplied by 10-9S/cm, ratio LLZTO-Li4(BH4)(NH2)3Lower by 5 orders of magnitude, indicating that the garnet oxide/coordinated boron nitrogen hydride composite electrolyte material prepared in example 1 has very high Li+Electrical conductivity.
As shown in fig. 5, the direct current polarization (DC) curve of the prepared garnet oxide/complex boron nitrogen hydride solid electrolyte material; at 30 ℃, according to the electron conductivity formula sigmae＝I0d/U0S, Experimental Steady State ElectricityStream I02.7nA, thickness d of electrolyte sheet 0.05cm, and voltage U applied0Calculated as 0.1V, the electron conductivity σe＝1.72×10-9S/cm, which is less than about 5 orders of magnitude of ionic conductivity and negligible.
As shown in FIG. 6, the garnet oxide/complex boron nitrogen hydride solid electrolyte material prepared was 0.15mA/cm at 30 deg.C2The constant current cycle curve at current density shows that the lithium symmetrical battery is very stable and has long cycle stability of 620 h. The excellent cycle performance can be attributed to three factors: comprising Li4(BH4)(NH2)3The outer layer filling of (2) is favorable for stable surface contact among particles, and flexible interstitial phase Li4(BH4)(NH2)3The filling of the voids between the LLZTO and the extremely low electron conductivity can effectively inhibit the growth of Li dendrites.
Example 2
In a glove box under argon atmosphere, 243mg LiBH was weighed4And 257mg of LiNH2(wherein, LiBH4And LiNH2The molar ratio is 1: 1) sequentially loading into a ball milling tank, wherein the ball material ratio is 120:1, and ball milling beads are made of stainless steel; ball-milling the mixture in a planetary ball mill at the rotating speed of 500rpm for 24 hours, taking out the obtained ball-milled product in an argon atmosphere glove box, wherein the ball-milled product is Li2(BH4)(NH2)。
Mixing LLZTO with Li2(BH4)(NH2) Mixing the powder in a mechanical ball mill for 8 hours according to the mass ratio of 90:10, wherein the rotating speed of the mixed powder is 10rpm, and obtaining the Li-containing powder2(BH4)(NH2) Coated garnet oxide/coordination boron nitrogen hydride composite electrolyte material LLZTO-10% Li2(BH4)(NH2) And carrying out subsequent electrochemical performance tests.
FIG. 7 a is a solid electrolyte material LLZTO + 10% Li of garnet oxide/complex boron nitride hydride composite prepared in example 22(BH4)(NH2) An XRD pattern of (a); b in FIG. 7 is the XRD pattern of the garnet-type oxide LLZTO raw material; e.g. c of FIG. 7PDF card 01-080 and 6143 of LLZTO. The composite electrolyte material LLZTO + 10% Li can be seen from the figure4(BH4)(NH2)3With primary Li6.4La3Zr1.4Ta0.6O12Compared with the method without generating new crystalline phase, the matrix structure of the electrolyte material is not changed.
As shown in FIG. 8, the impedance (EIS) curve of the garnet oxide/complex boronitride-hydride solid electrolyte material prepared in example 2 is a semicircle in the high frequency region, the intersection of the right end of the semicircle and the solid axis represents the total resistance of bulk phase and particle space, and an oblique line in the low frequency region reflects the ion blocking phenomenon, and it can be seen from the curve that LLZTO-Li is used at 30 deg.C2(BH4)(NH2) Has an impedance R of 653 Ω, an electrolyte sheet thickness d of 0.078cm, and a cross-sectional area S of 0.785cm2According to the formula σLi +Calculated as d/SR, Li+The conductivity can reach 1.52 x 10-4S/cm; and Li6.4La3Zr1.4Ta0.6O12Li of original sample+The conductivity is only 3.34 multiplied by 10-9S/cm。
As shown in fig. 9, the direct current polarization (DC) curve of the garnet oxide/coordinated boron nitrogen hydride composite electrolyte material prepared in example 2; at 30 ℃, according to the electron conductivity formula sigmae＝I0d/U0S, testing steady-state current I020nA, thickness d of electrolyte sheet 0.078cm, voltage U was applied0Calculated as 0.1V, the electron conductivity σe＝1.99×10- 8S/cm, which is nearly 4 orders of magnitude less than the ionic conductivity, and is negligible.
Example 3
In a glove box under argon atmosphere, 161mg LiBH was weighed4And 339mg of LiNH2(wherein, LiBH4And LiNH2The molar ratio is 1:2) are sequentially filled into a ball milling tank, the ball material ratio is 120:1, and ball milling beads are made of stainless steel; ball-milling the mixture in a planetary ball mill at the rotating speed of 500rpm for 24 hours, taking out the obtained ball-milled product in an argon atmosphere glove box, wherein the ball-milled product is Li3(BH4)(NH2)2。
Mixing LLZTO with Li3(BH4)(NH2)2A total of 500mg, was hand milled in a mortar at a mass ratio of 92.5:7.5 for 20 minutes to give a blend of Li3(BH4)(NH2)2Coated garnet oxide/coordination boron nitrogen hydride composite electrolyte material LLZTO-Li3(BH4)(NH2)2And carrying out subsequent electrochemical performance tests.
As shown in FIG. 10, the impedance (EIS) curve of the garnet oxide/complex boronitride-hydride solid electrolyte material prepared in example 3, which is a semicircle at a high frequency region, the intersection of the right end of the semicircle and the solid axis represents the total resistance of bulk phase and particle space, and an oblique line at a low frequency region, reflects the ion blocking phenomenon, and it can be seen from the curve that LLZTO-Li is used at 30 deg.C3(BH4)(NH2)2The resistance R of (1) was 920 Ω, the electrolyte sheet thickness d was 0.09cm, and the cross-sectional area S was 0.785cm2According to the formula σLi +Calculating Li as d/SR+The conductivity can reach 1.25 multiplied by 10-4S/cm; and Li6.4La3Zr1.4Ta0.6O12Li of original sample+The conductivity is only 3.34 multiplied by 10-9S/cm。
Examples 4 to 15
Examples 4 to 15 are composite solid electrolytes obtained by compositing different garnet-type oxides with different coordination boron nitrogen hydrides, and electrochemical properties thereof, respectively.
Basically the same as the method adopted in the above examples 1 to 3, the electrolyte materials obtained by compounding different garnet-type oxides and different coordination boron-nitrogen hydrides are obtained by adjusting the phase of the added reactants and the grinding preparation parameters (including the rotating speed, the time and the atmosphere). Table 1 lists the different composite solid electrolyte materials prepared under this ball milling process and their respective ionic conductivities at 30 ℃. It can be seen that the electrolyte material obtained by compounding the garnet-type oxide with boron-nitrogen hydride has high Li at near room temperature+Ion conductivity.
TABLE 1 solid electrolytes of various garnet oxide/complex boroazahydride and Li at 30 deg.C+Ionic conductivity
Application example
The LLZTO-Li prepared in example 1 was used4(BH4)(NH2)3Prepressing the mixture into sheets in a stainless steel mold under the pressure of 100MPa, and maintaining the pressure for 5 minutes; then, commercial LiCoO was added2With LLZTO-Li4(BH4)(NH2)3Grinding for 5 minutes according to the mass ratio of 5:5, taking 15mg of the obtained mixed material as a composite positive electrode; adding a lithium metal sheet with the diameter of 0.9cm on the other side as a negative electrode, and finally maintaining the pressure of the whole at 300MPa for 5 minutes to obtain LiCoO2|LLZTO-Li4(BH4)(NH2)3And | Li full cell.
Claims (9)
1. A method for preparing a garnet oxide/coordinated boron nitrogen hydride composite solid electrolyte, comprising:
under inert gas, garnet oxide and boron nitrogen hydride are mixed according to the mass ratio of 80-99:1-20, and then mechanically or manually ground at normal temperature to obtain the garnet oxide/coordination boron nitrogen hydride composite solid electrolyte, wherein the grinding time is 5min-15h, and the grinding speed is 45-300 rpm.
2. The method of claim 1, wherein the inert gas is argon, nitrogen or helium.
3. The method of claim 1, wherein the grinding time is 5min to 10 hours.
4. The method for preparing garnet oxide/complex boron nitrogen hydride solid electrolyte as claimed in claim 1, wherein the mechanical milling is mechanical ball milling, the rotation speed of the mechanical ball milling is 5min-10h, and the mechanical ball milling time is 60-300 rpm.
5. A garnet oxide/coordinated boron nitrogen hydride composite solid-state electrolyte prepared according to the method for preparing a garnet oxide/coordinated boron nitrogen hydride composite solid-state electrolyte as set forth in any one of claims 1 to 4.
6. The method of claim 5, wherein the garnet oxide/complex boron nitride hydride solid-state electrolyte comprises a garnet oxide substrate and a complex boron nitride hydride layer coated on the surface of the garnet oxide substrate.
7. The method of claim 5, wherein the garnet oxide/complex boron nitride hydride solid-state electrolyte is prepared by a method comprising forming a garnet cubic phase structure from the garnet oxide/complex boron nitride hydride solid-state electrolyte.
8. The method of claim 5, wherein the garnet oxide/complex boron nitrogen hydride solid-state electrolyte is prepared by the method of preparing the garnet oxide/complex boron nitrogen hydride solid-state electrolyte, wherein the garnet oxide matrix has a molecular formula of LiαGα’La3-βMβZr2-γRγO12Wherein G is Al, Fe, Ga or GeAny one of them; m is Sr or Rb; r is any one of Ta, Nb, Sb and Mo, wherein alpha is 3-7, alpha' is 0-0.8, beta is 0-0.8 and gamma is 0-0.8.
9. A method of preparing a garnet oxide/coordinated boron nitrogen hydride composite solid-state electrolyte according to any one of claims 5 to 8, for use in an all solid-state lithium ion battery, comprising:
pressing the garnet oxide/coordinated boron nitrogen hydride compounded solid electrolyte at the pressure of 100-500MPa to obtain a flaky garnet oxide/coordinated boron nitrogen hydride compounded solid electrolyte, and mixing the flaky garnet oxide/coordinated boron nitrogen hydride compounded solid electrolyte with LiCoO2、LiFePO4、LiMnxFe1-xPO4(0＜x＜1)、LiMnPO4、TiS2S or MoS2And matching the positive electrode with the lithium metal negative electrode to obtain the all-solid-state lithium ion battery.
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