CN111786014A - Garnet type solid electrolyte powder with superfine particle size and preparation method thereof - Google Patents
Garnet type solid electrolyte powder with superfine particle size and preparation method thereof Download PDFInfo
- Publication number
- CN111786014A CN111786014A CN202010775480.4A CN202010775480A CN111786014A CN 111786014 A CN111786014 A CN 111786014A CN 202010775480 A CN202010775480 A CN 202010775480A CN 111786014 A CN111786014 A CN 111786014A
- Authority
- CN
- China
- Prior art keywords
- powder
- ball milling
- llzo
- solid electrolyte
- particle size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 158
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002245 particle Substances 0.000 title claims abstract description 21
- 239000002223 garnet Substances 0.000 title claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 133
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 239000011882 ultra-fine particle Substances 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 60
- 238000001035 drying Methods 0.000 claims description 48
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 22
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 58
- 239000000919 ceramic Substances 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 42
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 28
- 238000001816 cooling Methods 0.000 description 25
- 235000015895 biscuits Nutrition 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 16
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 15
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 238000007605 air drying Methods 0.000 description 10
- 229910000484 niobium oxide Inorganic materials 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 235000012054 meals Nutrition 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000002001 electrolyte material Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910008088 Li-Mn Inorganic materials 0.000 description 1
- 229910006327 Li—Mn Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
-
- 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 garnet type solid electrolyte powder with ultrafine granularity and a preparation method thereof, belonging to the field of preparation of solid electrolyte materials of all-solid-state lithium batteries. The garnet type solid electrolyte powder with ultrafine particle size is in a cubic phase structure, the particle size of the powder is less than 1 mu m, the particle size distribution is unimodal distribution, and the garnet type solid electrolyte powder has high specific surface area>1500m2·Kg‑1). And crushing the garnet type solid electrolyte powder with the ultrafine particle size by adopting a wet ball milling process. When the ball milling process is used for preparing ultrafine powder, the viscosity of slurry is controlled to be 20-100mPa & s. The garnet type solid electrolyte powder with ultra-fine particle size prepared by the invention has high sintering rateThe sintering can be completed at lower temperature or shorter time due to the activity, and the electrolyte ceramic sheet with high density and high ionic conductivity is obtained.
Description
Technical Field
The invention relates to the field of preparation of all-solid-state lithium battery solid electrolyte materials, in particular to garnet-type Lanthanum Lithium Zirconate (LLZO) solid electrolyte powder with ultrafine particle size and a preparation method thereof.
Background
Today, as society develops rapidly, various electronic products, new energy vehicles, smart grids and the like using lithium ion batteries are widely used in social life. Meanwhile, along with the development of society, people put forward demands on lithium ion batteries which are safer, lighter and higher in capacity. However, the conventional lithium ion battery using an organic electrolyte as a lithium ion transmission medium has many safety problems while continuously improving the specific capacity and the working voltage. Therefore, all-solid-state batteries using lithium ion solid electrolytes are becoming a focus of public attention, and it is expected that the safety performance of the batteries can be increased while the energy density of the batteries is increased. Garnet type solid electrolyte LLZO is receiving attention because it has the advantages of high lithium ion conductivity, low electron conductivity, wide voltage window, low activation energy and lithium stability. However, it also has problems such as instability of cubic phase at room temperature, complicated sintering process, and high interfacial resistance with the positive electrode material. Therefore, the garnet-type solid electrolyte LLZO at present cannot fully satisfy the application requirements in the all-solid-state lithium battery.
Currently, researchers mainly perform works such as doping stable cubic phase LLZO, adding a sintering aid to promote sintering, and performing interface engineering between LLZO and positive and negative electrode materials, aiming at the problems in LLZO, but the research work for preparing powder of LLZO is very little. In the traditional ceramic sintering process, the particle size and the distribution of the powder have important influences on the sintering process of the ceramic and the performance of a ceramic product; in the sintering process of the LLZO ceramic, the granularity and the distribution of the LLZO powder also have important influence on the performance of the LLZO ceramic, such as the density, the ionic conductivity and the like.
For the preparation of LLZO powder, researchers at home and abroad mainly adopt a traditional solid phase method, a coprecipitation method, a sol-gel method and the like. The above methods all require mixing of raw materials in different ways and then high temperature calcination of the mixed raw materials or material precursors to obtain the LLZO coarse powder. Meanwhile, although the ultrafine LLZO powder with uniform particle size can be theoretically obtained by adopting a coprecipitation method, a sol-gel method and the like, in the process of high-temperature calcination synthesis, the precursor is agglomerated, so that the final product still needs to be crushed by a ball-milling process. Therefore, the development of the preparation method of the LLZO powder which is simple and convenient to operate, high in yield and efficiency, has ultra-fine granularity and has a pure cubic phase structure has important practical significance.
Disclosure of Invention
The invention aims to provide garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder with ultra-fine granularity and a preparation method thereof. The ultra-fine particle size garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder has micron-sized and submicron-sized particle sizes, and simultaneously has high specific surface area. The electrolyte material can be closely contacted with the positive electrode layer and the electrolyte layer in the composite positive electrode, and is favorable for reducing interface impedance.
In order to achieve the above object, the present invention provides the following technical solutions:
the garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder with ultrafine particle size is characterized in that the powder phase has a cubic phase structure, the powder particle size is less than 1 mu m, the particle size distribution is unimodal distribution, and the garnet-type lithium lanthanum zirconate solid electrolyte powder has a high specific surface area (LLZO)>1500m2·Kg-1) The viscosity of the slurry is 20-100 mPas.
In the technical scheme of the invention, the LLZO solid electrolyte powder comprises lithium, lanthanum, zirconium and doping elements, wherein the doping elements comprise aluminum, iron, gallium, yttrium, cerium, antimony, tantalum and niobium; the doping dosage ratio is 0.01mol to 0.6mol according to the given dosage ratio.
In addition, the invention also provides a method for preparing the garnet-type solid electrolyte powder with ultra-fine particle size by using a ball milling method.
The object of the present invention can be achieved by at least one of the following methods.
The invention also provides a preparation method of the garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder with the ultrafine particle size, which comprises the following steps:
(1) preparing mixed slurry: li is prepared by weighing each compound including lithium, lanthanum, zirconium and doping elements according to a certain metering ratio (for example, taking Nb doping as an example, 6.6 parts of lithium hydroxide, 1.5 parts of lanthanum oxide, 1.6 parts of zirconium oxide and 0.2 part of niobium oxide6.6La3Zr1.6Nb0.4O12Powder) and mixing with a ball-milling solvent and a ball-milling medium according to respective proportions to prepare mixed slurry;
(2) ball milling and drying the mixed slurry: performing ball milling treatment on the mixture obtained in the step (1) to obtain uniform slurry, and drying to obtain mixed raw material powder;
(3) calcining mixed raw material powder: carrying out high-temperature calcination treatment on the mixed raw material powder obtained in the step (2) to obtain cubic phase LLZO coarse powder;
(4) preparing cubic phase LLZO slurry: mixing the cubic phase LLZO coarse powder obtained in the step (3) with a ball milling solvent and a ball milling medium according to respective proportions;
(5) ball-milling and drying the cubic phase LLZO slurry: performing ball milling treatment on the mixture obtained in the step (4) to obtain uniform slurry, and drying to obtain the superfine cubic phase LLZO powder.
Optionally, in the step (1), the content is as follows by mass ratio of elements: 6.4 to 7 portions of lithium, 2.6 to 3 portions of lanthanum, 1.4 to 2 portions of zirconium and 0.01 to 0.6 portion of doping element
Alternatively, the compound forms of lithium, lanthanum, zirconium and doping elements described in step (1) include, but are not limited to, oxides, nitrates, carbonates, hydroxides, and the like.
Optionally, the doping element in step (1) includes, but is not limited to, aluminum, iron, gallium, yttrium, cerium, antimony, tantalum, niobium, and the like.
Optionally, the ball milling solvent in step (1) is an organic solvent, preferably an alcohol solvent including but not limited to alcohol, isopropanol, and the like, and the mass ratio of the ball milling solvent to the material is 1: 2-2: 1.
optionally, the ball milling media in step (1) include, but are not limited to, yttrium-stabilized zirconia, agate, etc., the diameter of the milling media is 0.8mm to 40mm, and the ball-to-material ratio is 1: 1-5: 1.
alternatively, the ball milling process described in step (2) may be of a mechanical type including, but not limited to, a tumbling ball mill, a planetary ball mill, a horizontal sand mill, and the like.
Optionally, the rotation speed of the ball milling treatment in the step (2) is 200-.
Optionally, the drying temperature in the step (2) is 70-80 ℃, and the drying time is 10-40 h.
Optionally, the calcination treatment temperature in the step (3) is 700-.
Alternatively, the ball milling solvent described in step (4) includes, but is not limited to, alcohol, isopropanol, and the like; the mass ratio of the ball-milling solvent to the materials is 1: 2-2: 1.
optionally, the ball milling media described in step (4) include, but are not limited to, yttrium stabilized zirconia, agate, and the like; the diameter of the grinding medium is 0.8mm-40 mm.
Alternatively, the ball milling process described in step (5) may be of a mechanical type including, but not limited to, a tumbling ball mill, a planetary ball mill, a horizontal sand mill, and the like.
Optionally, the rotation speed of the ball milling treatment in the step (5) is 200-.
Optionally, the drying temperature in the step (5) is 70-80 ℃, and the drying time is 10-40 h.
In addition, the invention also provides a preparation method of the mother powder-free sintered LLZO electrolyte ceramic, which comprises the following steps:
(a) biscuit molding: mixing the superfine cubic phase LLZO powder prepared by the invention with a binder, loading the mixture into a mold, and maintaining the pressure for a certain time to form under a certain pressure to prepare a LLZO biscuit;
(b) and (3) sintering: loading the LLZO biscuit prepared in the step (a) into a crucible, and sintering the LLZO biscuit into LLZO ceramic at a certain temperature;
optionally, the binder described in step (a) may or may not be added; the binder types include but are not limited to PVA, PVB, and the like;
alternatively, the mold in step (a) includes, but is not limited to, a general steel mold, a split mold, etc.; the molding mode includes but is not limited to a uniaxial dry pressing mode, a biaxial dry pressing mode, an isostatic pressing mode and the like;
optionally, the molding pressure in the step (a) is 150-400Mpa, and the pressure maintaining time is 1-10 min;
alternatively, the crucible material in step (b) includes, but is not limited to, alumina crucible, magnesia crucible, zirconia crucible, platinum crucible, etc.;
optionally, the sintering temperature in step (b) is 1000-1250 ℃, and the sintering time is 10-1440 min.
Compared with the prior art, the invention adopts wet ball milling and crushing to prepare the ultrafine garnet solid electrolyte powder, and the method has simple preparation flow and low cost and can be used for mass industrial production.
Compared with the prior art, the method for preparing the garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder with ultra-fine particle size, provided by the invention, has the advantages that the cubic phase of the prepared garnet-type electrolyte powder is stabilized by doping, the ball milling process parameters are adjusted, the garnet-type electrolyte powder has smaller particle size and more concentrated particle size distribution, and the electrolyte powder prepared by the method is used as a raw material for ceramic sintering, so that the waste of the raw material and energy can be greatly reduced.
The invention discloses garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder with ultrafine granularity and a preparation method thereof. The method comprises the following steps: mixing compounds of lithium, lanthanum, zirconium and doping elements with a ball-milling medium and a ball-milling solvent in proportion, then carrying out ball-milling treatment to obtain slurry of mixed raw materials, and drying to obtain mixed raw material powder. Calcining the mixed raw material powder at high temperature to obtain cubic-phase LLZO powder (coarse powder), mixing the cubic-phase LLZO powder (coarse powder) with a ball-milling medium and a ball-milling solvent according to a certain proportion, carrying out ball-milling treatment to obtain cubic-phase LLZO powder slurry, and drying to obtain superfine cubic-phase LLZO powder. The superfine garnet type solid electrolyte powder prepared by the ball milling method has small granularity, the grain diameter is less than 1 mu m, and the granularity distribution is concentrated. The method has simple preparation process and large preparation amount, can be used for continuous preparation and is suitable for the requirement of industrial large-scale production. Meanwhile, the electrolyte ceramic prepared by the powder can be sintered at low temperature in a short time without mother powder, so that the waste of raw materials and energy is greatly reduced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with other methods, the preparation method of the ultra-fine particle size garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder can prepare the ultra-fine garnet-type solid electrolyte powder more rapidly, massively and easily, and is suitable for large-scale industrial production;
(2) when the ultrafine garnet type solid electrolyte powder provided by the invention is applied to the sintering process of the LLZO electrolyte ceramic, the sintering temperature can be reduced, the sintering time can be shortened, meanwhile, the waste of raw materials is avoided by adopting mother powder-free sintering, and the production cost is greatly reduced.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an XRD pattern of ultra-fine particle size garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder prepared in examples 1 to 5 of the present invention;
FIG. 2 is a graph showing a particle size distribution of an ultra-fine particle size garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder obtained in example 5 of the present invention;
FIG. 3 is an SEM photograph of an ultra-fine particle size garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder prepared in example 5 of the present invention;
FIG. 4 is a cross-sectional SEM photograph of an electrolyte ceramic sheet prepared using the ultra-fine particle size garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder prepared in example 5 of the present invention.
FIG. 5 the LLZO electrolyte material of the present invention in Li2MnO4The cycling performance and the coulombic efficiency of the Li all-solid-state battery.
FIG. 6 the LLZO electrolyte material of the present invention in Li2MnO4Solid state of/LiAnd the first turn, the second turn, the fifth turn, the tenth turn, the twentieth turn and the fifty-th turn of the battery are subjected to charge-discharge curve charts.
FIG. 7 is an AC impedance diagram of the LLZO electrolyte material of the present invention in a lithium rich manganese/Li all solid state battery.
Detailed Description
The invention provides garnet type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder with ultrafine granularity and a preparation method thereof, wherein the method adopts a ball milling treatment mode, adjusts process parameters in the ball milling treatment process to obtain the garnet type solid electrolyte powder with ultrafine granularity, and meanwhile, the powder has better particle size distribution, is narrower and has higher specific surface energy, so that when the powder is applied to sintering, the powder has higher sintering activity, the sintering process is promoted, sintering can be completed in a short time at low temperature without mother powder, and the LLZO solid electrolyte ceramic with excellent performance is obtained.
The invention adopts a ball milling treatment mode to prepare garnet type solid electrolyte powder with ultra-fine granularity, wherein the garnet type solid electrolyte powder has submicron granularity (<1 μm), monomodal particle size distribution and high powder specific surface area: (>1500m2·Kg-1) Therefore, the sintering agent has high sintering activity, can promote the sintering process in the sintering process, reduce the sintering temperature and shorten the sintering time, and can also reduce the instability of a ceramic phase caused by lithium volatilization in the high-temperature sintering process, thereby adopting a sintering mode of supplementing lithium volatilization under high-temperature sintering without adding mother powder.
The garnet-type Lithium Lanthanum Zirconate (LLZO) solid electrolyte powder with the ultrafine particle size and the preparation method thereof specifically comprise the following steps:
(1) preparing mixed slurry: l is prepared by weighing the compounds of lithium, lanthanum, zirconium and doping elements according to the given proportion (for example, taking Nb doping as an example, 6.6 parts of lithium hydroxide, 1.5 parts of lanthanum oxide, 1.6 parts of zirconium oxide and 0.2 part of niobium oxidei6.6La3Zr1.6Nb0.4O12Powder) and mixing with a ball-milling solvent and a ball-milling medium according to respective proportions to prepare mixed slurry;
in step (1), the compound forms of lithium, lanthanum, zirconium and doping elements include, but are not limited to, oxides, nitrates, carbonates, hydroxides, etc. Preferably, lithium hydroxide, lanthanum oxide, zirconium oxide, and niobium oxide are used in this embodiment. The doping element includes, but is not limited to, aluminum, iron, gallium, yttrium, cerium, antimony, tantalum, niobium, and the like, and may be one or more of the elements. Preferably, niobium oxide is used in this embodiment. The given ratio includes, but is not limited to, a stoichiometric ratio, a mass ratio, or other ratio that meets the requirements of the formulation, etc. Preferably, in this embodiment, L is prepared using a stoichiometric ratio of 6.6 parts lithium hydroxide, 1.5 parts lanthanum oxide, 1.6 parts zirconium oxide, and 0.2 parts niobium oxidei6.6La3Zr1.6Nb0.4O12And (3) powder. The ball milling solvent is an organic solvent, preferably an alcohol, including but not limited to alcohol, isopropanol and the like. Preferably, isopropanol is selected for use in this embodiment. The ball milling media include, but are not limited to, yttrium stabilized zirconia, agate, and the like. Preferably, yttrium-stabilized zirconia is used in this embodiment. The respective proportions include the proportion between the ball milling solvent and the raw materials, the proportion between the raw materials of the ball milling medium, and the grading proportion of the ball milling medium, wherein the proportions include but are not limited to stoichiometric ratio, mass ratio, other proportions according with the formula requirements, and the like. Preferably, in this embodiment, the mass ratio is selected, and the ratio of the ball milling solvent to the raw materials is 1: 2-2: 1, the proportion of the ball milling medium to the ball milling raw material is 1: 1-5: 1, the diameter of the ball milling medium is 0.8-40mm, and the proportion of the ball milling medium with each size is 20-70%.
(2) Ball milling and drying the mixed slurry: performing ball milling treatment on the mixture obtained in the step (1) to obtain uniform slurry, and drying to obtain mixed raw material powder;
in the step (2), the ball milling treatment is carried out by using mechanical types including, but not limited to, a tumbling ball mill, a planetary ball mill, a horizontal sand mill, etc. Preferably, a planetary ball mill is used in this embodiment. The technological parameters of the ball milling treatment comprise ball milling time and ball milling rotating speed. Preferably, in this embodiment, the ball milling time is 2-6h, and the ball milling rate is 200-. In the drying process, the drying equipment adopted has no special requirement, and the drying equipment familiar in the research field can be adopted, such as an air-blast drying oven. The drying process comprises drying temperature, drying time and the like. Preferably, the drying temperature is 70-80 ℃ and the drying time is 10-40h in the embodiment.
(3) Calcining mixed raw material powder: carrying out high-temperature calcination treatment on the mixed raw material powder obtained in the step (2) to obtain cubic phase LLZO coarse powder;
in the step (3), the calcining equipment is not particularly required, and electric furnace equipment well known to researchers in the field, such as a silicon carbide rod furnace, can be adopted. The calcination treatment process comprises calcination temperature, calcination time, heating rate, cooling rate, atmosphere conditions and the like. Preferably, in this embodiment, the calcination temperature is 700-950 ℃, the calcination time is 6-12h, the temperature-increasing rate is 2-10 ℃/min, the temperature-decreasing rate is natural cooling, and the atmosphere condition is natural air atmosphere.
(4) Preparing cubic phase LLZO slurry: mixing the cubic phase LLZO coarse powder obtained in the step (3) with a ball milling solvent and a ball milling medium according to respective proportions;
in step (4), the ball milling solvent includes, but is not limited to, alcohol, isopropanol, and the like. Preferably, isopropanol is selected for use in this embodiment. The ball milling media include, but are not limited to, yttrium stabilized zirconia, agate, and the like. Preferably, yttrium-stabilized zirconia is used in this embodiment. The respective proportions include the proportion between the ball milling solvent and the raw materials, the proportion between the raw materials of the ball milling medium, and the grading proportion of the ball milling medium, wherein the proportions include but are not limited to stoichiometric ratio, mass ratio, other proportions according with the formula requirements, and the like. Preferably, in this embodiment, the mass ratio is selected, and the ratio of the ball milling solvent to the raw materials is 1: 2-2: 1, the proportion of the ball milling medium to the ball milling raw material is 1: 1-5: 1, the diameter of the ball milling medium is 0.8-40mm, and the proportion of the ball milling medium with each size is 20-70%.
(5) Ball-milling and drying the cubic phase LLZO slurry: performing ball milling treatment on the mixture obtained in the step (4) to obtain uniform slurry, and drying to obtain the superfine cubic phase LLZO powder.
In the step (5), the ball milling treatment is carried out by using mechanical types including, but not limited to, a tumbling ball mill, a planetary ball mill, a horizontal sand mill, etc. Preferably, a planetary ball mill and a horizontal sand mill are selected in this embodiment. The technological parameters of the ball milling treatment comprise ball milling time and ball milling rotating speed. Preferably, in this embodiment, the ball milling time is 2-8h, and the ball milling rate is 200-. The uniform slurry is submicron-sized LLZO powder slurry, and in the present embodiment, the viscosity of the slurry is preferably controlled to be 20 to 100 mPas. In the drying process, the drying equipment adopted has no special requirement, and the drying equipment familiar in the research field can be adopted, such as an air-blast drying oven. The drying process comprises drying temperature, drying time and the like. Preferably, the drying temperature is 70-80 ℃ and the drying time is 10-40h in the embodiment.
Meanwhile, the invention also provides a preparation method of the mother powder-free sintered LLZO electrolyte ceramic, which comprises the following steps:
(a) biscuit molding: mixing the superfine cubic phase LLZO powder prepared in the technical scheme with a binder, loading the mixture into a mold, and maintaining the pressure for a certain time under a certain pressure to form the LLZO biscuit.
In the step (a), the binder may be added or not added, and the binder may be selected from PVA, PVB and the like. Preferably, the present embodiment adopts a method without adding a binder. The mold includes, but is not limited to, a general steel mold, a split mold, etc. Preferably, a common steel mold is used in this embodiment. The molding method includes but is not limited to uniaxial dry pressing, biaxial dry pressing, isostatic pressing and the like. Preferably, the present embodiment is formed by uniaxial dry pressing. Preferably, in the present embodiment, the molding pressure is 200MPa, and the dwell time is 3 min.
(b) And (3) sintering: loading the LLZO biscuit prepared in (a) into a crucible, covering the crucible, and sintering at a certain temperature to obtain the LLZO ceramic.
In the step (b), the crucible material includes, but is not limited to, an alumina crucible, a magnesia crucible, a zirconia crucible, a platinum crucible, and the like. Preferably, a magnesium oxide crucible is used in the present embodiment. The sintering system comprises sintering temperature, sintering time, heating rate, cooling rate, sintering atmosphere, mother powder cover sintering condition and the like. Preferably, in this embodiment, the sintering temperature is 1000-1250 ℃, the sintering time is 10-1440min, the temperature rising rate is 2-10 ℃/min, the cooling rate is natural cooling, the sintering atmosphere is natural air atmosphere, and the cover sintering condition of the mother powder is no cover sintering of the mother powder.
The present invention will be described in detail with reference to examples, but it should not be construed as limiting the scope of the present invention.
Example 1
Lithium hydroxide, lanthanum oxide, zirconium oxide and niobium oxide are weighed according to the stoichiometric ratio, wherein the lithium hydroxide is 6.6 parts, the lanthanum oxide is 1.5 parts, the zirconium oxide is 1.6 parts, and the niobium oxide is 0.2 part, so as to prepare Li6.6La3Zr1.6Nb0.4O12And (3) powder. Adding the raw materials into a nylon ball milling tank, wherein the mass ratio of the raw materials to the raw materials is 1.5: 1, and 5: 1 mass ratio of yttrium-stabilized zirconia ball milling media, wherein the diameters of yttrium-stabilized zirconia are 3mm and 6mm, and the mass ratio of yttrium-stabilized zirconia ball milling media is 1: 1.4. and (3) placing the mixed raw materials into a planetary ball mill for ball milling treatment, wherein the ball milling speed is 800r/min, and the ball milling time is 6 h. And (3) placing the obtained mixed raw material slurry into a forced air drying box, and drying for 20 hours at 70 ℃ to obtain mixed raw material powder. Placing the mixed raw material powder in a corundum crucible, placing the powder in a muffle furnace after the powder is vibrated, heating to 950 ℃ at the heating rate of 5 ℃/min, and preserving the heat at the temperature for 12 hours to obtain cubic phase LLZO coarse powder, wherein the cooling rate is natural cooling, and the calcining atmosphere condition is natural air condition. Cubic phase LLZO meal was mixed with isopropanol and yttrium stabilized zirconia and added to a nylon jar, wherein the isopropanol was added at a ratio of 1.5: 1, adding yttrium-stabilized zirconia in a ratio of 2: 1, wherein yttrium stabilizes zirconium oxideThe diameter is 3mm and 6mm, and the mass ratio is 1: 2. placing cubic phase LLZO coarse powder in a planetary ball mill for ball milling treatment, wherein the ball milling speed is 800r/min, and the ball milling time is 6 h. Controlling the viscosity of the obtained superfine cubic phase LLZO slurry to be 20mPa & s, putting the slurry in a forced air drying box, and drying for 20h at 70 ℃ to obtain superfine cubic phase LLZO powder.
Taking 1g of the obtained superfine cubic phase LLZO powder, placing the powder in a steel mould, and preparing a ceramic biscuit in a dry pressing mode in a binder-free mode, wherein the forming pressure is 200MPa, and the pressure maintaining time is 3 min. And placing the prepared biscuit in a magnesium oxide crucible, sintering in a cover-sintering-free mode at 1250 ℃ for 40min at a cooling rate of natural cooling under a natural air condition in a sintering atmosphere condition, and then obtaining the LLZO electrolyte ceramic.
Example 2
Lithium hydroxide, lanthanum oxide, zirconium oxide and niobium oxide are weighed according to the stoichiometric ratio, wherein the lithium hydroxide is 6.8 parts, the lanthanum oxide is 1.5 parts, the zirconium oxide is 1.8 parts, and the niobium oxide is 0.1 part, so as to prepare Li6.8La3Zr1.8Nb0.2O12And (3) powder. Adding the raw materials into a nylon ball milling tank, wherein the mass ratio of the raw materials to the raw materials is 1.5: 1, and 5: 1 mass ratio of yttrium-stabilized zirconia ball milling media, wherein the diameters of yttrium-stabilized zirconia are 3mm and 6mm, and the mass ratio of yttrium-stabilized zirconia ball milling media is 1: 1.4. and (3) placing the mixed raw materials into a planetary ball mill for ball milling treatment, wherein the ball milling speed is 800r/min, and the ball milling time is 6 h. And (3) placing the obtained mixed raw material slurry into a forced air drying box, and drying for 20 hours at 70 ℃ to obtain mixed raw material powder. Placing the mixed raw material powder in a corundum crucible, placing the powder in a muffle furnace after the powder is vibrated, heating to 850 ℃ at the heating rate of 5 ℃/min, and preserving the heat at the temperature for 12 hours to obtain cubic phase LLZO coarse powder, wherein the cooling rate is natural cooling, and the calcining atmosphere condition is natural air condition. Cubic phase LLZO meal was mixed with isopropanol and yttrium stabilized zirconia and added to a nylon jar, wherein the isopropanol was added at a ratio of 1.5: 1, adding yttrium-stabilized zirconia in a ratio of 5: 1, wherein the diameter of the yttrium stabilized zirconia is 3mm and 6mm, and the mass ratio of the yttrium stabilized zirconia to the yttrium stabilized zirconia is 1: 2. will stand upAnd placing the square-phase LLZO coarse powder in a planetary ball mill for ball milling treatment, wherein the ball milling speed is 800r/min, and the ball milling time is 6 h. Controlling the viscosity of the obtained superfine cubic phase LLZO slurry to be 20mPa & s, putting the slurry in a forced air drying box, and drying for 20h at 70 ℃ to obtain superfine cubic phase LLZO powder.
Taking 1g of the obtained superfine cubic phase LLZO powder, placing the powder in a steel mould, and preparing a ceramic biscuit in a dry pressing mode in a binder-free mode, wherein the forming pressure is 200MPa, and the pressure maintaining time is 3 min. And placing the prepared biscuit in a magnesium oxide crucible, sintering in a cover-sintering-free mode at 1250 ℃ for 40min at a cooling rate of natural cooling under a natural air condition in a sintering atmosphere condition, and then obtaining the LLZO electrolyte ceramic.
Example 3
Lithium hydroxide, lanthanum oxide, zirconium oxide and niobium oxide are weighed according to the stoichiometric ratio, wherein the weight ratio of lithium hydroxide is 6.28 parts, the weight ratio of lanthanum oxide is 1.5 parts, the weight ratio of zirconium oxide is 2 parts, and the weight ratio of aluminum oxyhydroxide is 0.08 part, so as to prepare Li6.28La3Zr2Al0.24O12And (3) powder. Adding the raw materials into a nylon ball milling tank, wherein the mass ratio of the raw materials to the raw materials is 1.5: 1, and 5: 1 mass ratio of yttrium-stabilized zirconia ball milling media, wherein the diameters of yttrium-stabilized zirconia are 3mm and 6mm, and the mass ratio of yttrium-stabilized zirconia ball milling media is 1: 1.4. and (3) placing the mixed raw materials into a planetary ball mill for ball milling treatment, wherein the ball milling speed is 800r/min, and the ball milling time is 4 h. And (3) placing the obtained mixed raw material slurry into a forced air drying box, and drying for 20 hours at 70 ℃ to obtain mixed raw material powder. Placing the mixed raw material powder in a corundum crucible, placing the powder in a muffle furnace after the powder is vibrated, heating to 750 ℃ at the heating rate of 5 ℃/min, and preserving the heat at the temperature for 12 hours to obtain cubic phase LLZO coarse powder, wherein the cooling rate is natural cooling, and the calcining atmosphere condition is natural air condition. Cubic phase LLZO meal was mixed with isopropanol and yttrium stabilized zirconia and added to a nylon jar, wherein the isopropanol was added at a ratio of 1.5: 1, adding yttrium-stabilized zirconia in a ratio of 5: 1, wherein the diameters of the yttrium-stabilized zirconia are 1.5mm, 3mm and 6mm, and the mass ratio of the yttrium-stabilized zirconia is 3: 4: 3. placing cubic phase LLZO coarse powder in planetary typeBall milling treatment is carried out in a ball mill, the ball milling speed is 800r/min, and the ball milling time is 6 h. Controlling the viscosity of the obtained superfine cubic phase LLZO slurry to be 100 mPas, putting the slurry in a forced air drying oven, and drying for 20h at 70 ℃ to obtain superfine cubic phase LLZO powder.
Taking 1g of the obtained superfine cubic phase LLZO powder, placing the powder in a steel mould, and preparing a ceramic biscuit in a dry pressing mode in a binder-free mode, wherein the forming pressure is 200MPa, and the pressure maintaining time is 3 min. And placing the prepared biscuit in a magnesium oxide crucible, sintering in a cover-sintering-free mode at the sintering temperature of 1200 ℃, for 30min, at the cooling rate of natural cooling under the condition of natural air atmosphere, and then obtaining the LLZO electrolyte ceramic.
Example 4
Lithium hydroxide, lanthanum oxide, zirconium oxide and niobium oxide are weighed according to the stoichiometric ratio, wherein the lithium hydroxide is 6.73 parts, the lanthanum oxide is 1.5 parts, the zirconium oxide is 1.85 parts, the aluminum hydroxide is 0.04 part and the niobium oxide is 0.15 part, so as to prepare Li6.73Al0.04La3Zr1.85Nb0.15O12And (3) powder. Adding the raw materials into a nylon ball milling tank, wherein the mass ratio of the raw materials to the raw materials is 1.5: 1, and 5: 1 mass ratio of yttrium-stabilized zirconia ball milling media, wherein the diameters of yttrium-stabilized zirconia are 3mm and 6mm, and the mass ratio of yttrium-stabilized zirconia ball milling media is 1: 1.4. and (3) placing the mixed raw materials into a planetary ball mill for ball milling treatment, wherein the ball milling speed is 800r/min, and the ball milling time is 6 h. And (3) placing the obtained mixed raw material slurry into a forced air drying box, and drying for 20 hours at 70 ℃ to obtain mixed raw material powder. Placing the mixed raw material powder in a corundum crucible, placing the powder in a muffle furnace after the powder is vibrated, heating to 1050 ℃ at the heating rate of 5 ℃/min, and preserving the heat at the temperature for 12 hours to obtain cubic phase LLZO coarse powder, wherein the cooling rate is natural cooling, and the calcining atmosphere condition is natural air condition. Cubic phase LLZO meal was mixed with isopropanol and yttrium stabilized zirconia and added to a nylon jar, wherein the isopropanol was added at a ratio of 1.5: 1, adding yttrium-stabilized zirconia in a ratio of 2: 1, wherein the diameters of the yttrium-stabilized zirconia are 1.5mm, 3mm and 6mm, and the mass ratio of the yttrium-stabilized zirconia is 3: 4: 3. placing cubic phase LLZO coarse powderBall milling treatment is carried out in a planetary ball mill, the ball milling speed is 800r/min, and the ball milling time is 6 h. Controlling the viscosity of the obtained superfine cubic phase LLZO slurry to be 100 mPas, putting the slurry in a forced air drying oven, and drying for 20h at 70 ℃ to obtain superfine cubic phase LLZO powder.
Taking 1g of the obtained superfine cubic phase LLZO powder, placing the powder in a steel mould, and preparing a ceramic biscuit in a dry pressing mode in a binder-free mode, wherein the forming pressure is 200MPa, and the pressure maintaining time is 3 min. And placing the prepared biscuit in a magnesium oxide crucible, sintering in a cover-sintering-free mode at the sintering temperature of 1200 ℃, for 30min, at the cooling rate of natural cooling under the condition of natural air atmosphere, and then obtaining the LLZO electrolyte ceramic.
Example 5
Lithium hydroxide, lanthanum oxide, zirconium oxide and niobium oxide are weighed according to the stoichiometric ratio, wherein the lithium hydroxide is 6.6 parts, the lanthanum oxide is 1.5 parts, the zirconium oxide is 1.6 parts, and the vanadium oxide is 0.2 part, so as to prepare Li6.6La3Zr1.6V0.4O12And (3) powder. Adding the raw materials into a nylon ball milling tank, wherein the mass ratio of the raw materials to the raw materials is 1.5: 1, and 5: 1 mass ratio of yttrium-stabilized zirconia ball milling media, wherein the diameters of yttrium-stabilized zirconia are 3mm and 6mm, and the mass ratio of yttrium-stabilized zirconia ball milling media is 1: 1.4. and (3) placing the mixed raw materials into a planetary ball mill for ball milling treatment, wherein the ball milling speed is 800r/min, and the ball milling time is 6 h. And (3) placing the obtained mixed raw material slurry into a forced air drying box, and drying for 20 hours at 70 ℃ to obtain mixed raw material powder. Placing the mixed raw material powder in a corundum crucible, placing the powder in a muffle furnace after the powder is vibrated, heating to 900 ℃ at the heating rate of 5 ℃/min, and preserving the heat at the temperature for 12 hours to obtain cubic phase LLZO coarse powder, wherein the cooling rate is natural cooling, and the calcining atmosphere condition is natural air condition. Cubic phase LLZO meal was mixed with isopropanol and yttrium stabilized zirconia, wherein the ratio of isopropanol added was 1.5: 1, adding yttrium-stabilized zirconia in a ratio of 2: 1, wherein the diameter of the yttrium stabilized zirconia is 0.8mm, and the cubic phase LLZO coarse powder is put into a horizontal sand mill for ball milling treatment, the ball milling speed is 2000r/min, and the ball milling time is 2 h. Controlling the gain of a superThe viscosity of the fine cubic phase LLZO slurry is 50 mPa.s, the slurry is placed in a forced air drying oven and dried for 20h at 70 ℃ to obtain the superfine cubic phase LLZO powder.
Taking 1g of the obtained superfine cubic phase LLZO powder, placing the powder in a steel mould, and preparing a ceramic biscuit in a dry pressing mode in a binder-free mode, wherein the forming pressure is 200MPa, and the pressure maintaining time is 3 min. And placing the prepared biscuit in a magnesium oxide crucible, sintering in a cover sintering mode without mother powder, wherein the sintering temperature is 1150 ℃, the sintering time is 60min, the cooling rate is natural cooling, and the sintering atmosphere condition is a natural air condition, so that the LLZO electrolyte ceramic is obtained.
FIG. 1 is an XRD pattern of the sub-micron level LLZO powder prepared in examples 1-5, and it can be seen that the prepared LLZO powder has a cubic phase crystal structure. FIG. 2 is a distribution diagram of particle size of sub-micron-sized LLZO powder in example 5, which shows that the particle size of LLZO powder is unimodal distribution and is less than 1 μm. FIG. 3 is an SEM photograph of LLZO powder in example 5, showing that the LLZO powder has uniform particle size and all particle sizes are smaller than 1 μm, thus having high specific surface area. FIG. 4 is a sectional SEM photograph of an LLZO electrolyte ceramic sheet sintered using the ultra-fine LLZO powder prepared in example 5, and it can be seen that the powder having a high degree of uniformity, a small particle size and a specific surface area, which has a high sintering activity during sintering, is used, so that sintering can be completed in a short time, and the crystal grain size is uniform and the crystal growth is complete.
Example 6 all-solid-state battery performance study containing LLZO powder of the present invention as electrolyte
Lithium manganate, acetylene black, PVDF and the LLZO powder prepared in example 1 of the present invention were weighed in proportions of 8 parts, 0.5 parts and 2 parts, respectively, and 20 parts of N-methylpyrrolidone was added thereto and sufficiently ground to prepare a positive electrode slurry. And then uniformly coating the positive electrode slurry on the surface of an aluminum foil through a scraper, wherein the thickness of the scraper is 200 mu m, and then placing the coated positive electrode plate in a vacuum drying oven for drying for 4 hours at 120 ℃. Micron-sized (1-10 mu m) LLZO powder, LITFSI and PVDF are respectively added into 20 parts of N-methyl pyrrolidone according to the proportion of 8 parts, 1 part and 1 part to prepare uniform slurry. Subsequently drying the obtained productThe positive pole piece is used as a substrate, electrolyte slurry is coated on the upper layer of the positive pole piece by adopting a scraper, and the thickness of the scraper is 200 mu m, so that a uniform electrolyte coating is obtained. And then placing the anode plate in a vacuum drying oven to be dried for 4 hours at 120 ℃ to obtain the composite anode plate. Rolling the composite positive pole piece by a roll-to-roll machine, wherein the density of the rolled and compacted composite pole piece is 2.5-3.0g/cm3(on-chip amount). And cutting the composite positive electrode into an electrode plate with the diameter of 12mm, taking a lithium plate as a negative electrode, assembling and packaging in a glove box filled with argon atmosphere to obtain the CR2025 button all-solid-state battery. Fig. 5 is a cycle performance and coulombic efficiency of Li2MnO4/Li all-solid-state battery, and fig. 6 is a charge and discharge graph of the first, second, fifth, tenth, twentieth and fifty th turns of Li2MnO4/Li all-solid-state battery.
Example 7 AC impedance study of all-solid-state battery containing LLZO powder as electrolyte
The lithium-rich manganese-based positive electrode material, acetylene black, PVDF and the LLZO powder prepared in example 1 of the present invention were weighed in proportions of 7 parts, 1 part and 2 parts, respectively, and 20 parts of N-methylpyrrolidone was added thereto and sufficiently ground to prepare a positive electrode slurry. And then uniformly coating the positive electrode slurry on the surface of an aluminum foil through a scraper, wherein the thickness of the scraper is 200 mu m, and then placing the coated positive electrode plate in a vacuum drying oven for drying for 4 hours at 120 ℃. Submicron (0.1-0.9 μm) LLZO powder, LITFSI and PVDF are respectively added in a proportion of 9 parts and 1 part, and 10 parts of N-methyl pyrrolidone and 10 parts of isopropanol are added to prepare uniform slurry. And then, taking the obtained dry positive pole piece as a substrate, and coating electrolyte slurry on the upper layer of the dry positive pole piece by adopting a spin coating process, wherein the spin coating speed is 1000rpm, and the number of the coatings is 3, so that a uniform electrolyte coating is obtained. And then placing the anode plate in a vacuum drying oven to be dried for 8 hours at the temperature of 80 ℃ to obtain the composite anode plate. Rolling the composite positive pole piece by a roll-to-roll machine, wherein the density of the rolled and compacted composite pole piece is 2.5-3.0g/cm3(on-chip amount). And cutting the composite positive electrode into an electrode plate with the diameter of 16mm, taking a lithium plate as a negative electrode, assembling and packaging in a glove box filled with argon atmosphere to obtain the CR2025 button type all-solid-state battery. FIG. 7 is the AC impedance of a Li-Mn/Li-rich all-solid-state batteryFigure (a).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The garnet solid electrolyte powder with superfine granularity is characterized in that the powder phase has a cubic phase structure, the powder particle size is less than 1 mu m, the particle size distribution is unimodal distribution, and the garnet solid electrolyte powder with superfine granularity has high specific surface area (a)>1500m2·Kg-1)。
2. The ultrafine particle size garnet-type solid electrolyte powder of claim 1, wherein the LLZO powder comprises lithium, lanthanum, zirconium and doping elements, wherein the doping elements comprise aluminum, iron, gallium, yttrium, cerium, antimony, tantalum, niobium, vanadium; the doping metering ratio is 0.01-0.6 parts according to the quantity ratio of the element substances.
3. A method for preparing the ultra-fine particle size garnet-type solid electrolyte powder of any one of claims 1 to 2 by wet ball milling, comprising the steps of:
(1) weighing each compound comprising lithium, lanthanum, zirconium and doping elements according to a set metering ratio, and mixing the compound with a ball-milling solvent and a ball-milling medium according to respective proportions to prepare mixed slurry;
wherein the compound forms of lithium, lanthanum, zirconium and doping elements include, but are not limited to, oxides, nitrates, carbonates, hydroxides thereof;
(2) performing ball milling treatment on the mixture obtained in the step (1) to obtain uniform slurry, and drying to obtain mixed raw material powder;
(3) carrying out high-temperature calcination treatment on the mixed raw material powder obtained in the step (2) to obtain cubic phase LLZO coarse powder;
(4) mixing the cubic phase LLZO coarse powder obtained in the step (3) with a ball milling solvent and a ball milling medium according to respective proportions;
(5) and (4) performing ball milling treatment on the mixture obtained in the step (4) to obtain uniform slurry, and drying to obtain the electrolyte powder.
4. The preparation method according to claim 3, wherein the content in step (1) is, in terms of element mass ratio: 6.4-7 parts of lithium, 2.6-3 parts of lanthanum, 1.4-2 parts of zirconium and 0.01-0.6 part of doping element.
5. The preparation method according to claim 3, wherein the ball milling solvent in the steps (1) and (3) is an organic solvent, preferably an alcohol solvent such as alcohol and isopropanol, and the mass ratio of the ball milling solvent to the material is 1: 2-2: 1, the ball milling medium in the step (1) comprises but is not limited to yttrium stabilized zirconia, agate and the like, and the diameter of the ball milling medium is 0.8mm-40 mm.
6. The method of claim 3, wherein the ball milling and crushing in step (2) is carried out by using mechanical types including, but not limited to, tumbling ball mill, planetary ball mill, horizontal sand mill, etc.; the rotation speed of the ball milling treatment is 200-.
7. The method according to claim 3, wherein the drying temperature in the step (2) and the drying time in the step (5) are 70-80 ℃ and 10-40 h.
8. The method as claimed in claim 3, wherein the calcination treatment temperature in step (3) is 700-950 ℃, the calcination time is 6-12h, and the temperature rise rate is 2-10 ℃/min. The method of claim 4, wherein the ball milling process of step (5) is carried out using mechanical types including, but not limited to, a tumbling ball mill, a planetary ball mill, a horizontal sand mill, etc.; the rotation speed of ball milling treatment is 200-2000r/min, the ball milling treatment time is 2-8h, and the viscosity of the slurry is controlled to be 20-100 mPa.s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010775480.4A CN111786014A (en) | 2020-08-05 | 2020-08-05 | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010775480.4A CN111786014A (en) | 2020-08-05 | 2020-08-05 | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111786014A true CN111786014A (en) | 2020-10-16 |
Family
ID=72766465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010775480.4A Pending CN111786014A (en) | 2020-08-05 | 2020-08-05 | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111786014A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670564A (en) * | 2020-12-31 | 2021-04-16 | 宁波容百新能源科技股份有限公司 | Preparation method of nano solid electrolyte powder material |
| CN113517466A (en) * | 2021-06-29 | 2021-10-19 | 浙江锋锂新能源科技有限公司 | High-dispersion superfine solid electrolyte powder, preparation method and slurry dispersion method |
| CN114447420A (en) * | 2021-12-09 | 2022-05-06 | 电子科技大学长三角研究院(湖州) | Cerium-doped garnet-type LLZO solid electrolyte for inhibiting growth of lithium dendrites and preparation method thereof |
| CN115799607A (en) * | 2022-10-31 | 2023-03-14 | 海南大学 | Oxide-based composite solid electrolyte and solid lithium battery thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160149260A1 (en) * | 2014-11-26 | 2016-05-26 | Corning Incorporated | Stabilized solid garnet electrolyte and methods thereof |
| US20180277890A1 (en) * | 2016-03-31 | 2018-09-27 | Hitachi Metals, Ltd. | Solid electrolyte for all-solid-state lithium ion secondary battery, all-solid-state lithium ion secondary battery using the same, and method for producing solid electrolyte for all-solid-state lithium ion secondary battery |
| CN108727025A (en) * | 2017-04-17 | 2018-11-02 | 中国科学院上海硅酸盐研究所 | Lithium garnet composite ceramics, Its Preparation Method And Use |
| CN109244549A (en) * | 2018-09-03 | 2019-01-18 | 江西理工大学 | Method for preparing garnet electrolyte sheet with high density and high conductivity by guiding crystal growth |
| CN109659603A (en) * | 2017-10-11 | 2019-04-19 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of ultra-fine solid electrolyte and preparation method thereof |
| CN109830740A (en) * | 2019-02-14 | 2019-05-31 | 北京工业大学 | A kind of solid electrolyte and all-solid-state battery |
| CN110790573A (en) * | 2019-11-25 | 2020-02-14 | 北京科技大学 | Method for thoroughly eliminating lithium carbonate by garnet type lithium ion solid electrolyte |
-
2020
- 2020-08-05 CN CN202010775480.4A patent/CN111786014A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160149260A1 (en) * | 2014-11-26 | 2016-05-26 | Corning Incorporated | Stabilized solid garnet electrolyte and methods thereof |
| US20180277890A1 (en) * | 2016-03-31 | 2018-09-27 | Hitachi Metals, Ltd. | Solid electrolyte for all-solid-state lithium ion secondary battery, all-solid-state lithium ion secondary battery using the same, and method for producing solid electrolyte for all-solid-state lithium ion secondary battery |
| CN108727025A (en) * | 2017-04-17 | 2018-11-02 | 中国科学院上海硅酸盐研究所 | Lithium garnet composite ceramics, Its Preparation Method And Use |
| CN109659603A (en) * | 2017-10-11 | 2019-04-19 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of ultra-fine solid electrolyte and preparation method thereof |
| CN109244549A (en) * | 2018-09-03 | 2019-01-18 | 江西理工大学 | Method for preparing garnet electrolyte sheet with high density and high conductivity by guiding crystal growth |
| CN109830740A (en) * | 2019-02-14 | 2019-05-31 | 北京工业大学 | A kind of solid electrolyte and all-solid-state battery |
| CN110790573A (en) * | 2019-11-25 | 2020-02-14 | 北京科技大学 | Method for thoroughly eliminating lithium carbonate by garnet type lithium ion solid electrolyte |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670564A (en) * | 2020-12-31 | 2021-04-16 | 宁波容百新能源科技股份有限公司 | Preparation method of nano solid electrolyte powder material |
| CN113517466A (en) * | 2021-06-29 | 2021-10-19 | 浙江锋锂新能源科技有限公司 | High-dispersion superfine solid electrolyte powder, preparation method and slurry dispersion method |
| CN114447420A (en) * | 2021-12-09 | 2022-05-06 | 电子科技大学长三角研究院(湖州) | Cerium-doped garnet-type LLZO solid electrolyte for inhibiting growth of lithium dendrites and preparation method thereof |
| CN114447420B (en) * | 2021-12-09 | 2024-04-09 | 电子科技大学长三角研究院(湖州) | Cerium doped garnet type LLZO solid electrolyte for inhibiting growth of lithium dendrites and preparation method thereof |
| CN115799607A (en) * | 2022-10-31 | 2023-03-14 | 海南大学 | Oxide-based composite solid electrolyte and solid lithium battery thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111786014A (en) | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof | |
| CN112397776B (en) | Ga and Al co-doped LLZO solid electrolyte, multi-element solid battery and preparation method thereof | |
| JPH0855624A (en) | Layer structured oxide and secondary battery | |
| CN110885246A (en) | High-conductivity solid electrolyte prepared by sol-gel method | |
| Zhao et al. | Self-consolidation mechanism and its application in the preparation of Al-doped cubic Li7La3Zr2O12 | |
| CN109626996A (en) | A kind of ferro-aluminum codope carbuncle type Li7La3Zr2O12Lithium Ionic Conducting Materials and preparation method thereof | |
| CN108793987A (en) | A kind of new type lithium ion conductive oxide solid electrolyte and preparation method thereof | |
| CN115275329A (en) | Preparation method and application of garnet type solid electrolyte | |
| CN107681195A (en) | The preparation method of nanometer garnet-type solid electrolyte material | |
| CN110922187A (en) | Preparation method of garnet type lithium ion solid electrolyte for removing lithium carbonate | |
| CN112939601A (en) | Electrolyte material, preparation method and application thereof | |
| CN112573574A (en) | Method for preparing garnet type solid electrolyte by regulating and controlling content of lithium vacancy | |
| CN110128140A (en) | A kind of ytterbium aluminium codope carbuncle type Li7La3Zr2O12Lithium Ionic Conducting Materials and preparation method thereof | |
| CN114520318A (en) | High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method thereof | |
| CN113564708B (en) | Method for preparing single crystal lithium nickel cobalt aluminum oxide | |
| WO2017005077A1 (en) | Electrochemical preparation method for perovskite-type solid electrolyte lithium-lanthanum-titanium oxide compound | |
| CN113372110A (en) | Method for preparing perovskite type solid electrolyte lanthanum lithium titanate based on high-temperature and high-pressure synthesis | |
| Gabriel et al. | Dense m-Li2ZrO3 formed by aqueous slip casting technique: Colloidal and rheological characterization | |
| CN114447420B (en) | Cerium doped garnet type LLZO solid electrolyte for inhibiting growth of lithium dendrites and preparation method thereof | |
| CN114497714B (en) | Preparation method of garnet type solid electrolyte with high ion conductivity | |
| CN111786015A (en) | Novel composite anode and manufacturing method of all-solid-state lithium battery | |
| CN111106380A (en) | Preparation method of solid electrolyte with surface coating and solid electrolyte battery | |
| CN112537958B (en) | Lanthanum lithium zirconate solid electrolyte and preparation method thereof | |
| CN115101806A (en) | Oxide solid electrolyte, preparation method thereof, lithium battery and battery pack | |
| CN114478002B (en) | Lithium lanthanum zirconium oxygen-based solid electrolyte ceramic body and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201016 |
|
| RJ01 | Rejection of invention patent application after publication |