CN106898821A - A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method - Google Patents

A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method Download PDF

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CN106898821A
CN106898821A CN201710156310.6A CN201710156310A CN106898821A CN 106898821 A CN106898821 A CN 106898821A CN 201710156310 A CN201710156310 A CN 201710156310A CN 106898821 A CN106898821 A CN 106898821A
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lithium
solid electrolyte
lithium lanthanum
powder
oxygen solid
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赵鹏程
曹高萍
祝夏雨
张松通
文越华
徐艳
金朝庆
明海
向宇
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63971 Troops of PLA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of preparation method of lithium lanthanum niobium oxygen solid electrolyte diaphragm, belong to Electrochemical Engineering and ceramic industry field.The method is lithium source using lithium carbonate, acetic acid or lithium hydroxide, and it is lithium lanthanum niobium oxygen solid electrolyte powder that the material powder that will mix is fired in advance, and then powder is placed in crucible, is directly sintered at high temperature after jolt ramming, obtains the block of densification；Block is cut, is polished, obtained lithium lanthanum zirconium oxygen solid electrolyte diaphragm thin slice.This method avoid mould tableting processes numerous and diverse in conventional method, without high-tension apparatus, without addition sintering aid, using the liquid phase surface tension of lithium salts melting generation under high temperature, make powder reuniting into compact block.The method has the advantages that smooth fine and close, the easy scale of process is simple, finished product, is particularly suitable for the preparation of lithium lanthanum zirconium oxygen solid electrolyte diaphragm in solid state battery.

Description

A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method
Technical field
The present invention relates to a kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method, belong to Electrochemical Engineering and ceramic industry Field.
Background technology
There is the potential danger such as burning and blast due to using organic electrolyte in conventional lithium ion battery.Lithium of new generation from Sub- battery is so-called " all-solid-state battery ", and flammable organic electrolyte is replaced using solid electrolyte, fundamentally solves electricity The safety problem in pond.Solid electrolyte can be roughly divided into high molecular polymerization species and inorganic species.High molecular polymerization species are in room The lower ionic conductivity of temperature is low, it is difficult to applied in all-solid-state battery.Although and inorganic solid electrolyte scale masking difficulty is big.
Inorganic solid electrolyte species is various, and current research focus mainly has sulfide solid electrolyte, Ca-Ti ore type solid Body electrolyte and garnet structure solid electrolyte etc..Wherein with sulfide solid electrolyte conductance highest, at room temperature up to 1.2 ×10-2S/cm, but its preparation is both needed to be carried out under Ar protective atmospheres, and complex operation, electrolyte is very sensitive to moisture, stability It is in urgent need to be improved.With lanthanium titanate lithium (Li in perovskite structure solid electrolyte3xLa2/3-xTiO3, x~0.1) the most typical, its structure Change with the change of Li+ contents, ionic conductivity is up to 10 at room temperature-3The redox of Ti in S/cm, but Li-La-Ti oxygen Potential is less than 1.8V vs.Li/Li+, contact unstable with lithium metal.With lithium lanthanum zirconium oxygen in garnet structure solid electrolyte (Li7La3Zr2O12) the most popular, Venkataraman Thangadura etc. prepare cubic phase crystal structure solid electricity in the recent period Xie Zhi, its ionic conductivity is up to 5 × 10-4S/cm, one to two orders of magnitude are improve compared with pure state Tetragonal lithium lanthanum zirconium oxygen.Garnet Structure solid electrolyte not only has the advantages that electron conduction is small, grain boundary resistance is small, electrochemical stability good, is also unique one Class shows to contact the solid oxide electrolyte of good stability with lithium metal.Relative to lithium lanthanum zirconium oxygen, lithium lanthanum niobium oxygen (Li5La3Nb2O12) it is the earliest garnet structure solid electrolyte for finding.1988, H.Hyooma and K.Hayashi were closed first Into lithium lanthanum niobium oxygen and its crystal structure is characterized, be typical Emission in Cubic., Venkataraman Thangadura hairs in 2003 The lithium ion conduction ability of lithium lanthanum niobium oxygen is showed, ionic conductivity is about 10 at 25 DEG C-6S/cm.With more high conductivity lithium lanthanum zirconium The rise of oxygen solid electrolyte research, lithium lanthanum niobium oxygen solid electrolytic Quality Research is rarely reported.Shingo Ohta etc. make for 2011 For cube crystalline phase lithium lanthanum niobium oxygen solid electrolyte is gone out, its ionic conductivity is also only 3 × 10-5S/cm.Cause lithium lanthanum niobium oxygen solid A low major reason of electrolyte ion conductance is exactly the low relative density of sample, and conventional method is usually less than 90%, and Lithium lanthanum zirconium oxygen sample report highest relative density up to 99.9%, close to extreme value.Conventional solid reaction method is the lithium having been reported Lanthanum niobium oxygen solid electrolyte often uses synthetic method, first by the grinding of primitive reaction thing or ball milling mixing, then at a certain temperature Roasting obtains lithium lanthanum niobium oxygen powder, then lithium lanthanum niobium oxygen powder is compacted into by cold isostatic pressing process under high pressure (more than 100MPa) Thin slice, finally sintering is prepared into solid electrolyte at high temperature.This kind of method is high to equipment requirement, ball mill grinding, compressing tablet, sintering Process is complicated, and powder compression molding is difficult, and mortality is high, and the cleaning bruting process after sintering process, the shaping of thin slice is all easy Situations such as occurring broken, while there is tableting processes grinding tool pollutes hidden danger to sample, wastes time and energy, is difficult to scale.
The content of the invention
When preparing lithium lanthanum niobium oxygen solid electrolyte diaphragm present invention aim to address conventional method, process complexity is cumbersome, Waste time and energy, the problems such as sample easily pollutes, there is provided a kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method.
The present invention solves the above problems the technical scheme of use, and lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method step is such as Under：
1~24h of ball milling obtains just expecting after lithium-containing compound, lanthana, niobium oxide are mixed；Just material is at 500~1500 DEG C 1~30h of lower pre-burning, then 1~24h of ball milling obtains solid oxide electrolyte powder, and diameter of particle is 1~30 micron；In gas Under protection, powder is placed in crucible, then 1~72h is incubated at 500~1500 DEG C, obtain solid electrolyte block；By solid Electrolyte slug is cut into the thick solid electrolyte diaphragm pieces of 0.05~5mm；
The lithium-containing compound is one or more of lithium carbonate, lithium acetate, lithium hydroxide；Lithium carbonate or lithium acetate and oxygen Change lanthanum, the mixing mol ratio 2.5~4: 3: 2 of niobium oxide；Lithium hydroxide, lanthana, the mixing mol ratio of niobium oxide are：5~8: 3 ∶2；
The gas is one or more of oxygen, air, nitrogen, helium, argon gas.
The principle of solid oxide electrolyte barrier film preparation method proposed by the present invention is：Under in the high-temperature sintering process, The melting of lithiumation thing is liquid, while the liquid has affinity in lithium lanthanum niobium oxygen particle surface, is distributed in other solid phase particles Surface, can tense together solid particle in the presence of liquid phase surface tension, form dense solid electrolyte mass body.
Beneficial effects of the present invention：Numerous and diverse mould tableting processes in conventional solid reaction method are avoided, without high pressure Equipment, method is simple, and success rate is high, is adapted to scale and prepares.The lithium lanthanum niobium oxygen solid electrolyte diaphragm prepared, finished product consistency Up to more than 96%, and nearly hundred microns of particle size, make the crystalline substance as lithium ion conduction impedance main source in solid electrolyte Boundary's impedance is substantially reduced, and room-temperature ion conductance is up to 10-4More than S/cm is higher by 1~2 than sample prepared by conventional solid reaction method The individual order of magnitude, is particularly suitable for the preparation of lithium lanthanum niobium oxygen solid electrolyte diaphragm.
Brief description of the drawings
Fig. 1 lithiums lanthanum niobium oxygen solid electrolyte block and section outward appearance picture
Fig. 2 lithium lanthanum niobium oxygen barrier film finished products section electron micrograph
Specific embodiment
Example 1
Lithium carbonate (Li is weighed respectively2CO3, excessive 15%) 14.6031g, lanthana (La2O3) 23.2793g and oxidation Niobium (Nb2O5) 10.0966g, it is placed in ball grinder, 20ml absolute ethyl alcohols are added, drum's speed of rotation is 400 revs/min, ball milling 10h；The slurry for obtaining dries 10h at 80 DEG C, and grinding is expected at the beginning of obtaining oxide；Just expect the corundum crucible being placed in temperature control furnace It is interior, it is rapidly heated and is incubated 10h at 1150 DEG C；First material after high-temperature process is directly crushed simultaneously by modes such as grinding, ball millings again It is well mixed, lithium lanthanum niobium oxygen powder is obtained after being sieved with 100 mesh sieve, its average grain diameter is tested using Malvern laser particle analyzer About 12 microns；The powder that will be obtained is placed in cylindrical corundum crucible, is placed in temperature control furnace, in atmosphere, high at 1150 DEG C Temperature sintering 10h, obtains the solid electrolyte block of densification；Use platform grind cutting machine by block cutting into thickness for 2mm is a diameter of The thin slice of 1.5cm, then carries out surface polishing using 1000 mesh diamond chips, obtains solid electrolyte diaphragm thin slice.Using row Water law test block body relative density is 96%；SEM tests show that barrier film sheet surface is dense non-porous, as shown in figure 1, sintering Form the large granule that size is up to 87 μm；Show that sample lithium ion conducting rate at 30 DEG C reaches using AC impedence method test 1.08×10-4S/cm。
Solid electrolyte finished product relative density up to 96%, burn by the traditional dies pressed disc method higher than document report in above example Knot prepares the consistency 55~80% of sample, and sintering forms size, and up to 87 μm of large granule, (document report is usually several micro- Rice), the formation of fine and close huge particle greatly reduces intergranular Intergranular impedance, makes the ionic conductivity of sample compared with literature value Improve one to two orders of magnitude.

Claims (1)

1. a kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method, it is characterised in that prepared by lithium lanthanum niobium oxygen solid electrolyte diaphragm Method and step is as follows：
1~24h of ball milling obtains just expecting after lithium-containing compound, lanthana, niobium oxide are mixed；Just material is pre- at 500~1500 DEG C 1~30h is burnt, then 1~24h of ball milling obtains solid oxide electrolyte powder, diameter of particle is 1~30 micron；In gas shield Under, powder is placed in crucible, then 1~72h is incubated at 500~1500 DEG C, obtain solid electrolyte block；By solid electrolytic Mass body is cut into the thick solid electrolyte diaphragm pieces of 0.05~5mm；
The lithium-containing compound is one or more of lithium carbonate, lithium acetate, lithium hydroxide；Lithium carbonate or lithium acetate and oxidation The mixing mol ratio 2.5~4: 3: 2 of lanthanum, niobium oxide；Lithium hydroxide, lanthana, the mixing mol ratio of niobium oxide are：5~8: 3: 2；
The gas is one or more of oxygen, air, nitrogen, helium, argon gas.
CN201710156310.6A 2017-03-16 2017-03-16 A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method Pending CN106898821A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638348A (en) * 2018-12-20 2019-04-16 天津市捷威动力工业有限公司 A method of lithium lanthanum zirconium oxygen solid electrolyte is prepared using rheological phase reaction
CN109950616A (en) * 2019-03-13 2019-06-28 江西星盈科技有限公司 Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process
CN110451800A (en) * 2019-08-27 2019-11-15 江西理工大学 One kind solid electrolyte of glass containing niobium and preparation method thereof
CN111370627A (en) * 2020-03-27 2020-07-03 中国人民解放军军事科学院防化研究院 Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm

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CN106384801A (en) * 2016-10-09 2017-02-08 中国人民解放军63971部队 Preparation method of oxide solid electrolyte diaphragm

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CN106384801A (en) * 2016-10-09 2017-02-08 中国人民解放军63971部队 Preparation method of oxide solid electrolyte diaphragm

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638348A (en) * 2018-12-20 2019-04-16 天津市捷威动力工业有限公司 A method of lithium lanthanum zirconium oxygen solid electrolyte is prepared using rheological phase reaction
CN109950616A (en) * 2019-03-13 2019-06-28 江西星盈科技有限公司 Lacking oxygen solid electrolyte and positive electrode and positive plate and lithium ion battery and preparation process
CN110451800A (en) * 2019-08-27 2019-11-15 江西理工大学 One kind solid electrolyte of glass containing niobium and preparation method thereof
CN110451800B (en) * 2019-08-27 2021-12-07 江西理工大学 Niobium-containing glass solid electrolyte and preparation method thereof
CN111370627A (en) * 2020-03-27 2020-07-03 中国人民解放军军事科学院防化研究院 Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm

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