CN106384801A - Preparation method of oxide solid electrolyte diaphragm - Google Patents

Preparation method of oxide solid electrolyte diaphragm Download PDF

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Publication number
CN106384801A
CN106384801A CN201610877257.4A CN201610877257A CN106384801A CN 106384801 A CN106384801 A CN 106384801A CN 201610877257 A CN201610877257 A CN 201610877257A CN 106384801 A CN106384801 A CN 106384801A
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oxide
solid electrolyte
lithium
block
electrolyte
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CN106384801B (en
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赵鹏程
曹高萍
文越华
徐艳
程杰
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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 invention relates to a preparation method of an oxide solid electrolyte diaphragm, belonging to the fields of electro chemical engineering and ceramic industry. The method comprises the following steps: by using lithium carbonate or lithium hydroxide as a lithium source, putting previously prepared solid electrolyte powder in a crucible, and directly sintering at high temperature to obtain a compact block; and carrying out cutting and sanding on the block to obtain the solid electrolyte diaphragm sheet. The method avoids the complex mold preforming process in the conventional method; and the mechanical energy is converted into the surface free energy of the powder granules by ball milling, the excessive low-melting-point lithium salt is molten at high temperature to generate the liquid phase which is covered on the powder particle surfaces, and the powder automatic aggregates under the action of surface tension, so that the surface free energy is lowered, thereby forming the compact solid electrolyte block. The method has the advantages of simple technique, smooth and compact finished product and the like, can easily implement large-scale production, and is especially suitable for preparing oxide solid electrolyte diaphragms in the solid secondary battery.

Description

A kind of solid oxide electrolyte barrier film preparation method
Technical field
The present invention relates to a kind of preparation method of solid oxide electrolyte barrier film, belong to Electrochemical Engineering and ceramic industry Field.
Background technology
Due to adopting organic electrolyte, there is the potential danger such as burning and blast in conventional lithium ion battery.Lithium of new generation from Sub- battery is so-called " all-solid-state battery ", replaces flammable organic electrolyte 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 Temperature descends ionic conductivity low it is difficult to apply in all-solid-state battery.And although inorganic solid electrolyte scale masking difficulty is big, But ionic conductivity is high, selectivity is good, long service life, becomes the research main flow of all-solid-state battery barrier film.
Inorganic solid electrolyte species is various, and current research focus mainly has sulfide solid electrolyte, lanthanium titanate lithium And Li (LLTO)7La3Zr2O12(LLZO) etc..Wherein with sulfide solid electrolyte conductivity highest, but its preparation is both needed in Ar Carry out under protective atmosphere, complex operation, electrolyte is very sensitive to moisture, stability is poor.Under room temperature, LLTO ionic conductivity can Reach 10-3S/cm, but in LLTO, the redox potential of Ti is less than 1.8V vs.Li/Li+, contact unstable with lithium metal, unsuitable Use directly as solid state battery barrier film.Murugan etc. prepares a cube crystalline phase LLZO solid electrolyte, its ionic conduction in the recent period Rate up to 5 × 10-4S/cm.LLZO not only has the advantages that electron conduction very little, grain boundary resistance be little, electrochemical stability is good, Also show and contact good stability with lithium metal, thus having caused the upsurge of LLZO solid electrolyte research.
The synthetic method of existing LLZO powder body mainly has conventional solid reaction method, sol-gel process, spraying-pyrolysismethod, field Assisted sintering method and chemical vapour deposition technique etc..However, no matter using which kind of method preparation LLZO powder body, be finally all intended to by LLZO powder-compacting flakiness, then sinter ceramic diaphragm at high temperature into.During by die methods tabletting, the tableting processes of powder body take When, laborious, and be difficult to prevent the pollution to sample for the grinding tool.Additionally, chip sample is susceptible to torsional deformation in sintering process The even phenomenon such as rupture, there is also the sintering pollution to sample for the environment simultaneously.Front using as battery diaphragm, generally also need into Row removing surface, polishing, especially in bruting process, ceramic diaphragm is easily damaged.If it is not complete to sinter the ceramic diaphragm obtaining Entirely smooth, in solid state battery pressurization assembling process, also easily stress crushes, and assembling is difficult.
Content of the invention
Present invention aim to address need before conventional solid-state method septation sintering in advance tabletting, yielding in sintering process, The problems such as later stage processes cracky, provides a kind of process is simple, finished product smooth fine and close, easy scale high ion conductivity oxidation Thing solid electrolyte diaphragm preparation method.
The solve the above problems technical scheme of employing of the present invention is：By lithium carbonate or Lithium hydrate, lanthana, zirconium oxide and Doping oxide ball milling 1～24h is mixed to get just material；Just material pre-burning 1～15h at 700～1200 DEG C, then ball milling 1～24h obtains To solid oxide electrolyte powder body, diameter of particle is 1～30 micron；Under gas shield, powder body is placed in crucible, then It is incubated 1～48h at 1000～1500 DEG C, obtain solid oxide electrolyte block；Using cutting machine by block cutting be 0.1～ The thick solid electrolyte diaphragm piece of 2mm；
Lithium carbonate, lanthana, zirconium oxide, the mol ratio of doping oxide are：3.5～6: 3: 2: 0.001～0.5；Hydrogen-oxygen Change lithium, lanthana, zirconium oxide, the mol ratio of doping oxide are：7～12: 3: 2: 0.001～0.5.
Doping oxide is one or more of aluminium oxide, tantalum oxide, niobium oxide, tungsten oxide, stannum oxide.
Protective gas is one or more of oxygen, air, nitrogen, helium, argon.
The principle of the solid oxide electrolyte barrier film preparation method of the present invention：First pass through ball milling to be changed into mechanical energy The surface free energy of powder granule；Then melt generation liquid phase at high temperature using excessive low melting point lithium salts to cover in LLZO powder Body particle surface, makes powder body automatically reunite under surface tension effects, and surface free energy reduces, and forms dense solid electrolyte mass Body；Obtain solid electrolyte diaphragm finally by cutting block, thus it is variable in sintering process septation to avoid conventional method A difficult problem for shape, simultaneously block in sintering process only outer surface easily in sintering process be subject to environmental pollution, therefore also significantly drop Low contaminated probability in sintering process for the barrier film sample.
Beneficial effects of the present invention：Need not add binding agent, it is to avoid binding agent in sintering process discharge gas to solid The impact of body electrolyte；Without numerous and diverse mould tableting processes in conventional method, solid electrolyte finished product consistency is up to 96% More than；Barrier film then cuts preparation by powder body direct sintering in bulk, and finished product flatness is high and is easy to mass production.Therefore, should Method has the advantages that smooth fine and close, the easy scale of process is simple, finished product, and the method is prepared lithium ion at 30 DEG C for the finished product and led Electric rate is up to 10-4More than S/cm, is particularly suitable for the preparation of solid oxide electrolyte barrier film in solid secondary batteries.
Brief description
Fig. 1 solid oxide electrolyte barrier film finished surface electron micrograph
Specific embodiment
Example 1
Press Li first7La3Zr2O12Proportioning, weighs Lithium hydrate (LiOH, excessive 15%) 12.3135g, zirconium oxide respectively (ZrO2) 8.8930g, lanthana (La2O3) 17.4594g, it is placed in ball grinder, adds 20ml dehydrated alcohol, drum's speed of rotation is 400 revs/min, ball milling 10h；The slurry obtaining is dried 10h at 120 DEG C, then grinds and obtains material at the beginning of oxide；Just material is placed in control In corundum crucible in warm stove, be rapidly heated at 1150 DEG C insulation 10h；First material after high-temperature process passes through grinding, ball milling again Directly pulverize and mix homogeneously, obtain LLZO powder body with after 100 mesh sieve screenings, it is tested using Malvern laser particle analyzer and puts down All particle diameter is 10.88 microns；The powder obtaining is placed in corundum crucible, is placed in temperature control furnace, in atmosphere, high at 1150 DEG C Temperature sintering 15h, obtains the solid oxide electrolyte block of densification；Using platform mill cutting machine, block cutting is become the thickness to be 1.640cm × 1.178cm thin slice of 1.456mm, then carries out surface polishing using 1000 mesh diamond chips, obtains solid electrolytic Matter barrier film thin slice.It is 4.7336g/cm3 using drainage test block density, consistency is 92.64%；Silver is brushed in barrier film both sides Slurry, adopts AC impedence method to test, at 30 DEG C, its lithium ion conducting rate is 6.47 × 10 in calorstat-5S/cm.
Example 2
Weigh lithium carbonate (Li respectively2CO3, excessive 10%) 10.3704g, zirconium oxide (ZrO2) 8.8930g, lanthana (La2O3) 17.4594g and tantalum oxide (Ta2O5) 1.0525g, it is placed in ball grinder, adds 20ml dehydrated alcohol, ball mill turns Speed is 400 revs/min, ball milling 10h；The slurry obtaining is dried 10h at 120 DEG C, grinds and obtains material at the beginning of oxide；Just material is placed in In corundum crucible in temperature control furnace, be rapidly heated at 1150 DEG C insulation 10h；First material after high-temperature process passes through grinding, ball again The modes such as mill are directly pulverized and mix homogeneously, obtain LLZO powder body with after 100 mesh sieve screenings；The powder obtaining is placed in corundum In crucible, it is placed in temperature control furnace, in atmosphere, high temperature sintering 20h at 1150 DEG C, obtain the solid oxide electrolyte block of densification Body；Block cutting is become by 1.730cm × 1.528cm thin slice that thickness is 1.490mm using platform mill cutting machine, then adopts 1000 Mesh diamond chip carries out surface polishing, obtains solid electrolyte diaphragm thin slice.Using drainage test block density it is 4.9261g/cm3, consistency is 96.44%；SEM test shows, barrier film sheet surface is dense non-porous, as shown in Figure 1；Barrier film Silver paste is brushed in both sides, adopts AC impedence method to test in calorstat, and at 30 DEG C, its lithium ion conducting rate is 3.60 × 10-4S/ cm.
In above example 1,2, solid electrolyte finished product consistency is respectively 92.64% and 96.44%, is above document report The traditional dies pressed disc method sintering in road prepares the consistency 70～90% of sample；In example 2 doping tantalum oxide after sample lithium from Electronic conduction rate significantly improves.

Claims (1)

1. a kind of solid oxide electrolyte barrier film preparation method it is characterised in that：By lithium carbonate or Lithium hydrate, lanthana, Zirconium oxide and doping oxide ball milling 1～24h are mixed to get just material；Just material pre-burning 1～15h at 700～1200 DEG C, then ball milling 1～24h obtains solid oxide electrolyte powder body, and diameter of particle is 1～30 micron；Under gas shield, powder body is placed in earthenware In crucible, then it is incubated 1～48h at 1000～1500 DEG C, obtain solid oxide electrolyte block；Using cutting machine, block is cut It is segmented into the thick solid electrolyte diaphragm piece of 0.1～2mm；
Described lithium carbonate, lanthana, zirconium oxide, the mol ratio of doping oxide are：3.5～6: 3: 2: 0.001～0.5；Hydrogen-oxygen Change lithium, lanthana, zirconium oxide, the mol ratio of doping oxide are：7～12: 3: 2: 0.001～0.5；
Described doping oxide is one or more of aluminium oxide, tantalum oxide, niobium oxide, tungsten oxide, stannum oxide；
Described gas is one or more of oxygen, air, nitrogen, helium, argon.
CN201610877257.4A 2016-10-09 2016-10-09 Preparation method of oxide solid electrolyte diaphragm Active CN106384801B (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106898821A (en) * 2017-03-16 2017-06-27 中国人民解放军63971部队 A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method
CN108408708A (en) * 2018-03-14 2018-08-17 华侨大学 The preparation method of crystalline state LAGP solid electrolyte sheets
CN108808075A (en) * 2018-06-14 2018-11-13 东华大学 A kind of flexible inorganic solid electrolyte film and its preparation and application
CN109369182A (en) * 2018-11-29 2019-02-22 江苏海基新能源股份有限公司 A kind of preparation method of cubic phase garnet solid electrolyte material
CN109755637A (en) * 2018-12-29 2019-05-14 浙江南都电源动力股份有限公司 Oxide ceramics composite solid electrolyte, preparation method and its application
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
CN113161607A (en) * 2021-02-04 2021-07-23 广西科技大学 Preparation method of high-conductivity solid-state battery electrolyte for battery of energy storage charging system
CN113186535A (en) * 2021-04-22 2021-07-30 海信(广东)厨卫系统股份有限公司 Solid electrolyte, preparation method thereof and cathode protection system
CN113880577A (en) * 2021-10-13 2022-01-04 上海交通大学 Dry preparation process of solid electrolyte
CN115724662A (en) * 2022-12-01 2023-03-03 淄博火炬能源有限责任公司 Oxide solid electrolyte and preparation process thereof
TWI806196B (en) * 2021-10-18 2023-06-21 芯量科技股份有限公司 Solid electrolyte film, manufacturing method of the same, and battery including the same

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JP2011073962A (en) * 2009-09-03 2011-04-14 Ngk Insulators Ltd Ceramic material and preparation method therefor
CN104159869A (en) * 2012-03-02 2014-11-19 日本碍子株式会社 Solid electrolyte ceramic material and production method therefor
CN105914396A (en) * 2016-06-01 2016-08-31 浙江大学 Preparation method of ultrathin nano-lithium lanthanum zirconium oxygen all-solid-state electrolyte layer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011073962A (en) * 2009-09-03 2011-04-14 Ngk Insulators Ltd Ceramic material and preparation method therefor
CN104159869A (en) * 2012-03-02 2014-11-19 日本碍子株式会社 Solid electrolyte ceramic material and production method therefor
CN105914396A (en) * 2016-06-01 2016-08-31 浙江大学 Preparation method of ultrathin nano-lithium lanthanum zirconium oxygen all-solid-state electrolyte layer

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106898821A (en) * 2017-03-16 2017-06-27 中国人民解放军63971部队 A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method
CN108408708A (en) * 2018-03-14 2018-08-17 华侨大学 The preparation method of crystalline state LAGP solid electrolyte sheets
CN108808075A (en) * 2018-06-14 2018-11-13 东华大学 A kind of flexible inorganic solid electrolyte film and its preparation and application
CN108808075B (en) * 2018-06-14 2020-06-23 东华大学 Flexible inorganic solid electrolyte film and preparation and application thereof
CN109369182A (en) * 2018-11-29 2019-02-22 江苏海基新能源股份有限公司 A kind of preparation method of cubic phase garnet solid electrolyte material
CN109755637B (en) * 2018-12-29 2022-04-19 浙江南都电源动力股份有限公司 Oxide ceramic composite solid electrolyte, preparation method and application thereof
CN109755637A (en) * 2018-12-29 2019-05-14 浙江南都电源动力股份有限公司 Oxide ceramics composite solid electrolyte, preparation method and its application
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
CN113161607A (en) * 2021-02-04 2021-07-23 广西科技大学 Preparation method of high-conductivity solid-state battery electrolyte for battery of energy storage charging system
CN113186535A (en) * 2021-04-22 2021-07-30 海信(广东)厨卫系统股份有限公司 Solid electrolyte, preparation method thereof and cathode protection system
CN113880577A (en) * 2021-10-13 2022-01-04 上海交通大学 Dry preparation process of solid electrolyte
TWI806196B (en) * 2021-10-18 2023-06-21 芯量科技股份有限公司 Solid electrolyte film, manufacturing method of the same, and battery including the same
CN115724662A (en) * 2022-12-01 2023-03-03 淄博火炬能源有限责任公司 Oxide solid electrolyte and preparation process thereof

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