CN105406118A - Ceramic solid electrolyte and preparation method thereof - Google Patents

Ceramic solid electrolyte and preparation method thereof Download PDF

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Publication number
CN105406118A
CN105406118A CN201511016931.1A CN201511016931A CN105406118A CN 105406118 A CN105406118 A CN 105406118A CN 201511016931 A CN201511016931 A CN 201511016931A CN 105406118 A CN105406118 A CN 105406118A
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Prior art keywords
solid electrolyte
ceramic solid
preparation
lithium
ceramic
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CN201511016931.1A
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Chinese (zh)
Inventor
高云智
李琴
曹毅
付传凯
尹鸽平
左朋建
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic 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

Abstract

The invention discloses a ceramic solid electrolyte and a preparation method thereof. The ceramic solid electrolyte comprises at least one of NASICON structure type (LiM<2>(PO<4>)<3>, M=Zr, Ge, Mg, Al), oxide (Li<3x>La<2/3-x>TiO<3>) of perovskite structure and oxide (Li<5>La<3>M<2>O<12>) of garnet structure. The preparation method of the ceramic solid electrolyte comprises the following steps of: a) weighing raw materials according to molar ratio of elements in chemical formula of the ceramic solid electrolyte, dissolving the raw materials in solvent, and obtaining mixed solution; b) preparing ceramic solid electrolyte precursor powder from the mixed solution through a spray drying process; c) sintering the precursor powder obtained by spray drying in the air, and finally obtaining the ceramic solid electrolyte with relatively high ionic conductivity and relatively low electronic conductivity. In the method provided by the invention, the spray drying process is used for preparing the ceramic solid electrolyte, spray drying has the advantages that the drying procedure is fast, the mixed solution is directly dried into powder and particle size distribution of the powder is uniform, and thus, large-scale preparation of the ceramic solid electrolyte is expected to be realized, and the method has practical value.

Description

A kind of ceramic solid electrolyte and preparation method thereof
Technical field
The invention belongs to battery material preparing technical field, relate to a kind of ceramic solid electrolyte and preparation method thereof.
Background technology
Current lithium ion liquid state electrolyte battery has high operating voltage, energy density, mass density, long cycle life, is therefore considered to the optimal selection of Future New Energy Source automobile medium power battery.But most of commercial lithium ion battery is owing to using liquid electrolyte at present, there is the potential safety hazards such as burning, blast, leakage, seriously limits the application of lithium ion battery at electric automobile field, energy-accumulating power station etc.
Use inorganic solid electrolyte to replace the solid lithium battery of liquid electrolyte, fundamentally can solve the potential safety hazard of lithium ion battery, serviceability temperature scope and the storage life of lithium ion battery can be improved simultaneously.But require that inorganic solid electrolyte has higher ionic conductivity (> 10 -4s/cm), simultaneously electrolyte preparation technology is simple, and synthesis condition is gentle, so that the requirement of extensive preparation and high-performance all-solid lithium-ion battery.
At present, in order to solve the problem, numerous researcher has carried out large quantity research:
As CN103113107A discloses a kind of ceramic solid electrolyte Li 7-xla 3zr 2-xta xo 12preparation method.This invention adopts liquid sintering technology, adds the liquid-phase sintering auxiliary agent containing lithium ion, achieves under lower sintering temperature, obtain the Li of the garnet structure of high-compactness in ceramic powders 7-xla 3zr 2-xta xo 12ceramic solid electrolyte, and prepared electrolyte has higher room-temperature conductivity, but its sintering temperature (1170 DEG C) still awaits further reduction, ionic conductivity (10 -4s/cm) further raising is awaited.
CN104051782A discloses a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3grain boundary layer zr element composition.This invention gained composite solid lithium-ion electrolyte material improves grain boundary conductivities and the total conductivity of lithium lanthanum titanium oxide, and preparation technology is simple.But sintering temperature (1250-1350 DEG C) also needs further reduction.
CN103594725A discloses lithium ion battery solid electrolyte material Li 7la 3zr 2o 12preparation method, be intended to solve the operating condition harshness of prior art preparation method, processed complex, deficiency that production cost is high.The method will in stock dispersion medium ball milling mix, dry after mix precalcining with glucose or sucrose, the predecessor after precalcining is ball milling dispersion treatment again, and then mixing with glucose or sucrose must Li after calcining 7la 3zr 2o 12.The described method of this invention is carried out under normal pressure, air atmosphere, and processing is simple, and obtained freeze thaw stability is good, conductivity is high.But in preparation process, ball milling, calcining repeatedly, can cause a large amount of losses of material.
Summary of the invention
The object of the invention is to solve the problems such as electrolytic conductivity is lower, sintering temperature is higher, preparation in enormous quantities difficulty, provide a kind of simple to operate, production cost is lower, the ceramic solid electrolyte that can produce in enormous quantities and preparation method thereof, gained electrolyte ion conductivity is higher, sintering temperature is lower, has stronger practicality.
The object of the invention is to be achieved through the following technical solutions:
A kind of ceramic solid electrolyte, comprises NASICON structural type (LiM 2(PO 4) 3, M=Zr, Ge, Mg, Al), the oxide (Li of perovskite structure 3xla 2/3-xtiO 3), the oxide (Li of garnet structure 5la 3m 2o 12) at least one.
A preparation method for above-mentioned ceramic solid electrolyte, adopt spray drying process to be prepared, concrete implementation step is as follows:
A) take raw material by the mol ratio of element in ceramic solid electrolyte chemical formula, be dissolved in solvent, obtain mixed solution;
B) utilize spray drying process to prepare ceramic solid electrolyte precursor powder above-mentioned mixed solution, spray dryer charging rate, nozzle outlet temperature, blast pressure are set;
C) sinter in spraying dry gained precursor powder air, finally prepare the ceramic solid electrolyte had compared with high ionic conductivity and lower electronic conductivity.
Above-mentioned steps a) in, preparing solid electrolyte lithium salts used is at least one in lithium nitrate, lithium acetate, lithium hydroxide, lithium chloride, and lithium salts excessive 1 ~ 30% in preparation process.
Above-mentioned steps a) in, prepared solid electrolyte be Ca-Ti ore type and carbuncle type oxide time, titanium source used is the one in butyl titanate, isopropyl titanate, and other metal cation salts are at least one in its nitrate, acetate, chlorate.
Above-mentioned steps a) in, described solvent is at least one in deionized water, ethanol.
Above-mentioned steps a) in, in described solution, lithium salt is 0.0001 ~ 1M.
Above-mentioned steps b) in, described spraying dry charging rate is 0.1 ~ 10r/min, and described nozzle outlet temperature is 80 ~ 250 DEG C, and described blast pressure is 0.05 ~ 0.8MPa.
Above-mentioned steps c) in, sintering temperature is 300 ~ 1500 DEG C, and heating rate is 0.5 ~ 5 DEG C/min, and sintering time is 1 ~ 50h.
Advantage of the present invention is as follows:
(1) the inventive method adopts spray drying process to prepare ceramic solid electrolyte, spraying dry have dry run rapidly, convection drying powdered and the uniform advantage of powder particle size distribution, be expected to the extensive preparation realizing ceramic solid electrolyte, there is practical value;
(2) the electrolyte sintering temperature prepared by the present invention is lower, lithium ion conductivity is higher.
Accompanying drawing explanation
Fig. 1 is that the solid electrolyte presoma SEM that embodiment 1 obtains schemes;
Fig. 2 be embodiment 1 obtain solid electrolyte sintering after SEM figure;
Fig. 3 is the solid electrolyte XRD collection of illustrative plates that embodiment 1 obtains;
Fig. 4 is the solid electrolyte EIS collection of illustrative plates that embodiment 1 obtains;
Fig. 5 is the solid electrolyte presoma SEM that embodiment 3 obtains.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
embodiment 1:
First get 600ml deionized water, add citric acid 5.53g and dissolve, then press Li 7la 3zr 2o 12stoichiometric proportion takes lithium nitrate 4.45g, lanthanum nitrate 4.68g, zirconyl nitrate 1.12g adds in above-mentioned citric acid solution, wherein lithium salts excessive 10%, is uniformly mixed solution 12h, then carries out spraying dry.Spraying charging rate is set to 2r/min, nozzle outlet temperature is 180 DEG C, blast pressure is 0.2MPa.Gained spraying material is warming up to 800 DEG C with 1 DEG C/min and sinters, sintering time 6h.
Carry out morphology characterization to gained solid electrolyte and presoma thereof, as shown in Figure 1, 2, visible presoma material is spherical, and after sintering, pattern has significant change, is because electrolyte degree of crystallinity under high temperature improves.
Carry out XRD test to gained electrolyte, as shown in Figure 3, visible gained ceramic solid electrolyte degree of crystallinity is better, has garnet type structure for acquired results.
By gained electrolyte compressing tablet, then carry out EIS test, as shown in Figure 4, after matching, calculating, gained electrolytic conductivity is 1.2 × 10 to gained collection of illustrative plates -4s/cm.
embodiment 2:
First get 600ml deionized water, add citric acid 5.53g and dissolve, then press Li 7la 3zr 2o 12stoichiometric proportion takes lithium nitrate 4.45g, lanthanum nitrate 4.68g, zirconyl nitrate 1.12g adds in above-mentioned citric acid solution, wherein lithium salts excessive 10%, is uniformly mixed solution 12h, then carries out spraying dry.Spraying charging rate is set to 2r/min, nozzle outlet temperature is 180 DEG C, blast pressure is 0.2MPa.Gained spraying material is warming up to 800 DEG C with 5 DEG C/min and sinters, sintering time 6h.
embodiment 3:
First get 600ml deionized water, add citric acid 1.38g and dissolve, then press Li 7la 3zr 2o 12stoichiometric proportion takes lithium nitrate 4.45g, lanthanum nitrate 4.68g, zirconyl nitrate 1.12g adds in above-mentioned citric acid solution, wherein lithium salts excessive 10%, is uniformly mixed solution 12h, then carries out spraying dry.Spraying charging rate is set to 2r/min, nozzle outlet temperature is 180 DEG C, blast pressure is 0.2MPa.Gained spraying material is warming up to 800 DEG C with 1 DEG C/min and sinters, sintering time 6h.
Carry out morphology characterization to gained solid electrolyte presoma, as shown in Figure 5, the presoma material of visible embodiment 2 and the presoma pattern of embodiment 1 have certain difference.
embodiment 4:
First get in 600ml deionized water and alcohol mixeding liquid (volume ratio 1:1), add citric acid and dissolve, then press Li 0.3la 0.56tiO 3stoichiometric proportion takes lithium acetate, lanthanum nitrate, isopropyl titanate add in above-mentioned citric acid solution, wherein lithium salts excessive 10%, is uniformly mixed solution 12h, then carries out spraying dry.Spraying charging rate is set to 2r/min, nozzle outlet temperature is 100 DEG C, blast pressure is 0.2MPa.Gained spraying material is warming up to 800 DEG C with 1 DEG C/min and sinters, sintering time 6h.
embodiment 5:
First get 600ml deionized water and alcohol mixeding liquid (volume ratio 1:1), add citric acid and dissolve, then press Li 0.5la 0.5tiO 3stoichiometric proportion takes lithium acetate, lanthanum nitrate, isopropyl titanate add in above-mentioned citric acid solution, wherein lithium salts excessive 10%, is uniformly mixed solution 12h, then carries out spraying dry.Spraying charging rate is set to 2r/min, nozzle outlet temperature is 100 DEG C, blast pressure is 0.2MPa.Gained spraying material is warming up to 800 DEG C with 1 DEG C/min and sinters, sintering time 6h.
embodiment 6:
First get 600ml deionized water and alcohol mixeding liquid (volume ratio 1:1), add citric acid and dissolve, then press Li 1.5al 0.5ge 1.5p 3o 12stoichiometric proportion takes lithium acetate, aluminum acetate, isopropyl alcohol germanium, ammonium dihydrogen phosphate add in above-mentioned citric acid solution, wherein lithium salts excessive 10%, is uniformly mixed solution 12h, then carries out spraying dry.Spraying charging rate is set to 2r/min, nozzle outlet temperature is 100 DEG C, blast pressure is 0.2MPa.Gained spraying material is warming up to 800 DEG C with 1 DEG C/min and sinters, sintering time 6h.
embodiment 7:
First get 600ml deionized water and alcohol mixeding liquid (volume ratio 1:1), add citric acid and dissolve, then press Li respectively 7la 3zr 2o 12, Li 0.5la 0.5tiO 3stoichiometric proportion takes lithium acetate, lanthanum nitrate, zirconium nitrate, isopropyl titanate add in above-mentioned citric acid solution, wherein design Li 7la 3zr 2o 12, Li 0.5la 0.5tiO 3mol ratio be 1:1, lithium salts excessive 10%, is uniformly mixed solution 12h, then carries out spraying dry.Spraying charging rate is set to 2r/min, nozzle outlet temperature is 100 DEG C, blast pressure is 0.2MPa.Gained spraying material is warming up to 800 DEG C with 1 DEG C/min and sinters, sintering time 6h.

Claims (7)

1. a ceramic solid electrolyte, is characterized in that described ceramic solid state electrolyte comprises NASICON structural type LiM 2(PO 4) 3, perovskite structure oxide Li 3xla 2/3-xtiO 3, garnet structure oxide Li 5la 3m 2o 12in at least one, M=Ti, Zr, Ge, Mg, Al.
2. a preparation method for ceramic solid electrolyte described in claim 1, is characterized in that described method step is as follows:
A) take raw material by the mol ratio of element in ceramic solid electrolyte chemical formula, be dissolved in solvent, obtain mixed solution;
B) utilize spray drying process to prepare ceramic solid electrolyte precursor powder above-mentioned mixed solution, spray dryer charging rate, nozzle outlet temperature, blast pressure are set;
C) sinter in spraying dry gained precursor powder air, finally prepare the ceramic solid electrolyte had compared with high ionic conductivity and lower electronic conductivity.
3. the preparation method of ceramic solid electrolyte according to claim 2, is characterized in that described ceramic solid electrolyte is NASICON structural type LiM 2(PO 4) 3, perovskite structure oxide Li 3xla 2/3-xtiO 3, garnet structure oxide Li 5la 3m 2o 12time, lithium salts is at least one in lithium nitrate, lithium acetate, lithium hydroxide, lithium chloride, and lithium salts excessive 1 ~ 30% in preparation process.
4. the preparation method of ceramic solid electrolyte according to claim 2, it is characterized in that described solid electrolyte be Ca-Ti ore type and carbuncle type oxide time, titanium source used is the one in butyl titanate, isopropyl titanate, and other metal cation salts are at least one in its nitrate, acetate, chlorate.
5. the preparation method of ceramic solid electrolyte according to claim 2, is characterized in that described solvent is at least one in deionized water, ethanol.
6. the preparation method of ceramic solid electrolyte according to claim 2, it is characterized in that described spraying dry charging rate is 0.1 ~ 10r/min, described nozzle outlet temperature is 80 ~ 250 DEG C, and described blast pressure is 0.05 ~ 0.8MPa.
7. the preparation method of ceramic solid electrolyte according to claim 2, it is characterized in that described sintering temperature is 300 ~ 1500 DEG C, heating rate is 0.5 ~ 5 DEG C/min, and sintering time is 1 ~ 50h.
CN201511016931.1A 2015-12-30 2015-12-30 Ceramic solid electrolyte and preparation method thereof Pending CN105406118A (en)

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Cited By (21)

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CN105932327A (en) * 2016-05-16 2016-09-07 北京科技大学 Preparation method for cubic-phase lithium lanthanum zirconium oxide solid-state electrolyte nano material
CN108091929A (en) * 2017-12-13 2018-05-29 武汉佰起科技有限公司 A kind of solid electrolyte and preparation method thereof
CN108091928A (en) * 2017-12-13 2018-05-29 桑顿新能源科技有限公司 A kind of Organic-inorganic composite solid electrolyte and preparation method
CN109148947A (en) * 2018-07-10 2019-01-04 南京航空航天大学 Solid-state sodium ion conductor material and preparation method thereof
CN109690862A (en) * 2016-09-13 2019-04-26 新加坡国立大学 Solid electrolyte
CN109721042A (en) * 2018-12-20 2019-05-07 长江大学 A kind of all solid state lithium ion electrolyte and preparation method thereof
CN109935900A (en) * 2017-12-19 2019-06-25 成都英诺科技咨询有限公司 Solid electrolyte and its lithium battery, lithium battery electric core and preparation method thereof
KR20190114211A (en) * 2018-03-29 2019-10-10 울산과학기술원 Manufacturing Method of solid electrolyte
CN110372367A (en) * 2019-07-12 2019-10-25 成都新柯力化工科技有限公司 A kind of lithium battery high-ductility ceramic solid electrolyte material and preparation method
CN110534681A (en) * 2018-05-25 2019-12-03 浙江锋锂新能源科技有限公司 Conduct the tubular ceramic film and preparation method thereof of ion
CN111937213A (en) * 2018-04-05 2020-11-13 （株）七王能源 Method for manufacturing ceramic solid electrolyte for lithium secondary battery
CN113224378A (en) * 2021-04-27 2021-08-06 长江大学 Lithium battery, solid electrolyte, and preparation method and application thereof
CN113372110A (en) * 2021-05-28 2021-09-10 北京高压科学研究中心 Method for preparing perovskite type solid electrolyte lanthanum lithium titanate based on high-temperature and high-pressure synthesis
CN113511675A (en) * 2021-08-03 2021-10-19 重庆锦添翼新能源科技有限公司 Crown-shaped structure solid electrolyte and preparation method thereof
CN113889660A (en) * 2021-09-04 2022-01-04 浙江锋锂新能源科技有限公司 Spherical lithium-containing oxide electrolyte powder material and preparation method thereof
US11223066B2 (en) 2018-08-01 2022-01-11 Samsung Electronics Co., Ltd. Solid-state electrolyte and method of manufacture thereof
US11251460B2 (en) 2018-08-01 2022-02-15 Samsung Electronics Co., Ltd. Solution-processed solid-state electrolyte and method of manufacture thereof
CN114171786A (en) * 2020-09-11 2022-03-11 中国科学院上海硅酸盐研究所 Garnet type solid electrolyte with three-dimensional cross-linking modification layer and preparation method and application thereof
CN115160011A (en) * 2022-07-26 2022-10-11 浙江固泰动力技术有限公司 Method for preparing straight-hole solid-state lithium battery ceramic electrolyte by one-step sintering and application thereof
CN115180946A (en) * 2022-06-16 2022-10-14 江苏大学 Multifunctional ceramic material capable of resisting ultra-fast temperature rise and drop and preparation method and application thereof
US11757127B2 (en) 2019-06-18 2023-09-12 Samsung Electronics Co., Ltd. Lithium solid electrolyte and method of manufacture thereof

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CN105932327A (en) * 2016-05-16 2016-09-07 北京科技大学 Preparation method for cubic-phase lithium lanthanum zirconium oxide solid-state electrolyte nano material
CN109690862A (en) * 2016-09-13 2019-04-26 新加坡国立大学 Solid electrolyte
CN108091929A (en) * 2017-12-13 2018-05-29 武汉佰起科技有限公司 A kind of solid electrolyte and preparation method thereof
CN108091928A (en) * 2017-12-13 2018-05-29 桑顿新能源科技有限公司 A kind of Organic-inorganic composite solid electrolyte and preparation method
CN109935900A (en) * 2017-12-19 2019-06-25 成都英诺科技咨询有限公司 Solid electrolyte and its lithium battery, lithium battery electric core and preparation method thereof
KR102069715B1 (en) * 2018-03-29 2020-01-23 울산과학기술원 Manufacturing Method of solid electrolyte
KR20190114211A (en) * 2018-03-29 2019-10-10 울산과학기술원 Manufacturing Method of solid electrolyte
CN111937213A (en) * 2018-04-05 2020-11-13 （株）七王能源 Method for manufacturing ceramic solid electrolyte for lithium secondary battery
CN110534681A (en) * 2018-05-25 2019-12-03 浙江锋锂新能源科技有限公司 Conduct the tubular ceramic film and preparation method thereof of ion
CN109148947A (en) * 2018-07-10 2019-01-04 南京航空航天大学 Solid-state sodium ion conductor material and preparation method thereof
US11223066B2 (en) 2018-08-01 2022-01-11 Samsung Electronics Co., Ltd. Solid-state electrolyte and method of manufacture thereof
US11251460B2 (en) 2018-08-01 2022-02-15 Samsung Electronics Co., Ltd. Solution-processed solid-state electrolyte and method of manufacture thereof
CN109721042A (en) * 2018-12-20 2019-05-07 长江大学 A kind of all solid state lithium ion electrolyte and preparation method thereof
US11757127B2 (en) 2019-06-18 2023-09-12 Samsung Electronics Co., Ltd. Lithium solid electrolyte and method of manufacture thereof
CN110372367A (en) * 2019-07-12 2019-10-25 成都新柯力化工科技有限公司 A kind of lithium battery high-ductility ceramic solid electrolyte material and preparation method
CN114171786A (en) * 2020-09-11 2022-03-11 中国科学院上海硅酸盐研究所 Garnet type solid electrolyte with three-dimensional cross-linking modification layer and preparation method and application thereof
CN114171786B (en) * 2020-09-11 2024-02-06 中国科学院上海硅酸盐研究所 Garnet type solid electrolyte with three-dimensional crosslinking modification layer, and preparation method and application thereof
CN113224378B (en) * 2021-04-27 2023-02-28 长江大学 Lithium battery, solid electrolyte, and preparation method and application thereof
CN113224378A (en) * 2021-04-27 2021-08-06 长江大学 Lithium battery, solid electrolyte, and preparation method and application thereof
CN113372110A (en) * 2021-05-28 2021-09-10 北京高压科学研究中心 Method for preparing perovskite type solid electrolyte lanthanum lithium titanate based on high-temperature and high-pressure synthesis
CN113511675A (en) * 2021-08-03 2021-10-19 重庆锦添翼新能源科技有限公司 Crown-shaped structure solid electrolyte and preparation method thereof
CN113889660A (en) * 2021-09-04 2022-01-04 浙江锋锂新能源科技有限公司 Spherical lithium-containing oxide electrolyte powder material and preparation method thereof
CN115180946A (en) * 2022-06-16 2022-10-14 江苏大学 Multifunctional ceramic material capable of resisting ultra-fast temperature rise and drop and preparation method and application thereof
CN115160011A (en) * 2022-07-26 2022-10-11 浙江固泰动力技术有限公司 Method for preparing straight-hole solid-state lithium battery ceramic electrolyte by one-step sintering and application thereof

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