[go: up one dir, main page]

WO2017147793A1 - Procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion - Google Patents

Procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion Download PDF

Info

Publication number
WO2017147793A1
WO2017147793A1 PCT/CN2016/075261 CN2016075261W WO2017147793A1 WO 2017147793 A1 WO2017147793 A1 WO 2017147793A1 CN 2016075261 W CN2016075261 W CN 2016075261W WO 2017147793 A1 WO2017147793 A1 WO 2017147793A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
skeleton
lithium ion
air
battery
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.)
Ceased
Application number
PCT/CN2016/075261
Other languages
English (en)
Chinese (zh)
Inventor
金超
杨瑞枝
王章俊
罗勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to PCT/CN2016/075261 priority Critical patent/WO2017147793A1/fr
Publication of WO2017147793A1 publication Critical patent/WO2017147793A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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

Definitions

  • the present invention relates to a lithium-air battery, and in particular to a method for preparing a lithium air battery based on a lithium ion solid electrolyte, which belongs to the field of high performance chemical power sources.
  • a lithium-air battery is a battery that uses oxygen as a positive electrode active material and metal lithium as a negative electrode active material. Since oxygen does not need to be stored inside a battery, its theoretical energy density is as high as 5.21.
  • lithium-air batteries are also known as next-generation lithium batteries or ultimate batteries.
  • the oxygen molecules in the air are converted into oxygen anions or peroxy anions by the catalyst, and combined with the lithium ions transferred from the anode to form lithium oxide or lithium peroxide; discharge ⁇ , generated lithium
  • the oxide or lithium peroxide is re-decomposed to generate oxygen and lithium metal to achieve a reversible cycle of discharge and charge; this is quite different from conventional metal air batteries such as aluminum air batteries and zinc air batteries, aluminum air and zinc air batteries. Mainly working in alkaline solution, mainly used once for battery use.
  • Lithium-air batteries as a new generation of high energy density power sources, have broad application prospects in the fields of portable electronic products and communication equipment, and particularly meet the high energy density requirements of electric vehicle power sources.
  • lithium-air battery research is based on existing lithium ion batteries, using an organic carbonate electrolyte as an organic electrolyte solution, but the organic electrolyte is flammable and explosive, which leads to electrolyte leakage and the resulting electrolyte. Battery explosions and fires have occurred.
  • the most direct and effective method is to no longer use flammable and explosive organic electrolyte solution, using non-combustible non-explosive all-solid lithium Ionic electrolyte, which simplifies battery safety devices and significantly reduces battery manufacturing costs
  • the prior art reports a solid state lithium-air battery based on a phosphate solid electrolyte, but both use a phosphate-based solid electrolyte material having a NASICON structure, such as Li L3 A1. . 3 Ti 1 7 (PO 4 ) 3 (LATP) and Li 1+x Al y Ge 2 _ x (P0 4 ) 3 (LAGP), such solid electrolyte materials are unstable and easily react with lithium metal anodes; In these reported solid-state lithium-air batteries, a separator material saturated with a liquid organic electrolyte is required between the lithium metal anode and the solid electrolyte, which increases the battery operation and the lithium ion transport path.
  • a separator material saturated with a liquid organic electrolyte is required between the lithium metal anode and the solid electrolyte, which increases the battery operation and the lithium ion transport path.
  • Garnet or perovskite lithium ion solid electrolyte has high lithium ion conductivity and room temperature conductivity up to ⁇ 10 3 ⁇ 4 cm
  • An object of the present invention is to provide a method for preparing a lithium air battery based on a lithium ion solid electrolyte, which is controlled and optimized by a contact interface between a lithium metal anode, an air electrode, and a lithium ion solid electrolyte.
  • the invention provides an all-solid lithium-air battery, which has the advantages of high charge and discharge capacity, good rate performance, high cycle stability, wide operating temperature range, and the like, and is suitable for various mobile electronic devices and power battery fields.
  • a method for preparing a lithium air battery based on a lithium ion solid electrolyte comprising: preparing an electrolyte skeleton, preparing an air electrode, preparing a metal electrode, and preparing a battery lead; [0010]
  • the electrolyte skeleton is prepared by adding a garnet-type or perovskite-type lithium ion solid electrolyte material, an organic additive to ethanol, and ball milling for 3 to 5 hours to obtain an impregnating slurry; a titanium-titanium-type lithium ion solid electrolyte material is mixed with ethyl cellulose, and then ground for 2 to 4 hours, and then 1,5-dimethyl-2-pyrrolidone is added to obtain a mixture; and then the mixture is prepared into an electrolyte skeleton green body; Further, the electrolyte skeleton green body is sintered at 1000 to 1100 ° C for 12 to 24 hours, and naturally cooled to obtain a solid skeleton; then
  • the air electrode is prepared by adding a raw material for preparing an air electrode catalyst to water to be configured as an air electrode catalyst precursor solution; a garnet type or perovskite type lithium ion solid electrolyte material, polyvinyl condensate Aldehyde, ethyl cellulose-terpineol and tetrapropylammonium hydroxide, polystyrene microspheres are mixed, and ethanol is added to prepare a brushing slurry; then the coating slurry is applied to the surface of the electrolyte skeleton, at 1000 ⁇ Squeeze at 10 °C for 4 ⁇ 8 hours, and obtain a porous skeleton after natural cooling.
  • the porous skeleton After compounding the porous skeleton with the air electrode catalyst precursor solution, it is 380 ⁇ 650 °C in a tube furnace with high purity argon or nitrogen. Calcining 2 ⁇ 8 hours, preparing an air electrode on the outer side wall of the electrolyte skeleton;
  • the electrolyte skeleton structure of the present invention is a tubular structure closed at one end, the other end is a mouth, the part wrapped by the side wall is an inner cavity, the outer side wall is sealed, and the inner side wall is a porous structure; the lithium metal anode is uniformly poured at one end and closed.
  • the inner cavity of the tubular structure is filled with a hole communicating with the inner cavity on the inner wall of the electrolyte skeleton, the direction of the hole is consistent with the direction of active material transport, the large hole is favorable for material transport, and the specific surface area of the small hole is large, which is favorable for increasing electrochemical reaction.
  • the air electrode is a porous film structure, and the distance between the edge of the electrolyte skeleton and the mouth of the electrolyte is 3 to 10 mm, and the end of the porous air electrode film is at a certain distance from the mouth end of the electrolyte skeleton to avoid
  • the air electrode and the anode are short-circuited at the mouth of the electrolyte tube;
  • the air electrode is catalytically supported on the porous air electrode film; and the electrolyte skeleton mouth (battery port end) is sealed with a conventional polypropylene sealant.
  • Current collector, battery anode lead, and battery air electrode The connection of the leads is a conventional setting for a lithium air battery.
  • the lithium ion solid electrolyte material is garnet type Li 7 La 3 Zr 2 0 12 or Li 7 La 3 Zr 2 _ X M x0 12 , wherein M is Ta, Nb, Sb, Bi, Ti, Y or Al; or Li 3x La 2 X D 1 2x TiO 3 perovskite oxide, spaces in the formula indicate vacancies; metal electrode leads are silver wires, air electrode leads are silver wires; air electrode catalyst is N miscellaneous carbon
  • the materials include mesoporous carbons with different N contents and different graphenes with different N contents.
  • the preparation of the impregnating slurry ⁇ , the organic additive is used in an amount of 10 ⁇ 3 ⁇ 4 ⁇ 12% of the mass of the lithium ion solid electrolyte material; preparing the mixture ⁇ , ethyl cellulose and garnet or perovskite type lithium
  • the mass ratio of the ionic solid electrolyte material is 0.5 to 0.8:1; in the organic additive, the mass ratio of ethyl orthosilicate, triethanolamine, dibutyl phthalate and polyethylene glycol is 0.8:1:1.1:1.2 .
  • ethyl cellulose and a lithium ion solid electrolyte material powder are placed in a ball mill tank, and the solvent 1,5-dimethyl-2-pyrrolidone is added to the mixture to obtain a slurry mixture; the glass rod is used to impregnate the above.
  • the slurry after rotating evenly, is quickly placed in absolute ethanol, and is still semi-small.
  • a tubular green body closed at one end is obtained, and then sintered to obtain a solid skeleton.
  • the diameter and length of the solid skeleton can be The diameter of the glass rod and the amount of the slurry are used for regulation; the slurry can also be prepared by an existing injection molding apparatus.
  • the electrolyte skeleton of the present invention has a wall thickness of 1 to 3 mm and a long diameter (outer diameter) ratio of (0.06 to 0.5):1.
  • an air electrode crucible a garnet-type or perovskite-type lithium ion solid electrolyte material, polyvinyl butyral, ethyl cellulose-terpineol, tetrapropylammonium hydroxide, poly
  • the mass ratio of the styrene microspheres is 1:0.05:0.08:0.15:0.3; the porous skeleton is combined with the air electrode catalyst precursor solution in such a manner that the porous skeleton is impregnated into the air electrode catalyst precursor solution or the air electrode catalyst precursor solution is used. Drop on the porous skeleton.
  • the air electrode catalyst precursor is prepared according to the required air electrode catalyst (N-heterocarbon material), and may be subjected to multiple impregnation or multiple additions to make the catalyst grow uniformly in the porous air electrode film.
  • a metal electrode and a metal electrode lead wire are prepared, and in a glove box filled with high-purity argon gas (oxygen and water vapor content is less than 1 ppm), a molten metal metal is injected into the outer side wall with air. Electrode in the electrolyte skeleton inner cavity, then insert the metal electrode lead into the metal lithium; hold at 185 ° C for 20 to 40 minutes to ensure that the molten metal lithium is fully infiltrated into the porous lithium ion solid electrolyte pore; After the lithium is solidified, a metal electrode and a metal electrode lead are obtained.
  • high-purity argon gas oxygen and water vapor content is less than 1 ppm
  • the fabricated all-solid-state lithium air battery is static for 2 to 4 hours in air or pure oxygen, and then the charge and discharge performance of the battery under different conditions is tested by using a charge and discharge meter, and the battery exhibits a good magnification. Sex.
  • the all-solid lithium air battery prepared by the invention has excellent charge and discharge performance under different conditions, and has excellent output performance and good stability under different temperature range and different current densities.
  • the present invention has the following advantages over the prior art:
  • the present invention provides an all-solid lithium air battery based on a lithium ion solid electrolyte for the first time.
  • the metal lithium anode and the solid electrolyte are chemically compatible, avoiding the use of the separator and the organic electrolyte, and realizing the entire battery in a true sense.
  • the whole solid state is beneficial to improve the safety performance of the battery; firstly, a porous skeleton is prepared by using a lithium ion solid electrolyte material, and then an air electrode catalyst and a lithium metal are respectively disposed outside the porous skeleton and the inner cavity to form an air electrode and an anode.
  • the electrode is formed in this way, which can convert lithium ions from two-dimensional transmission to three-dimensional transmission, and expands the three-phase interface of the electrode reaction, which is beneficial to reducing the polarization resistance of the battery, greatly shortening the lithium ion transmission path, and reducing the ohmicity of the battery. resistance.
  • the whole battery structure is a tubular structure with one end closed, and the lithium metal anode is poured into the tube and sealed with a waterproof material; compared with the existing button battery,
  • the structure of the invention is convenient for battery packaging, can completely isolate the lithium metal anode from the reactive gas, avoid the occurrence of side reactions, and prolong the service life of the battery; and combine the key units constituting the lithium air battery by layer-by-layer sintering.
  • the interface between the adjacent layers is firm, which increases the structural stability of the battery.
  • the design of the porous layer makes the distribution of lithium metal and catalyst more stereoscopic, effectively increasing the transmission path of lithium ions; thereby greatly improving the electricity of the all-solid battery. Performance, stability of use, and security.
  • the all-solid-state lithium air battery assembly provided by the present invention is carried out in a glove box with high purity argon gas (99.999%), and the battery test is performed in air.
  • Battery charge and discharge test is in Wuhan Blue Electric Charge Discharge Instrument (LA ND CT Performed on 2001A), the charge and discharge voltage range is 2.2-4.5V, and the charge and discharge current density is 100-1000mA/g. Cyclic voltammetry and AC impedance testing were performed on the Shanghai Chenhua CHI 604B electrochemical workstation. The current used for charging and discharging the battery and the specific capacity of the battery are calculated based on the effective area of the air electrode.
  • 1,5-Dimethyl-2-pyrrolidone was placed in an agate ball mill jar, ball milled for 4 h to obtain a uniform viscous slurry, and the slurry was transferred to a test tube, and the slurry was impregnated with a glass rod having a diameter of about 0.3 cm. After pulling out, rotate at a constant speed. After the thickness is uniform, quickly soak into anhydrous ethanol to form a phase inversion process. After soaking for 20 minutes, remove the glass rod to obtain a tubular green body closed at one end, and finally heat up at rC/min. The rate was sintered at 1050 ° C for 12 h to obtain a tubular skeleton closed at one end, 4 cm long and 0.6 cm in outer diameter.
  • the slurry is impregnated with a tubular skeleton closed at one end, taken out and dried, and then immersed and dried again. This step is repeated three times, and finally sintered at 1150 ° C for 12 h at a heating rate of rC/min.
  • An electrolyte skeleton consisting of a tubular skeleton closed at one end and a dense electrolyte membrane having a thickness of about 15 ⁇ m.
  • the prepared all-solid lithium-air battery was taken out from the glove box, and was allowed to stand in the air for 2 hours, and then the charge and discharge performance of the battery under different conditions was tested by using a charge and discharge device, and the battery was first discharged at 200 mA/g.
  • the capacity reached 4150mAh/g, and the Coulomb efficiency was 75%. After 5 deep charge and discharge tests, the capacity remained above 50%, indicating that the battery has good cycleability.
  • the thickness is uniform, it is quickly soaked in absolute alcohol, and a phase inversion process occurs. After soaking for 20 minutes, the glass rod is taken out to obtain a tubular green body closed at one end, and finally The tube was sintered at 1050 ° C for 12 h at a heating rate of 1 ° C / min to obtain a tubular skeleton with a length of 4 cm and an outer diameter of 0.6 cm. Then the slurry was impregnated with a tubular skeleton closed at one end.
  • [0031] Accurately weigh 1 g of Li 6 . 4 La 3 Zr L4 Ta 04 O 12 and 0.05 ⁇ polyvinyl butyral, 0.08 g of ethyl cellulose - terpineol, 0.15 g of tetrapropylammonium hydroxide, 0.3 g of polystyrene microspheres were mixed, and 1.5 g of ethanol was added to grind to prepare a coating slurry. The slurry was brushed on the surface of the electrolyte membrane of the electrolyte membrane, dried, and then heated at a rate of rC/min.
  • a porous film having a thickness of about 60 ⁇ m is obtained, and a mixed aqueous solution of glucose and melamine is added dropwise to the porous film, dried, then added dropwise, dried, repeated 4 times, and then passed through.
  • a high-purity argon tube furnace was calcined at 550 ° C for 8 hours, and a N-miscelled mesoporous carbon nanoparticle catalyst was grown in situ on the porous film to obtain a porous air electrode film.
  • the prepared all-solid lithium-air battery was taken out from the glove box, and was allowed to stand in the air for 2 hours, and then the charge and discharge performance of the battery under different conditions was tested by using a charge and discharge device, and the battery was first discharged at 200 mA/g.
  • the capacity reached 4180mAh/g, and the coulombic efficiency was 76%. After 5 deep charge and discharge tests, the capacity was kept above 50%, indicating that the battery has good cycleability.
  • a porous film having a thickness of about 60 ⁇ m is obtained, and a mixed aqueous solution of glucose and melamine is added dropwise to the porous film, dried, then added dropwise, and baked. After drying, it was repeated 4 times, and then calcined at 600 ° C for 4 hours in a tube furnace with high purity argon gas to grow N-miscelled mesoporous carbon nanoparticle catalyst in situ in the porous film, thereby obtaining a porous air electrode film.
  • the prepared all-solid lithium-air battery was taken out from the glove box, and it was allowed to stand in the air for 2 hours. Then, the charge and discharge performance of the battery under different conditions was tested by using a charge and discharge device.
  • the initial discharge capacity of the battery at 200 mA/g reached 4080 mAh. /g, Coulomb efficiency is 75%. After 5 deep charge and discharge tests, the capacity is kept above 50%, indicating that the battery has good cycleability.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion, comprenant la préparation d'un squelette électrolytique, la préparation d'une électrode à air, la préparation d'une électrode métallique et la préparation d'un conducteur de batterie. La batterie au lithium-air tout solide obtenue utilise un support poreux constitué d'un matériau d'électrolyte solide lithium-ion de grenat ou de pérovskite, et un catalyseur d'électrode à air et un perméat d'anode de lithium métallique dans les pores, de façon à étendre une limite de trois phases pour une réaction de batterie, réduire la résistance de polarisation de batterie, raccourcir un trajet de transmission d'ion lithium et réduire la résistance ohmique d'une batterie. La batterie est dans une structure tubulaire fermée à une extrémité et l'anode de lithium métallique est versée dans un tube, de sorte que la batterie soit facile à sceller et adaptée pour fonctionner dans différentes conditions. La batterie possède une capacité élevée de charge et de décharge, une excellente capacité de débit, une grande stabilité de cycle et une large plage de température de fonctionnement, et peut être appliquée dans le domaine des appareils électroniques mobiles et des batteries d'alimentation.
PCT/CN2016/075261 2016-03-01 2016-03-01 Procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion Ceased WO2017147793A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/075261 WO2017147793A1 (fr) 2016-03-01 2016-03-01 Procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/075261 WO2017147793A1 (fr) 2016-03-01 2016-03-01 Procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion

Publications (1)

Publication Number Publication Date
WO2017147793A1 true WO2017147793A1 (fr) 2017-09-08

Family

ID=59743337

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/075261 Ceased WO2017147793A1 (fr) 2016-03-01 2016-03-01 Procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion

Country Status (1)

Country Link
WO (1) WO2017147793A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200119391A1 (en) * 2018-10-11 2020-04-16 Samsung Electronics Co., Ltd. Cathode and lithium-air battery including the cathode
US20200119346A1 (en) * 2018-10-11 2020-04-16 Samsung Electronics Co., Ltd. Perovskite material, method of preparing the same, and secondary battery including the perovskite material
US20210098821A1 (en) * 2019-09-26 2021-04-01 Samsung Electronics Co., Ltd. Solid electrolyte, preparation method thereof, lithium-air battery including the solid electrolyte, and electrochemical device including the solid electrolyte
US20210257628A1 (en) * 2020-02-04 2021-08-19 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
CN114074934A (zh) * 2020-08-14 2022-02-22 中国科学院上海硅酸盐研究所 一种非晶无机固态电解质及其制备方法
US11658306B2 (en) 2020-02-04 2023-05-23 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
US11909028B2 (en) * 2019-10-23 2024-02-20 Samsung Electronics Co., Ltd. Cathode for metal-air battery, preparing method thereof, and metal-air battery comprising the same
CN120809957A (zh) * 2025-09-12 2025-10-17 湖北允升科技工业园有限公司 一种固态电解质前驱体、固态电解质及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102610842A (zh) * 2012-03-28 2012-07-25 南京工业大学 中高温碳-空气电池
WO2013093044A1 (fr) * 2011-12-22 2013-06-27 Cic Energigune Dispositif de stockage d'énergie électrochimique
US20130171527A1 (en) * 2011-12-30 2013-07-04 Itn Energy Systems, Inc. Rechargeable, thin-film, all solid-state metal-air battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013093044A1 (fr) * 2011-12-22 2013-06-27 Cic Energigune Dispositif de stockage d'énergie électrochimique
US20130171527A1 (en) * 2011-12-30 2013-07-04 Itn Energy Systems, Inc. Rechargeable, thin-film, all solid-state metal-air battery
CN102610842A (zh) * 2012-03-28 2012-07-25 南京工业大学 中高温碳-空气电池

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200119346A1 (en) * 2018-10-11 2020-04-16 Samsung Electronics Co., Ltd. Perovskite material, method of preparing the same, and secondary battery including the perovskite material
US12009514B2 (en) * 2018-10-11 2024-06-11 Samsung Electronics Co., Ltd. Perovskite material, method of preparing the same, and secondary battery including the perovskite material
US11848411B2 (en) * 2018-10-11 2023-12-19 Samsung Electronics Co., Ltd. Cathode and lithium-air battery including the cathode
US20200119391A1 (en) * 2018-10-11 2020-04-16 Samsung Electronics Co., Ltd. Cathode and lithium-air battery including the cathode
US11742515B2 (en) * 2019-09-26 2023-08-29 Samsung Electronics Co., Ltd. Solid electrolyte, preparation method thereof, lithium-air battery including the solid electrolyte, and electrochemical device including the solid electrolyte
US20210098821A1 (en) * 2019-09-26 2021-04-01 Samsung Electronics Co., Ltd. Solid electrolyte, preparation method thereof, lithium-air battery including the solid electrolyte, and electrochemical device including the solid electrolyte
US11909028B2 (en) * 2019-10-23 2024-02-20 Samsung Electronics Co., Ltd. Cathode for metal-air battery, preparing method thereof, and metal-air battery comprising the same
US11764364B2 (en) * 2020-02-04 2023-09-19 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
US11658306B2 (en) 2020-02-04 2023-05-23 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
CN113285076A (zh) * 2020-02-04 2021-08-20 三星电子株式会社 正极、包括其的锂-空气电池、和制备所述正极的方法
US20210257628A1 (en) * 2020-02-04 2021-08-19 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
CN114074934B (zh) * 2020-08-14 2023-05-09 中国科学院上海硅酸盐研究所 一种非晶无机固态电解质及其制备方法
CN114074934A (zh) * 2020-08-14 2022-02-22 中国科学院上海硅酸盐研究所 一种非晶无机固态电解质及其制备方法
CN120809957A (zh) * 2025-09-12 2025-10-17 湖北允升科技工业园有限公司 一种固态电解质前驱体、固态电解质及其制备方法
CN120809957B (zh) * 2025-09-12 2025-11-28 湖北允升科技工业园有限公司 一种固态电解质前驱体、固态电解质及其制备方法

Similar Documents

Publication Publication Date Title
CN105742761B (zh) 一种全固态锂‑空气电池及其制备方法与应用
WO2017147793A1 (fr) Procédé de préparation d'une batterie au lithium-air à base d'électrolytes solides lithium-ion
Wang et al. Rechargeable solid-state lithium metal batteries with vertically aligned ceramic nanoparticle/polymer composite electrolyte
CN101626075B (zh) 锡碳复合纳米纤维薄膜负极材料及其制备方法
CN104916869B (zh) 多孔‑致密双层电解质陶瓷烧结体、锂离子电池、锂‑空气电池
CN105551815B (zh) 一种锂离子电容器及其制备方法
WO2020181681A1 (fr) Batterie de stockage au lithium à électrolyte solide-liquide hybride
CN105470515B (zh) 一种安全型锂离子动力电池正极及含有该正极的锂离子电池
CN103730645B (zh) 一种硅包覆碳纤维纳米复合材料及其制备方法和应用
CN114335701A (zh) 一种复合固态电解质膜及其制备方法
CN106505194A (zh) 改性钴酸锂及其制备方法、锂离子电池及其化成方法
Dai et al. A solid state energy storage device with supercapacitor–battery hybrid design
CN101621134A (zh) 一种凝胶态聚合物锂离子电池电解质及其制备方法和应用
CN103531756A (zh) 碳纳米纤维负载钛酸锂薄膜材料及其制备方法
CN116130748A (zh) 一种复合固态电解质膜及其制备方法
CN102299285A (zh) 一种用作锂离子电池隔膜的多孔无机膜及其制备方法
CN105762441B (zh) 基于锂离子固体电解质的锂空气电池的制备方法
CN113346126A (zh) 复合固态电解质、全固态锂离子电池及其制备方法
CN110890530A (zh) 基于多孔陶瓷复合锂金属负极的锂金属二次电池及其制备方法
Chen et al. High capacity and rate performance of LiNi 0.5 Co 0.2 Mn 0.3 O 2 composite cathode for bulk-type all-solid-state lithium battery
CN104282868B (zh) 修饰性多孔膜支撑的电解质陶瓷隔膜及其制备方法
CN111370753A (zh) 一种固态电解质复合膜及其制备方法和应用
CN115714201A (zh) 一种电极-电解质集成一体化复合材料及其制备方法和应用
CN104282867A (zh) 用于钠电池的电解质陶瓷隔膜及其制备方法
Hofstetter et al. Characterization of lithium-rich garnet-type Li6. 5La2. 5Ba0. 5ZrTaO12 for beyond intercalation chemistry-based lithium-ion batteries

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16891985

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 16891985

Country of ref document: EP

Kind code of ref document: A1