CN103456983A - Solid thin film electrolyte material and preparation method thereof - Google Patents

Solid thin film electrolyte material and preparation method thereof Download PDF

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CN103456983A
CN103456983A CN201310404223XA CN201310404223A CN103456983A CN 103456983 A CN103456983 A CN 103456983A CN 201310404223X A CN201310404223X A CN 201310404223XA CN 201310404223 A CN201310404223 A CN 201310404223A CN 103456983 A CN103456983 A CN 103456983A
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thin film
solid electrolyte
electrolyte material
film solid
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CN103456983B (en
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徐华蕊
俞兆喆
朱归胜
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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    • 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 solid thin film electrolyte material and a preparation method thereof. The solid thin film electrolyte material has a structure as shown in the formula: Li-(Mn1-Xm1x)-(Til-yM2y)-O, wherein, 0<=x<=1, 0<=y<=1, M1 is selected from at least one of La, Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb and Ba, and M2 is selected from at least one of Mg, W, Al, Ge, Ru, Nb, Ni, Ta, Co, Fe, Zr, Hf, Fe, Cr and Ga. The solid thin film electrolyte material is obtained by using a sol-gel method or radio frequency magnetron sputtering method. The solid thin film electrolyte material has relatively high Li ion conductivity, relatively low electron conductivity and favorable thermodynamic stability, and is particularly suitable for producing solid lithium ion batteries.

Description

Thin film solid electrolyte material and preparation method thereof
Technical field
The present invention relates to thin film solid electrolyte material that a kind of lithium-ion-conducting is good and preparation method thereof.
Background technology
Since the commercialization of eighties of last century the nineties, lithium ion battery due to have energy density high, have extended cycle life, do not have memory effect, advantages of environment protection, become the substitute of Ni-MH battery and nickel-cadmium cell soon.But the safety issue of lithium ion battery is the focus that people pay close attention to always.Contain flammable organic substance in lithium-ion battery electrolytes, easily occur that corroding electrode, leakage, decomposition produce gas and make the air pressure inside rising that the important safety hidden danger such as burning even occur.Use polymer dielectric can alleviate to a certain extent above safety problem, but can't fundamentally solve.
Abroad in Recent Years is very active to the R and D of all solid state inorganic thin film lithium battery; in aerospace industry; film lithium cell and solar cell constitute jointly power supply; this energy storage power supply is more more advantageous than the Ni-Cd power supply of original use; because for aerospace craft, miniaturization, lightweight are important indicators.Under the support energetically of NASA, the technology that the ITN energy resource system subordinate's of company of Colorado ITN advanced optical battery group adopts U.S.'s Oak Ridge National Laboratory (ORNL) to provide has been produced power supply and the power management circuit that all solid state thin lithium battery combines with flexible Cu-In-Ga-Se (CIGS) solar cell, and develops the special-purpose integrated flexible integration power module of satellite.The Bitsy satellite (1Kg) of the Munin satellite of Sweden (5 Kg) and the U.S. has all adopted this secondary cell, the full solid thin film battery has become the optimal selection of energy storage in the nanometer satellite, in addition, its purposes also comprises the aspects such as miniature robot surveillance plane electrical source of power, microsensor, RF smart card.
Why thin film lithium/lithium ion battery is also not by large-scale commercial, except its price is not also accepted by the public, main reason or its performance also do not reach the stage that can replace conventional batteries fully, also have many actual application problem urgently to be resolved hurrily, as the capacity that improves battery, simplify preparation technology, reduce battery cost etc.
In the middle of the solid electrolyte used at the full solid thin film battery, Chinese patent CN102473958A discloses the good solid electrolyte material of a kind of Li ionic conduction performance.Utilize the method for reactive evaporation to form the film of the densification of Li-La-Ti-O.The method of evaporation makes crystal grain good combining each other, and the resistance that has suppressed grain boundaries increases.
The people such as Bates, Electrical properties of amorphous lithium electrolyte thin films, Solid State Ionics., 1992,53-56 adopts rf magnetron sputtering LiPO under nitrogen atmosphere<sub TranNum="57">4</sub>the method of target prepares LiPON and at room temperature has good ionic conductivity (2.3(± 0.7) * 10<sup TranNum="58">-6</sup>s/cm) and low-down electronic conductivity (<10<sup TranNum="59">-14</sup>s/cm), electrochemical stability window is 5.5V.At sputter LiPO<sub TranNum="60">4</sub>target forms in the process of LiPON film, and the N atom has replaced LiPO<sub TranNum="61">4</sub>(-O-) in structure or bridged bond (O) oxygen, two covalent bonds (-N=) or the three covalent bond (-N<=structures of formation nitrogen.The increase of LiPON film ionic conductivity is attributed to non-crystalline structure and the N content of LiPON film, and N content is higher, and its ionic conductivity is larger.
The people such as Lee, Crystal structure revision and identification of Li +-ion migration pathways in the garnet-like Li 5la 3m 2o 12(M=Nb, Ta) oxides, Chem. Mater. 2004,16, preparation there is the Garnet structure, general formula is Li 5la 3m 2o 12the solid electrolyte of (M=Nb, Ta) presents higher ionic conductivity, when using the lower valency ion (as Ba 2+, Sr 2+and K +) replacement La 3+the time, Li 6baLa 2ta 2o 12there is the highest ionic conductivity 4 * 10 -5s/cm(295K), activation energy is 0.40eV; And work as Ta 5+perhaps Nb 5+quilt is as In 3+while replacing, sample Li 5.5la 3nb 1.75in 0.25o 12in ionic conductivity can reach 1.8 * 10 -4s/cm(323K).
LiPON film ionic conductivity is high, and thermodynamic stability is good and electrochemical window is wide, but comparatively responsive to airborne water vapour and oxygen, Li 5la 3m 2o 12material preparation process more complicated such as (M=Nb, Ta), not too be applicable to suitability for industrialized production.
Summary of the invention
Purpose of the present invention: aim to provide the thin film solid electrolyte material that a kind of Li ionic conductivity is high, electronic conductivity is low and thermodynamic stability is good, and provide that technique is simple, the preparation method of constant product quality, lower-cost this thin film solid electrolyte material.
Technical scheme of the present invention is as follows:
The thin film solid electrolyte material, its material structure is Li-(Mn 1-xm1 x)-(Ti 1-ym2 y)-O thin film solid electrolyte, above-mentioned x meets the relation of 0≤x<1, above-mentioned y meets the relation of 0≤y<1, above-mentioned M1 is selected from least one in La, Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, Ba, and above-mentioned M2 is selected from least one in Mg, W, Al, Ge, Ru, Nb, Ni, Ta, Co, Fe, Zr, Hf, Fe, Cr, Ca.This film solid electrolyte has higher high, the lower electronic conductivity of Li ionic conductivity, its ionic conductivity/electronic conductivity>10 3.
The preparation method of film mainly contains: 1. physical vaporous deposition; 2. chemical vapour deposition technique; 3. solution coating method.And physical vaporous deposition can be divided into evaporation coating, sputter coating and ion film plating; The preparation method of thin film solid electrolyte material of the present invention adopts the magnetron sputtering embrane method, equipment can adopt home equipment or import equipment, JGP-800 type magnetic-controlled sputtering coating equipment as CAS Shenyang Scientific Instruments Co., Ltd., the magnetron sputtering coater that Beijing Tai Kenuo Science and Technology Ltd. produces, the Discovery of U.S. DENTON company, Explore series rf magnetron sputtering filming equipment.The preparation method is after at first according to material, the metal oxide of required chemical element ratio mixes, be pressed into target, and target at 550～1300 ℃ of lower sintering 6～12h, be cooled to room temperature, then use the rf magnetron sputtering device by target as sputter on cell cathode or anode film surface, make thin film solid electrolyte of the present invention.
The solution coating method can be divided into chemical reaction deposit method, sol-gel process, anode oxidation method, galvanoplastic and LB masking method, these methods do not need vacuum environment, equipment needed thereby is few, can be in various matrix surface film forming, the use sol-gel process is also being attempted in the preparation of thin film solid electrolyte material of the present invention.The sol-gel ratio juris is by some III, VI, V group element synthesizes hydrocarbon oxy compound, and utilize some inorganic salts as chloride, nitrate, acetates etc. are as the plated film material, these plated film things are dissolved in to some organic solvent, as ethanol, become the colloidal sol plating solution in acetic acid or acetone, the concentration aspect is generally to be adjusted to be beneficial to even glue film forming and to get final product, prepare sol-process and can add citric acid, EDTA etc. have the material of chelation to form metal complex, make the colloidal sol film forming made better, then adopt the methods such as dipping and centrifugal whirl coating to be coated on matrix surface, because occurring, hydrolysis forms colloidal film, then dewatered, sintering and be condensed into solid film.Concrete scheme of the present invention is: according to material, the slaine of required chemical element ratio mixes, and makes colloidal sol; With sol evenning machine by the colloidal sol uniform spreading on cell cathode or anode film surface; Subsequently at 100～150 ℃ of drying 5～20min, then, at 550～1300 ℃ of lower sintering 6～12h, sintering, obtain thin film solid electrolyte of the present invention.
Described slaine is metal chloride, metal nitrate or metal acetate;
The process of making colloidal sol is in metal chloride, metal nitrate or metal acetate, to add citric acid ethanol, acetone or the acetic acid solution of weight content 5-15% to make colloidal sol; The concentration of slaine in solution is generally to be adjusted to be beneficial to even glue film forming and to get final product.
Described sol evenning machine can be the KW series sol evenning machine that Korea S INFINEX sol evenning machine, U.S.'s Cee BenchTop sol evenning machine or Microelectronics Institute of the Chinese Academy of Sciences produce.
The good effect that the present invention produces is:
1. Li-(the Mn that prepared by the present invention 1-xm1 x)-(Ti 1-ym2 y)-O solid electrolyte film has higher Li ionic conductivity, lower electronic conductivity, its ionic conductivity/electronic conductivity>10 3, relatively be applicable to doing film solid state battery electrolyte and use.
2. preparation method's operation of the present invention is simple, and easy operating, be applicable to suitability for industrialized production.
The present invention separately have that equipment requirement is simple, cost is low, handling safety, the advantage such as pollution-free.
Embodiment
Embodiment 1
Li-Mn-(Ti 0.8fe 0.2)-O thin film solid electrolyte, show Li-Mn-(Ti through the XRD test 0.8fe 0.2)-O solid electrolyte crystal formation is the spinelle crystal formation; Fitting result after ac impedance measurement shows Li-Mn-(Ti 0.8fe 0.2the electronic conductivity of)-O solid electrolyte is 1.15 * 10 -8s/cm, ionic conductivity is 1.43 * 10 -5s/cm, ionic conductivity/electronic conductivity=1.24*10 3.Its preparation method is:
1) the required chemical element ratio according to above-mentioned thin film solid electrolyte material, mix lithium nitrate, manganese chloride, titanium chloride, iron chloride, adds the citric acid ethanolic solution of weight content 10% to make colloidal sol;
2) with sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Mn-O cathode film for battery electrode surface; Described sol evenning machine can be Korea S INFINEX sol evenning machine.
3) dry 20min at 100 ℃ subsequently, then, at 1300 ℃ of sintering 6h, be cooled to room temperature, can obtain Li-Mn-(Ti of the present invention 0.8fe 0.2)-O thin film solid electrolyte.
Embodiment 2
Li-(Mn 0.76y 0.24)-Ti-O thin film solid electrolyte, show Li-(Mn through the XRD test 0.76y 0.24)-Ti-O solid electrolyte crystal formation is the spinelle crystal formation; Fitting result after ac impedance measurement shows Li-(Mn 0.76y 0.24the electronic conductivity of)-Ti-O solid electrolyte is 7.325 * 10 -9s/cm, ionic conductivity is 5.91 * 10 -5s/cm, ionic conductivity/electronic conductivity=8.07*10 3.Its preparation method is:
1) the required chemical element ratio according to above-mentioned thin film solid electrolyte material, mix lithium nitrate, manganese acetate, titanium tetrachloride, yttrium chloride, adds the citric acid acetic acid solution of weight content 5% to make colloidal sol;
2) with sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Ti-O battery anode thin-film electrode surface; Described sol evenning machine is U.S. Cee BenchTop sol evenning machine.
3) subsequently at 120 ℃ of dry 10min, then, at 900 ℃ of sintering 9h, be cooled to room temperature, can obtain Li-(Mn of the present invention 0.76y 0.24)-Ti-O thin film solid electrolyte.
Embodiment 3
Li-(Mn 0.98la 0.02)-(Ti 0.9mg 0.1)-O thin film solid electrolyte, show Li-(Mn through the XRD test 0.98la 0.02)-(Ti 0.9mg 0.1)-O solid electrolyte crystal formation is the spinelle crystal formation; Fitting result after ac impedance measurement shows Li-(Mn 0.98la 0.02)-(Ti 0.9mg 0.1the electronic conductivity of)-O solid electrolyte is 3.85 * 10 -9s/cm, ionic conductivity is 2.77 * 10 -5s/cm, ionic conductivity/electronic conductivity=7.19*10 3.Its preparation method is:
1) the required chemical element ratio according to above-mentioned thin film solid electrolyte material, mix lithium nitrate, manganous chloride, titanium tetrachloride, lanthanum nitrate, magnesium chloride, adds the citric acid acetone of weight content 15% to make colloidal sol;
2) with sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Ti-O battery anode thin-film electrode surface; The KW series sol evenning machine that Microelectronics Institute of the described sol evenning machine Chinese Academy of Sciences produces.
3) subsequently at 150 ℃ of dry 5min, then, at 550 ℃ of sintering 12h, be cooled to room temperature, can obtain Li-(Mn of the present invention 0.98la 0.02)-(Ti 0.9mg 0.1)-O thin film solid electrolyte.
Embodiment 4
Li-(Mn 0.85nd 0.15)-(Ti 0.8ta 0.2)-O thin film solid electrolyte, show Li-(Mn through the XRD test 0.85nd 0.15)-(Ti 0.8ta 0.2)-O solid electrolyte crystal formation is the spinelle crystal formation; Fitting result after ac impedance measurement shows Li-(Mn 0.85nd 0.15)-(Ti 0.8ta 0.2the electronic conductivity of)-O solid electrolyte is 5.62 * 10 -10s/cm, ionic conductivity is 7.55 * 10 -6s/cm, ionic conductivity/electronic conductivity=1.34*10 4.Its preparation method is:
1) the required chemical element ratio according to above-mentioned thin film solid electrolyte material, mix lithium nitrate, manganous chloride, titanium tetrachloride, columbium pentachloride, tantalic chloride salt, adds the citric acid ethanol of weight content 8% to make colloidal sol;
2) with sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Ti-O battery anode thin-film electrode surface;
3) subsequently at 125 ℃ of dry 8min, then, at 800 ℃ of sintering 10h, be cooled to room temperature, can obtain Li-(Mn of the present invention 0.85nd 0.15)-(Ti 0.8ta 0.2)-O thin film solid electrolyte.
Embodiment 5
Li-(Mn 0.9ba 0.1)-(Ti 0.9ca 0.1)-O thin film solid electrolyte, show Li-(Mn through the XRD test 0.9ba 0.1)-(Ti 0.9ca 0.1)-O solid electrolyte crystal formation is the spinelle crystal formation; Fitting result after ac impedance measurement shows Li-(Mn 0.9ba 0.1)-(Ti 0.9ca 0.1the electronic conductivity of)-O solid electrolyte is 1.98 * 10 -10s/cm, ionic conductivity is 2.33 * 10 -7s/cm, ionic conductivity/electronic conductivity=1.18*10 3.
Its preparation method is: the required chemical element ratio according to above-mentioned thin film solid electrolyte material, the oxide of lithium metal, manganese, titanium, barium, calcium is mixed, put into the target mould and be pressed into target, and target at 550 ℃ of lower sintering 12h, be cooled to room temperature, then utilize the radio frequency magnetron instrument that it is sputtered to Li-Mn-O cathode film for battery electrode surface, make Li-(Mn of the present invention 0.9ba 0.1)-(Ti 0.9ca 0.1)-O thin film solid electrolyte.
Described sputtering coating equipment is used the JGP-800 type magnetic-controlled sputtering coating equipment of CAS Shenyang Scientific Instruments Co., Ltd..
Embodiment 6
Li-(Mn 0.7gd 0.3)-(Ti 0.95nb 0.05)-O thin film solid electrolyte, show Li-(Mn through the XRD test 0.7gd 0.3)-(Ti 0.95nb 0.05)-O solid electrolyte film crystal formation is unformed; Fitting result after ac impedance measurement shows Li-(Mn 0.7gd 0.3)-(Ti 0.95nb 0.05the electronic conductivity of)-O solid electrolyte film is 4.22 * 10 -10s/cm, ionic conductivity is 1.96 * 10 -6s/cm, ionic conductivity/electronic conductivity=4.64*10 3.
Its preparation method is: the required chemical element ratio according to above-mentioned thin film solid electrolyte material, the oxide of metal Li, Mn, Ti, Gd, Nb is mixed, put into the target mould and be pressed into target, and target at 900 ℃ of lower sintering 9h, be cooled to room temperature, then utilize the radio frequency magnetron filming equipment that it is sputtered to Li-Mn-O cathode film for battery electrode surface, make Li-(Mn of the present invention 0.7gd 0.3)-(Ti 0.95nb 0.05)-O thin film solid electrolyte.The magnetron sputtering coater that described sputtering coating equipment is used Beijing Tai Kenuo Science and Technology Ltd. to produce.
Embodiment 7
Li-(Mn 0.75la 0.25)-(Ti 0.9al 0.1)-O solid electrolyte, show Li-(Mn through the XRD test 0.75la 0.25)-(Ti 0.9al 0.1)-O solid electrolyte crystal formation is unformed; Fitting result after ac impedance measurement shows Li-(Mn 0.75la 0.25)-(Ti 0.9al 0.1the electronic conductivity of)-O solid electrolyte film is 9.70 * 10 -10s/cm, ionic conductivity is 3.56 * 10 -6s/cm, ionic conductivity/electronic conductivity=3.67*10 3.
Its preparation method is: the required chemical element ratio according to above-mentioned thin film solid electrolyte material, the oxide of metal Li, Mn, Ti, La, Al is mixed, put into the target mould and be pressed into target, and target at 1100 ℃ of lower sintering 8h, be cooled to room temperature, then utilize the radio frequency magnetron filming equipment that it is sputtered to Li-Ti-O battery anode thin-film electrode surface, make Li-(Mn of the present invention 0.75la 0.25)-(Ti 0.9al 0.1)-O thin film solid electrolyte.Described sputtering coating equipment is used the Explore of U.S. DENTON company series rf magnetron sputtering filming equipment.
Embodiment 8
Li-(Mn 0.85ba 0.15)-(Ti 0.99al 0.01)-O solid electrolyte film, show Li-(Mn through the XRD test 0.85ba 0.15)-(Ti 0.99al 0.01)-O solid electrolyte crystal formation is unformed; Fitting result after ac impedance measurement shows Li-(Mn 0.85ba 0.15)-(Ti 0.99al 0.01the electronic conductivity of)-O solid electrolyte is 4.81 * 10 -10s/cm, ionic conductivity is 9.55 * 10 -7s/cm, ionic conductivity/electronic conductivity=1.99*10 3.
Its preparation method is: the required chemical element ratio according to above-mentioned thin film solid electrolyte material, the oxide of metal Li, Mn, Ti, Ba, Al is mixed, put into the target mould and be pressed into target, and target at 1300 ℃ of lower sintering 6h, be cooled to room temperature, then utilize the radio frequency magnetron instrument that it is sputtered to Li-Ti-O battery anode thin-film electrode surface, make Li-(Mn of the present invention 0.85ba 0.15)-(Ti 0.99al 0.01)-O thin film solid electrolyte.Described sputtering coating equipment is used the JGP-800 type magnetic-controlled sputtering coating equipment of CAS Shenyang Scientific Instruments Co., Ltd..
Embodiment 9
Li-(Mn 0.15sm 0.85)-(Ti 0.15co 0.85)-O solid electrolyte film, show Li-(Mn through the XRD test 0.15sm 0.85)-(Ti 0.15co 0.85)-O solid electrolyte crystal formation is unformed; Fitting result after ac impedance measurement shows Li-(Mn 0.15sm 0.85)-(Ti 0.15co 0.85the electronic conductivity of)-O solid electrolyte is 4.08 * 10 -10s/cm, ionic conductivity is 4.17 * 10 -7s/cm, ionic conductivity/electronic conductivity=1.02*10 3.
Its preparation method is: the required chemical element ratio according to above-mentioned thin film solid electrolyte material, the oxide of metal Li, Mn, Sm, Ti, Co is mixed, put into the target mould and be pressed into target, and target at 1000 ℃ of lower sintering 7h, be cooled to room temperature, then utilize the rf magnetron sputtering filming equipment that it is sputtered to Li-Ti-O battery anode thin-film electrode surface, make Li-(Mn of the present invention 0.15sm 0.85)-(Ti 0.15co 0.85)-O thin film solid electrolyte.Described sputtering coating equipment is used the U.S. Discovery of DENTON company rf magnetron sputtering filming equipment.

Claims (5)

1. a thin film solid electrolyte material, is characterized in that, its material structure is Li-(Mn 1-xm1 x)-(Ti 1-ym2 y)-O, wherein x meets the relation of 0≤x<1, and y meets the relation of 0≤y<1.
2. thin film solid electrolyte material as claimed in claim 1, is characterized in that, M1 is selected from least one in La, Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, Ba; M2 is selected from least one in Mg, W, Al, Ge, Ru, Nb, Ni, Ta, Co, Fe, Zr, Hf, Cr, Ca.
3. thin film solid electrolyte material as claimed in claim 1 or 2, is characterized in that, its ionic conductivity/electronic conductivity>10 3.
4. the preparation method of thin film solid electrolyte material as claimed in claim 1 or 2, is characterized in that, according to material, the slaine of required chemical element ratio mixes, and makes colloidal sol; By the colloidal sol uniform spreading on cell cathode or anode film surface; Subsequently at 100～150 ℃ of drying 5～20min, then, at 550～1300 ℃ of lower sintering 6～12h, sintering, obtain thin film solid electrolyte of the present invention;
Described slaine is metal chloride, metal nitrate or metal acetate;
The process of making colloidal sol is in metal chloride, metal nitrate or metal acetate, to add citric acid ethanol, acetone or the acetic acid solution of weight content 5-15% to make colloidal sol.
5. the preparation method of thin film solid electrolyte material as claimed in claim 1 or 2, it is characterized in that, after according to material, the metal oxide of required chemical element ratio mixes, be pressed into target, and target at 550～1300 ℃ of lower sintering 6～12h, be cooled to room temperature, then with the rf magnetron sputtering filming equipment, it sputtered to cell cathode or anode film surface, make thin film solid electrolyte of the present invention.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2596023C2 (en) * 2014-12-17 2016-08-27 Общество с ограниченной ответственностью "Литион" Anode material
CN106264849A (en) * 2016-08-18 2017-01-04 孟玲 It is precious that water is warmed up in the heating capable of circulation of a kind of charging property
CN106684440A (en) * 2016-07-28 2017-05-17 上海应用技术学院 Preparation method for LiBaLaZrWREAlO solid electrolyte
CN108134132A (en) * 2017-12-29 2018-06-08 成都新柯力化工科技有限公司 A kind of dynamic lithium battery microcapsules thin-film ceramics solid electrolyte and preparation method
CN109841853A (en) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 A kind of cathode material for solid-oxide fuel cell
CN113060769A (en) * 2021-03-24 2021-07-02 电子科技大学 Lithium cobaltate positive electrode material, preparation method thereof and lithium battery
CN113130976A (en) * 2019-12-30 2021-07-16 天津国安盟固利新材料科技股份有限公司 Garnet type solid electrolyte and preparation method thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080117563A1 (en) * 2006-11-21 2008-05-22 Kaoru Nagata All-solid-state electric double layer capacitor
CN101281985A (en) * 2007-03-29 2008-10-08 Tdk株式会社 All-solid-state lithium-ion secondary battery and production method thereof
CN101495666A (en) * 2006-07-27 2009-07-29 日矿金属株式会社 Lithium-containing transition metal oxide target, process for producing the same and lithium ion thin-film secondary battery
CN102473958A (en) * 2010-04-13 2012-05-23 丰田自动车株式会社 Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material
CN103066272A (en) * 2013-01-05 2013-04-24 宁波大学 Surface-modified Li-rich positive electrode material doped with Ni2+, mn4+, si4+, zn2+, F - and its preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101495666A (en) * 2006-07-27 2009-07-29 日矿金属株式会社 Lithium-containing transition metal oxide target, process for producing the same and lithium ion thin-film secondary battery
US20080117563A1 (en) * 2006-11-21 2008-05-22 Kaoru Nagata All-solid-state electric double layer capacitor
CN101281985A (en) * 2007-03-29 2008-10-08 Tdk株式会社 All-solid-state lithium-ion secondary battery and production method thereof
CN102473958A (en) * 2010-04-13 2012-05-23 丰田自动车株式会社 Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material
CN103066272A (en) * 2013-01-05 2013-04-24 宁波大学 Surface-modified Li-rich positive electrode material doped with Ni2+, mn4+, si4+, zn2+, F - and its preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2596023C2 (en) * 2014-12-17 2016-08-27 Общество с ограниченной ответственностью "Литион" Anode material
CN106684440A (en) * 2016-07-28 2017-05-17 上海应用技术学院 Preparation method for LiBaLaZrWREAlO solid electrolyte
CN106684440B (en) * 2016-07-28 2018-10-30 上海应用技术学院 A kind of LiBaLaZrW-M-AlO method for preparing solid electrolyte
CN106264849A (en) * 2016-08-18 2017-01-04 孟玲 It is precious that water is warmed up in the heating capable of circulation of a kind of charging property
CN109841853A (en) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 A kind of cathode material for solid-oxide fuel cell
CN108134132A (en) * 2017-12-29 2018-06-08 成都新柯力化工科技有限公司 A kind of dynamic lithium battery microcapsules thin-film ceramics solid electrolyte and preparation method
CN113130976A (en) * 2019-12-30 2021-07-16 天津国安盟固利新材料科技股份有限公司 Garnet type solid electrolyte and preparation method thereof
CN113060769A (en) * 2021-03-24 2021-07-02 电子科技大学 Lithium cobaltate positive electrode material, preparation method thereof and lithium battery
CN113336547A (en) * 2021-04-22 2021-09-03 海南大学 Oxide type solid electrolyte film and preparation method thereof
CN113336547B (en) * 2021-04-22 2022-05-31 海南大学 Oxide type solid electrolyte film and preparation method thereof
CN113258130A (en) * 2021-04-27 2021-08-13 燕山大学 Amorphous halide solid electrolyte, preparation and application in all-solid-state battery
CN116925762A (en) * 2023-06-14 2023-10-24 福建江夏学院 Mn-doped tunable wide rectangular red fluorescent material and preparation method thereof
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