CN103456983B - Solid thin film electrolyte material and preparation method thereof - Google Patents
Solid thin film electrolyte material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of solid thin film electrolyte material and preparation method thereof, its structure is Li (Mn1‑xM1x)‑(Ti1‑ yM2y) O represents, wherein x meets the relation of 0≤x ＜ 1, y meets the relation of 0≤y ＜ 1, at least one in La, Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, Ba of above-mentioned M1, at least one in Mg, W, Al, Ge, Ru, Nb, Ni, Ta, Co, Fe, Zr, Hf, Fe, Cr, Ga of M2.This thin film solid electrolyte is prepared through the method for sol-gal process or rf magnetron sputtering.This thin film solid electrolyte has higher Li ionic conductivity, relatively low electronic conductivity and good thermodynamic stability, is particularly well-suited to produce solid Li-ion battery.
Description
Technical field
The present invention relates to good solid thin film electrolyte material of a kind of lithium-ion-conducting and preparation method thereof.
Background technology
Since eighties of last century the nineties commercialization, lithium ion battery owing to having that energy density is high, have extended cycle life,
There is no memory effect, advantages of environment protection, become the succedaneum of Ni-MH battery and nickel-cadmium cell soon.But, lithium from
The safety issue of sub-battery is always focus of concern.Containing flammable Organic substance in lithium-ion battery electrolytes, hold
Easily occur that corrosion electrode, leakage, decomposition generation gas make air pressure inside raise the important safety hidden danger such as even generation burning.Use
Polymer dielectric can alleviate above safety problem to a certain extent, but cannot fundamentally solve.
Abroad in Recent Years is the most active to the R and D of all solid state inorganic thin film lithium battery, in aerospace industry, thin
Film lithium battery and solaode constitute jointly power supply, and this energy storage power supply is more superior than original Ni-Cd power supply
Many, because for aerospace craft, miniaturization, lightweight are important indicators.Under the support energetically of NASA, beautiful
The ITN advanced person light cell group of the ITN energy resource system company subordinate of the state state of Colorado uses Oak Ridge country of the U.S. real
The technology that testing room (ORNL) provides produces all solid state thin lithium battery and ties mutually with flexible Cu-In-Ga-Se (CIGS) solaode
The power supply closed and power management circuit, and develop the special integrated flexible integration power module of satellite.The Munin of Sweden defends
The Bitsy satellite (1Kg) of star (5 Kg) and the U.S. all have employed this secondary cell, and All-solid film batteries has become nanometer
The optimum selection of energy storage in satellite, additionally, its purposes also includes miniature robot surveillance plane electrical source of power, miniature
The aspects such as sensor, RF smart card.
Thin film lithium/lithium ion battery is not the most by large-scale commercial, except its price is not connect by the public
By outward, main reason or its performance do not reach to replace completely the stage of conventional batteries, also have many actual application to ask
Inscribe urgently to be resolved hurrily, as improved the capacity of battery, simplifying preparation technology, reduction battery cost etc..
In the middle of the solid electrolyte that All-solid film batteries is used, Chinese patent CN102473958A discloses one
The solid electrolyte material that Li ionic conduction performance is good.The method utilizing reactivity evaporation forms the densification of Li-La-Ti-O
Thin film.The method of evaporation makes the best the combining of crystal grain, it is suppressed that the resistance of grain boundaries increases.
Bates et al., Electrical properties of amorphous lithium electrolyte thin
Films, Solid State Ionics., 1992,53-56, use rf magnetron sputtering LiPO in a nitrogen atmosphere4The side of target
Method prepares LiPON and at room temperature has good ionic conductivity (2.3(± 0.7) × 10-6And low-down electricity S/cm)
Electron conductivity (＜ 10-14S/cm), electrochemical stability window is 5.5V.At sputtering LiPO4During target forms LiPON thin film,
Atom N instead of LiPO4(-O-) in structure or bridged bond (O) oxygen, form two covalent bonds (-N=) or three covalent bonds of nitrogen
(-N ＜=structure.The increase of LiPON membrane ion electrical conductivity is attributed to non-crystalline structure and the N content of LiPON thin film, N content
The highest, its ionic conductivity is the biggest.
Lee et al., Crystal structure revision and identification of Li+-ion
migration pathways in the garnet-like Li5La3M2O12(M=Nb, Ta) oxides, Chem.
Mater. 2004,16, preparation there is Garnet structure, formula is Li5La3M2O12The solid electrolyte of (M=Nb, Ta)
Present higher ionic conductivity, when with lower valency ion (such as Ba2+、Sr2+And K+) replace La3+Time, Li6BaLa2Ta2O12Tool
There is the highest ionic conductivity 4 × 10-5S/cm(295K), activation energy is 0.40eV;And work as Ta5+Or Nb5+By such as In3+Taken
Dai Shi, sample Li5.5La3Nb1.75In0.25O12In ionic conductivity can reach 1.8 × 10-4S/cm(323K).
LiPON membrane ion electrical conductivity is high, and thermodynamic stability is good and electrochemical window width, but to the water vapour in air
The most sensitive with oxygen, Li5La3M2O12Material preparation process such as (M=Nb, Ta) is more complicated, unsuitable for industry metaplasia
Produce.
Summary of the invention
The purpose of the present invention: aim to provide a kind of Li ionic conductivity height, electronic conductivity is low and thermodynamic stability good
Solid thin film electrolyte material, and provide that technique is simple, constant product quality, lower-cost this thin film solid electrolyte
The preparation method of material.
Technical scheme is as follows:
Solid thin film electrolyte material, its material structure is Li-(Mn1-xM1x)-(Ti1-yM2y)-O thin film solid electrolyte,
Above-mentioned x meets the relation of 0≤x ＜ 1, and above-mentioned y meets the relation of 0≤y ＜ 1, above-mentioned M1 selected from La, Sr, Na, Nd, Pr, Sm, Gd,
At least one in Dy, Y, Eu, Tb, Ba, above-mentioned M2 selected from Mg, W, Al, Ge, Ru, Nb, Ni, Ta, Co, Fe, Zr, Hf, Fe, Cr,
At least one in Ca.This thin film solid state electrolyte has the electronic conductivity that higher Li ionic conductivity is high, relatively low, its from
Electron conductivity/electronic conductivity > 103。
The preparation method of thin film mainly has: 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 thin film solid electrolyte material of the present invention
The preparation method of material uses magnetron sputtering embrane method, and equipment can use home equipment or import equipment, such as Chinese Academy of Sciences Shen
The JGP-800 type magnetic-controlled sputtering coating equipment of sun scientific instrument limited company, Beijing Technol Science Co., Ltd. produces
Magnetron sputtering coater, U.S.'s DENTON company Discovery, Explore train of radio frequency magnetic-controlled sputtering coating equipment.Preparation
After method is first according to the metal-oxide mix homogeneously of the chemical element ratio needed for material, it is pressed into target, and target
At 550～1300 DEG C, sinter 6～12h, be cooled to room temperature, then use rf magnetron sputtering device by target as sputter at cell cathode
Or anode film surface, prepare the thin film solid electrolyte of the present invention.
Solution coating method can be divided into chemical reaction deposit method, sol-gel process, anodizing, galvanoplastic and LB system
Embrane method, these methods need not vacuum environment, and equipment needed thereby is few, can be at various matrix surface film forming, the thin film solid of the present invention
Use sol-gel process is also attempted in the preparation of electrolyte.The principle of sol-gel process is by some unit of III, VI, V race
Element synthesis hydrocarbon oxy compound, and utilize some inorganic salts such as chloride, nitrate, acetate etc. as plated film material,
These plated film things are dissolved in some organic solvent, and as become colloidal sol plating solution in ethanol, acetic acid or acetone, concentration aspect is usually to be adjusted
Joint to beneficially spin coating film forming, is prepared sol-process and can be added citric acid, EDTA etc. and have the material of chelation with formation
Metal complex, makes the colloidal sol film property made more preferable, then uses the methods such as dipping and centrifugal whirl coating to be coated on matrix surface,
Forming colloidal film because there is hydrolysis, then carrying out being dehydrated, sintering and be condensed into solid film.The concrete scheme of the present invention
It is: according to the slaine mix homogeneously of the chemical element ratio needed for material, make colloidal sol；With sol evenning machine, colloidal sol uniform spreading is existed
On cell cathode or anode film surface；It is dried 5～20min at 100～150 DEG C subsequently, then at 550～1300 DEG C, sinters 6
～12h, sintering, obtain the thin film solid electrolyte of the present invention.
Described slaine is metal chloride, metal nitrate or metal acetate；
The process making colloidal sol is addition weight content 5-in metal chloride, metal nitrate or metal acetate
Citric acid ethanol, acetone or the acetic acid solution of 15% make colloidal sol；Slaine concentration in the solution is usually adjusted to the evenest
Glue film forming.
Described sol evenning machine can be that Korea S's INFINEX sol evenning machine, U.S.'s Cee BenchTop sol evenning machine or the Chinese Academy of Sciences are micro-
The KW series sol evenning machine that electron institute produces.
The good effect that the present invention produces is:
1. Li-(the Mn that prepared by the present invention1-xM1x)-(Ti1-yM2y)-O solid electrolyte film has higher Li ion-conductance
Conductance, relatively low electronic conductivity, its ionic conductivity/electronic conductivity > 103, compare and be suitable for doing the electrolysis of thin film solid battery
Matter uses.
Preparation method operation the most of the present invention is simple, it is easy to operation, it is adaptable to industrialized production.
3. the advantages such as the present invention separately has that equipment requirements is simple, low cost, operation are safe and pollution-free.
Detailed description of the invention
Embodiment 1
Li-Mn-(Ti0.8Fe0.2)-O thin film solid electrolyte, show Li-Mn-(Ti through XRD test0.8Fe0.2)-O solid
Electrolyte crystal formation is spinelle crystal formation；Fitting result after ac impedance measurement shows Li-Mn-(Ti0.8Fe0.2)-O solid electrolytic
The electronic conductivity of matter is 1.15 × 10-8S/cm, ionic conductivity is 1.43 × 10-5S/cm, ionic conductivity/electronic conductance
Rate=1.24*103.Its preparation method is:
1) according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by lithium nitrate, manganese chloride, chlorination
Titanium, iron chloride mix homogeneously, the citric acid ethanol solution adding weight content 10% makes colloidal sol；
2) use sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Mn-O cathode film for battery electrode surface；Described sol evenning machine
It can be Korea S's INFINEX sol evenning machine.
3) dry 20min at 100 DEG C subsequently, then sinter 6h at 1300 DEG C, be cooled to room temperature, i.e. can get the present invention's
Li-Mn-(Ti0.8Fe0.2)-O thin film solid electrolyte.
Embodiment 2
Li-(Mn0.76Y0.24)-Ti-O thin film solid electrolyte, show Li-(Mn through XRD test0.76Y0.24)-Ti-O solid
Electrolyte crystal formation is spinelle crystal formation；Fitting result after ac impedance measurement shows Li-(Mn0.76Y0.24)-Ti-O solid electrolytic
The electronic conductivity of matter is 7.325 × 10-9S/cm, ionic conductivity is 5.91 × 10-5S/cm, ionic conductivity/electronic conductance
Rate=8.07*103.Its preparation method is:
1) according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by lithium nitrate, manganese acetate, four chlorinations
Titanium, Yttrium chloride(Y2Cl6) mix homogeneously, the citric acid acetic acid solution adding weight content 5% makes colloidal sol；
2) use sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Ti-O battery anode thin-film electrode surface；Described sol evenning machine
It it is U.S.'s Cee BenchTop sol evenning machine.
3) subsequently at 120 DEG C of dry 10min, then sinter 9h at 900 DEG C, be cooled to room temperature, i.e. can get the Li-of the present invention
(Mn0.76Y0.24)-Ti-O thin film solid electrolyte.
Embodiment 3
Li-(Mn0.98La0.02)-(Ti0.9Mg0.1)-O thin film solid electrolyte, show Li-through XRD test
(Mn0.98La0.02)-(Ti0.9Mg0.1)-O solid electrolyte crystal formation is spinelle crystal formation；Fitting result table after ac impedance measurement
Bright Li-(Mn0.98La0.02)-(Ti0.9Mg0.1) electronic conductivity of-O solid electrolyte is 3.85 × 10-9S/cm, ionic conductance
Rate is 2.77 × 10-5S/cm, ionic conductivity/electronic conductivity=7.19*103.Its preparation method is:
1) according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by lithium nitrate, manganous chloride, tetrachloro
Changing titanium, Lanthanum (III) nitrate, magnesium chloride mix homogeneously, the citric acid acetone adding weight content 15% makes colloidal sol；
2) use sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Ti-O battery anode thin-film electrode surface；Described sol evenning machine
The KW series sol evenning machine that Microelectronics Institute of the Chinese Academy of Sciences produces.
3) subsequently at 150 DEG C of dry 5min, then sinter 12h at 550 DEG C, be cooled to room temperature, i.e. can get the Li-of the present invention
(Mn0.98La0.02)-(Ti0.9Mg0.1)-O thin film solid electrolyte.
Embodiment 4
Li-(Mn0.85Nd0.15)-(Ti0.8Ta0.2)-O thin film solid electrolyte, show Li-through XRD test
(Mn0.85Nd0.15)-(Ti0.8Ta0.2)-O solid electrolyte crystal formation is spinelle crystal formation；Fitting result table after ac impedance measurement
Bright Li-(Mn0.85Nd0.15)-(Ti0.8Ta0.2) electronic conductivity of-O solid electrolyte is 5.62 × 10-10S/cm, ionic conductance
Rate is 7.55 × 10-6S/cm, ionic conductivity/electronic conductivity=1.34*104.Its preparation method is:
1) according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by lithium nitrate, manganous chloride, tetrachloro
Changing titanium, Columbium pentachloride., tantalic chloride salt mix homogeneously, colloidal sol made by the citric acid ethanol adding weight content 8%；
2) use sol evenning machine above-mentioned colloidal sol uniform spreading at Li-Ti-O battery anode thin-film electrode surface；
3) subsequently at 125 DEG C of dry 8min, then sinter 10h at 800 DEG C, be cooled to room temperature, i.e. can get the Li-of the present invention
(Mn0.85Nd0.15)-(Ti0.8Ta0.2)-O thin film solid electrolyte.
Embodiment 5
Li-(Mn0.9Ba0.1)-(Ti0.9Ca0.1)-O thin film solid electrolyte, show Li-(Mn through XRD test0.9Ba0.1)-
(Ti0.9Ca0.1)-O solid electrolyte crystal formation is spinelle crystal formation；Fitting result after ac impedance measurement shows Li-
(Mn0.9Ba0.1)-(Ti0.9Ca0.1) 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*103。
Its preparation method is: according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by lithium metal,
Manganese, titanium, barium, the oxide mix homogeneously of calcium, put into and be pressed into target in target mould, and target is sintered at 550 DEG C
12h, is cooled to room temperature, then utilizes radio frequency magnetron instrument to be sputtered at Li-Mn-O cathode film for battery electrode surface, prepares this
Li-(the Mn of invention0.9Ba0.1)-(Ti0.9Ca0.1)-O thin film solid electrolyte.
Described sputtering coating equipment uses the JGP-800 type magnetic of CAS Shenyang Scientific Instruments Co., Ltd.
Control sputtering coating equipment.
Embodiment 6
Li-(Mn0.7Gd0.3)-(Ti0.95Nb0.05)-O thin film solid electrolyte, show Li-(Mn through XRD test0.7Gd0.3)-
(Ti0.95Nb0.05)-O solid electrolyte film crystal formation is unformed；Fitting result after ac impedance measurement shows Li-
(Mn0.7Gd0.3)-(Ti0.95Nb0.05) electronic conductivity of-O solid electrolyte film is 4.22 × 10-10S/cm, ionic conductivity
It is 1.96 × 10-6S/cm, ionic conductivity/electronic conductivity=4.64*103。
Its preparation method is: according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by metal Li,
The oxide mix homogeneously of Mn, Ti, Gd, Nb, puts into and is pressed into target in target mould, and target is sintered 9h at 900 DEG C,
It is cooled to room temperature, then utilizes radio frequency magnetron filming equipment to be sputtered at Li-Mn-O cathode film for battery electrode surface, prepare
Li-(the Mn of the present invention0.7Gd0.3)-(Ti0.95Nb0.05)-O thin film solid electrolyte.Described sputtering coating equipment uses Beijing
The magnetron sputtering coater that Tai Kenuo Science and Technology Ltd. produces.
Embodiment 7
Li-(Mn0.75La0.25)-(Ti0.9Al0.1)-O solid electrolyte, show Li-(Mn through XRD test0.75La0.25)-
(Ti0.9Al0.1)-O solid electrolyte crystal formation is unformed；Fitting result after ac impedance measurement shows Li-
(Mn0.75La0.25)-(Ti0.9Al0.1) electronic conductivity of-O solid electrolyte film is 9.70 × 10-10S/cm, ionic conductivity
It is 3.56 × 10-6S/cm, ionic conductivity/electronic conductivity=3.67*103。
Its preparation method is: according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by metal Li,
The oxide mix homogeneously of Mn, Ti, La, Al, puts into and is pressed into target in target mould, and target is sintered at 1100 DEG C
8h, is cooled to room temperature, then utilizes radio frequency magnetron filming equipment to be sputtered at Li-Ti-O battery anode thin-film electrode surface,
Prepare the Li-(Mn of the present invention0.75La0.25)-(Ti0.9Al0.1)-O thin film solid electrolyte.Described sputtering coating equipment uses
U.S.'s DENTON company Explore train of radio frequency magnetic-controlled sputtering coating equipment.
Embodiment 8
Li-(Mn0.85Ba0.15)-(Ti0.99Al0.01)-O solid electrolyte film, show Li-through XRD test
(Mn0.85Ba0.15)-(Ti0.99Al0.01)-O solid electrolyte crystal formation is unformed；Fitting result after ac impedance measurement shows
Li-(Mn0.85Ba0.15)-(Ti0.99Al0.01) electronic conductivity of-O solid electrolyte is 4.81 × 10-10S/cm, ionic conductance
Rate is 9.55 × 10-7S/cm, ionic conductivity/electronic conductivity=1.99*103。
Its preparation method is: according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by metal Li,
The oxide mix homogeneously of Mn, Ti, Ba, Al, puts into and is pressed into target in target mould, and target is sintered at 1300 DEG C
6h, is cooled to room temperature, then utilizes radio frequency magnetron instrument to be sputtered at Li-Ti-O battery anode thin-film electrode surface, prepares this
Li-(the Mn of invention0.85Ba0.15)-(Ti0.99Al0.01)-O thin film solid electrolyte.Described sputtering coating equipment uses China
The JGP-800 type magnetic-controlled sputtering coating equipment of Shenyang scientific instrument limited company of academy of science.
Embodiment 9
Li-(Mn0.15Sm0.85)-(Ti0.15Co0.85)-O solid electrolyte film, show Li-through XRD test
(Mn0.15Sm0.85)-(Ti0.15Co0.85)-O solid electrolyte crystal formation is unformed；Fitting result after ac impedance measurement shows
Li-(Mn0.15Sm0.85)-(Ti0.15Co0.85) electronic conductivity of-O solid electrolyte is 4.08 × 10-10S/cm, ionic conductance
Rate is 4.17 × 10-7S/cm, ionic conductivity/electronic conductivity=1.02*103。
Its preparation method is: according to the chemical element ratio needed for above-mentioned solid thin film electrolyte material, by metal Li,
The oxide mix homogeneously of Mn, Sm, Ti, Co, puts into and is pressed into target in target mould, and target is sintered at 1000 DEG C
7h, is cooled to room temperature, then utilizes rf magnetron sputtering filming equipment to be sputtered at Li-Ti-O battery anode thin-film electrode table
Face, prepares the Li-(Mn of the present invention0.15Sm0.85)-(Ti0.15Co0.85)-O thin film solid electrolyte.Described sputtering coating equipment
Use U.S.'s DENTON company Discovery rf magnetron sputtering filming equipment.
Claims (2)
1. the solid thin film electrolyte material for lithium ion battery, it is characterised in that its material structure is Li-(Mnl- XMlx)-(Ti1-YM2Y)-0, wherein x meets the relation of 0≤x ＜ l, and y meets the relation of 0≤y ＜ l；
At least one in La, Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, Ba of Ml；
At least one in Mg, W, Al, Ge, Ru, Nb, Ni, Ta, C0, Fe, Zr, Hf, Cr, Ca of M2；
Its ionic conductivity/electronic conductivity ＞ l03；
The preparation method of described solid thin film electrolyte material is as follows: according to the slaine of the chemical element ratio needed for material
Mix homogeneously, makes colloidal sol；By colloidal sol uniform spreading on cell cathode or anode film surface；It is dried 5 subsequently l00～150 DEG C
～20min, then at 550～1300 DEG C, sinter 6～12h, sinter, obtain the thin film solid electrolyte of the present invention；
Described slaine is metal chloride, metal nitrate or metal acetate；
The process making colloidal sol adds weight content 5-15% in metal chloride, metal nitrate or metal acetate
Citric acid ethanol, acetone or acetic acid solution make colloidal sol.
2. the solid thin film electrolyte material for lithium ion battery as described in claim l, it is characterised in that its preparation side
Method be according to material needed for chemical element ratio metal-oxide mix homogeneously after, be pressed into target, and target 550
～at 1300 DEG C, sinter 6～12h, it is cooled to room temperature, is then sputtered at cell cathode with rf magnetron sputtering filming equipment
Or anode film surface, prepare thin film solid electrolyte.
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| RU2596023C2 (en) * | 2014-12-17 | 2016-08-27 | Общество с ограниченной ответственностью "Литион" | Anode material |
| 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 |
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| CN108134132B (en) * | 2017-12-29 | 2019-11-05 | 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 |
| CN113336547B (en) * | 2021-04-22 | 2022-05-31 | 海南大学 | Oxide type solid electrolyte film and preparation method thereof |
| CN113258130B (en) * | 2021-04-27 | 2023-01-03 | 燕山大学 | Amorphous halide solid electrolyte, preparation and application in all-solid-state battery |
| CN116925762B (en) * | 2023-06-14 | 2024-04-30 | 福建江夏学院 | Mn-doped tunable wide rectangular red fluorescent material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5049565B2 (en) * | 2006-11-21 | 2012-10-17 | パナソニック株式会社 | All-solid-state electric double layer capacitor |
-
2013
- 2013-09-09 CN CN201310404223.XA patent/CN103456983B/en active Active
Patent Citations (4)
| 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 |
| 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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