CN105958051A - Heterojunction lithium-ion thin film battery electrode material and preparation method thereof - Google Patents
Heterojunction lithium-ion thin film battery electrode material and preparation method thereof Download PDFInfo
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- CN105958051A CN105958051A CN201610398675.5A CN201610398675A CN105958051A CN 105958051 A CN105958051 A CN 105958051A CN 201610398675 A CN201610398675 A CN 201610398675A CN 105958051 A CN105958051 A CN 105958051A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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 provides a heterojunction lithium-ion thin film battery electrode material and a preparation method thereof. The heterojunction lithium-ion thin film battery electrode material is characterized in that the thin film material with a heterojunction characteristic is prepared through alternating deposition on a substrate surface with a vacuum deposition technology. The dimension of the monolayer material is in the range of 0.5 nm to 10 nm, and the thickness ratio of each layer can be effectively regulated and controlled by changing deposition parameters. The growth of the thin film can be controlled in an extremely small dimension range through the vacuum thin film technology, the junction between layers is tighter, and the electrochemical characteristics of different materials can be complementary with one another. The mismatching of crystal boundary can be effectively reduced by selecting materials with similar lattice parameters to carry out alternating deposition, the insertion and deinsertion of Li+ in the material are facilitated, and the battery performance is improved.
Description
Technical field
The present invention relates to relate to lithium ion battery and thin-film material technical field, especially relate to a kind of hetero-junctions lithium-ion film cell electrode material and preparation method thereof.
Background technology
Lithium ion battery is because it has the various features such as light weight, energy and specific energy density are high, electric discharge is steady, it has also become research and the most widely used secondary cell at present.Main application fields is in electronic equipment and the electrical source of power of electric automobile.But it is as the gradually miniaturization of electronic equipment, electric current and the power requirement of some equipment is reduced to the milliampere even level of microampere, therefore has increasing need for the slimline battery of the New Lightweight of long-life and high-energy-density.On the other hand, due to the electrolyte of the liquid that existing lithium ion battery uses, although this electrolyte has the highest electrical conductivity, but easily burn the most in atmosphere, and self-discharge phenomenon is difficult to control.To from the eighties in last century, people have begun to be conceived to the research and development of novel All-solid film batteries.Although experienced by the research work of many, but the challenge that still there is many being promoted in the commercialization of hull cell, one of them is exactly the electrode material that preparation has long-life and high-energy-density.
Preparation have the composite of hetero-junctions be counted as improving electrode material can one of the maximally efficient method of density.By two or more material by be coated with, mix, be blended etc. and to operate after, the electrochemical properties of one-component can not only be retained, the chemical property of enhancing can also be embodied by cooperative effect, brand-new characteristic, such as β-MnO2Superficial growth α-Fe2O3.Although the growth pattern of hetero-junctions has a variety of, but the heterojunction material interface prepared by most methods is uneven and, size is difficult to regulate and control, and such material often can only regard being simply mixed of material as, wants to show brand-new electrochemistry the most difficult.Therefore the method preparing compound heterojunction material just seems the most crucial and important.
Summary of the invention
The present invention proposes a kind of hetero-junctions lithium-ion film cell electrode material and preparation method thereof, can not only effectively prepare the heterogenous junction film material of large area homoepitaxial by this method, and each layer thickness ratio can be regulated and controled, the single film layer THICKNESS CONTROL of alternating growth in 0.5-10 nanometer range, even epitaxial growth can reach the level of several structure cell.
A kind of technical scheme of the present invention is achieved in that a kind of hetero-junctions lithium-ion film cell electrode material, including substrate material layer, the negative electrode active material layer grown above of described substrate material layer or positive electrode active material layer, described negative electrode active material layer and positive electrode active material layer are formed by multi-layer compound film, and described negative electrode active material layer and positive electrode active material layer are by evaporating deposition technique alternating growth.
As the preferred technical scheme of one, described substrate material layer use carbon, silicon, copper, aluminum or stainless steel substrates any one.
As the preferred technical scheme of one, the surface roughness of described substrate material layer is less than 100 nanometers.
As the preferred technical scheme of one, the surface of described substrate material layer utilizes the metal current collector layer after magnetron sputtering technique one layer of 50-500 nanometer of deposition.As the preferred technical scheme of one, the THICKNESS CONTROL of monolayer material is in 0.5-10 nanometer range, and each thickness in monolayer thickness ratio is between 1-10；Overall film thickness can reach more than 1 micron.
As the preferred technical scheme of one, described negative electrode active material layer can select NiFe2O4, TiO2, Li4TiO4In any bi-material composition, described positive electrode active material layer can select LiCoO2, LiNiO2, LiMnO2In any bi-material composition.
The concrete steps of the program, include the following:
S1, choose substrate material layer, to the sand paper of 3000 mesh, substrate surface is mechanically polished with 500 mesh, until surface can occur direct reflection；
S2, employing film deposition techniques, use positive pole or negative electrode active material material as target, close sample presentation room and epitaxial chamber, utilize mechanical pump, molecular pump after installing target and substrate material layer, and epitaxial chamber's vacuum is evacuated to 1 × 10 by ionic pump-7Below Pa；
S3, the distance adjusted between target and substrate are 60mm, and autorotation speed is 10 revs/min, pre-sputtering more than 1 hour, to clear up oxide layer and the impurity of target material surface；
S4, use method to target alternating deposit, each piece of target laser bombardment 10 times, total sedimentation time 30 minutes；
S5, closedown precipitation equipment, take out substrate after cooling, put in vacuum heat treatment furnace, make annealing treatment under the atmosphere of air, according to 5 DEG C of heating rates per minute, temperature is risen to 550 DEG C, be incubated 1 hour, naturally cool to room temperature.
As the preferred technical scheme of one, described film deposition techniques uses pulsed laser deposition, other vacuum thin film technology, and such as molecule epitaxial deposition, laser molecular epitaxial deposition, magnetron sputtering or chemical gaseous phase deposition can also use.
Have employed technique scheme, the invention have the benefit that the MULTILAYER COMPOSITE lithium-ion film cell electrode that the present invention provides, utilize the thin film technique can be in the growth of minimum size range internal control made membrane, combining more tight between layers, the electrochemical properties of different materials can mutually make up.It is different from simple physical mixed, in the volume of tens structure cells, Li+Bi-material embed and deviates from, can preferably embody synergisticing performance.The material selecting lattice parameter acquaintance carries out alternating deposit and can effectively reduce the mismatch of crystal boundary, is conducive to reducing Li+Embed and destruction to crystal structure during abjection at storeroom.Meanwhile, the depositional mode of volume to volume can also large-area be prepared.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in describing below is only some embodiments of the present invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the hetero-junctions compound lithium ion hull cell electrode schematic diagram of the present invention.
Fig. 2 is the hetero-junctions compound lithium ion hull cell electrode scanning electron microscope exterior view of the present invention.
Fig. 3 is the hetero-junctions compound lithium ion hull cell electrode scanning electron microscope sectional view of the present invention.
Wherein: 1, substrate material layer；2, active substance 2；3, active material layer 3.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
As Figure 1-3, a kind of hetero-junctions lithium-ion film cell electrode material, including substrate material layer 1, the active material layer grown above 2 of described substrate material layer 1 and active material layer 3, described active material layer 2 and active material layer 3 by evaporating deposition technique alternating growth.
As the preferred technical scheme of one, described substrate material layer 1 use carbon, silicon, copper, aluminum or stainless steel substrates any one.
As the preferred technical scheme of one, the surface roughness of described substrate material layer 1 is less than 100 nanometers.
As the preferred technical scheme of one, the surface of described substrate material layer 1 utilizes the metal current collector layer after magnetron sputtering technique one layer of 50-500 nanometer of deposition.As the preferred technical scheme of one, the THICKNESS CONTROL of monolayer material is in 0.5-10 nanometer range, and each thickness in monolayer thickness ratio is between 1-10；Overall film thickness can reach more than 1 micron.
As the preferred technical scheme of one, described negative electrode active material layer can select NiFe2O4, TiO2, Li4TiO4In any bi-material composition, described positive electrode active material layer can select LiCoO2, LiNiO2, LiMnO2In any bi-material composition.
Embodiment one
Use the epitaxially grown method of laser molecular, use TiO2And NiFe2O4As target, it is desirable to target relative density is more than 99.8%, purity is more than 99.999%, a diameter of 50mm.Stainless steel substrates is as substrate material.
First, substrate surface is mechanically polished to the sand paper of 3000 mesh with 500 mesh, until surface can occur direct reflection.
Closing sample presentation room and epitaxial chamber after installing target and substrate, utilize mechanical pump, molecular pump, epitaxial chamber's vacuum is evacuated to 1 × 10 by ionic pump-7Below Pa.
Set range of laser energy 600mJ, frequency 5Hz；
The distance adjusted between target and substrate is 60mm, and autorotation speed is 10 revs/min；
Pre-sputtering, to clear up target material surface.
Set laser power 600mJ, sputter frequency 1Hz, sputtering pressure 1 × 10-5Pa.The method using alternating sputtering, each piece of target laser bombardment 10 times.Total sedimentation time 30 minutes.
Close precipitation equipment, substrate is directly taken out and carries out pattern and performance test.
Embodiment two
Use the growing method of magnetron sputtering, use LiMnO2、LiNiO2And LiCoO2As target, it is desirable to target relative density is more than 99.8%, purity is more than 99.999%, a diameter of 50mm.Monocrystalline silicon piece is as substrate material.
Silicon substrate surface utilizes electron beam evaporation to prepare by Ti/Pt (50nm/100nm) conductive layer.
Install and carefully close growth chamber after target and substrate, utilize mechanical pump, molecular pump, growth room's vacuum is evacuated to 1 × 10-3Below Pa.Being passed through oxygen and argon, flow velocity is respectively 30sccm and 10sccm.By adjusting molecular pump slide valve, the pressure of cavity is maintained about 2Pa.
Pre-sputtering 1h is to clean oxide layer and the impurity of target material surface.
Arranging radio-frequency power supply power is 45W, sinks to the bottom temperature 300 DEG C, target and substrate distance 100cm, sedimentation time 6h.
Depositional mode is to target alternating deposit, forms LiMnO2/LiNiO2/LiCoO2Different knot matter thin film.
After cooling substrate is taken out, put in vacuum heat treatment furnace, make annealing treatment under the atmosphere of air, according to 5 DEG C of heating rates per minute, temperature is risen to 550 DEG C, be incubated 1 hour, naturally cool to room temperature.
Substrate is directly taken out and carries out pattern and performance test.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (7)
1. a hetero-junctions lithium-ion film cell electrode material, it is characterized in that, including substrate material layer, the negative electrode active material layer grown above of described substrate material layer or positive electrode active material layer, described negative electrode active material layer and positive electrode active material layer are formed by multi-layer compound film, and described negative electrode active material layer and positive electrode active material layer are by evaporating deposition technique alternating growth.
2. hetero-junctions lithium-ion film cell electrode material as claimed in claim 1 a kind of, it is characterised in that described substrate material layer use carbon, silicon, copper, aluminum or stainless steel substrates any one.
3. a kind of hetero-junctions lithium-ion film cell electrode material as claimed in claim 1, it is characterised in that the surface roughness of described substrate material layer is less than 100 nanometers.
4. a kind of hetero-junctions lithium-ion film cell electrode material as claimed in claim 1, it is characterised in that the surface of described substrate material layer utilizes the metal current collector layer of magnetron sputtering technique one layer of 50-500 nanometer thickness of deposition.
5. a kind of hetero-junctions lithium-ion film cell electrode material as claimed in claim 1, it is characterised in that the single film layer THICKNESS CONTROL of alternating growth is in 0.5-10 nanometer range, and each layer thickness ratio is between 1-10；Overall film thickness can reach more than 1 micron.
6. a kind of hetero-junctions lithium-ion film cell electrode material as claimed in claim 1, it is characterised in that described negative electrode active material layer can select NiFe2O4, TiO2, Li4TiO4In any bi-material composition, described positive electrode active material layer can select LiCoO2, LiNiO2, LiMnO2In any bi-material composition.
7. the preparation method of a hetero-junctions lithium-ion film cell electrode material, it is characterised in that described film deposition techniques can use pulsed laser deposition, any one in laser molecular epitaxial deposition, magnetron sputtering or chemical gaseous phase deposition.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299237A (en) * | 2016-09-27 | 2017-01-04 | 柔电（武汉）科技有限公司 | Self-supporting pole piece and preparation method thereof, battery and battery core thereof |
| CN108413339A (en) * | 2018-03-01 | 2018-08-17 | 深圳市晟达机械设计有限公司 | A kind of Solar Street Lighting System |
| CN109950516A (en) * | 2019-04-23 | 2019-06-28 | 福州大学 | A kind of preparation method of InTe/GaS hetero-junctions li-ion electrode materials |
| CN110054259A (en) * | 2018-01-18 | 2019-07-26 | 浦项工科大学校产学协力团 | Oxidizing electrode, its manufacturing method and the electrolysis unit comprising it |
| CN113839028A (en) * | 2020-06-24 | 2021-12-24 | 比亚迪股份有限公司 | Positive plate and battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271974A (en) * | 2007-03-22 | 2008-09-24 | 中信国安盟固利新能源科技有限公司 | Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery |
| CN101414674A (en) * | 2008-08-05 | 2009-04-22 | 华南师范大学 | Cathode material for lithium ion battery tin/carbon nanometer multilayer film, and preparation method and application thereof |
-
2016
- 2016-06-06 CN CN201610398675.5A patent/CN105958051A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271974A (en) * | 2007-03-22 | 2008-09-24 | 中信国安盟固利新能源科技有限公司 | Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery |
| CN101414674A (en) * | 2008-08-05 | 2009-04-22 | 华南师范大学 | Cathode material for lithium ion battery tin/carbon nanometer multilayer film, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JUNG PIL NOH等: "《Microstructure and electrochemical properties of magnetron-sputtered LiCoO2/LiNiO2 multi-layer thin film electrode》", 《MATERIALS RESEARCH BULLETIN》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299237A (en) * | 2016-09-27 | 2017-01-04 | 柔电（武汉）科技有限公司 | Self-supporting pole piece and preparation method thereof, battery and battery core thereof |
| CN106299237B (en) * | 2016-09-27 | 2019-06-28 | 武汉艾特米克超能新材料科技有限公司 | Self-supporting pole piece and preparation method thereof, battery and its battery core |
| CN110054259A (en) * | 2018-01-18 | 2019-07-26 | 浦项工科大学校产学协力团 | Oxidizing electrode, its manufacturing method and the electrolysis unit comprising it |
| CN110054259B (en) * | 2018-01-18 | 2022-05-13 | 浦项工科大学校产学协力团 | Oxidation electrode, method for manufacturing same, and electrolysis device comprising same |
| CN108413339A (en) * | 2018-03-01 | 2018-08-17 | 深圳市晟达机械设计有限公司 | A kind of Solar Street Lighting System |
| CN109950516A (en) * | 2019-04-23 | 2019-06-28 | 福州大学 | A kind of preparation method of InTe/GaS hetero-junctions li-ion electrode materials |
| CN113839028A (en) * | 2020-06-24 | 2021-12-24 | 比亚迪股份有限公司 | Positive plate and battery |
| WO2021258900A1 (en) * | 2020-06-24 | 2021-12-30 | 比亚迪股份有限公司 | Positive electrode sheet and battery |
| CN113839028B (en) * | 2020-06-24 | 2023-02-10 | 比亚迪股份有限公司 | Positive plate and battery |
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