CN108390013A - A kind of lithium ion battery electrode material nano surface metal-modified method - Google Patents
A kind of lithium ion battery electrode material nano surface metal-modified method Download PDFInfo
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- CN108390013A CN108390013A CN201810342654.0A CN201810342654A CN108390013A CN 108390013 A CN108390013 A CN 108390013A CN 201810342654 A CN201810342654 A CN 201810342654A CN 108390013 A CN108390013 A CN 108390013A
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- Prior art keywords
- ion battery
- lithium ion
- electrode material
- battery electrode
- vacuum
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
-
- 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 kind of lithium ion battery electrode material nano surface metal-modified methods, include the following steps：(1) with slurry as raw material electric stirring using lithium ion battery electrode material, conductive agent, binder and secondary solvent NMP, electric or hand coating prepares electrode plates；(2) vacuum magnetron sputtering coating film technology is used, using the good metal of electric conductivity as target, by regulating and controlling vacuum magnetron sputtering coating film technological parameter, even metal-modified is realized on the electrode plates surface of above-mentioned preparation.The advantage of the invention is that：Provide a kind of lithium ion battery electrode material nano surface metal-modified method, it is easy to operate, electrode plates nano surface metal-modified thickness can be accurately controlled, the conductivity between lithium ion battery electrode material particle can be significantly improved, and then being obviously improved for lithium ion battery multiplying power and cycle performance may be implemented, for high-performance can designing and preparing for fast charging and discharging lithium ion battery put forward a new idea.
Description
Technical field
The present invention relates to new energy materials fields more particularly to a kind of lithium ion battery electrode material nano surface metal to repair
Decorations method.
Background technology
Lithium ion battery is quite rapid by its unique glamour development, and the situation of rapid growth is presented in industry.Anode
Material is the key core material of lithium ion battery.But that generally there are intrinsic conductivities is low for positive electrode current material, lithium ion diffusion
The small problem of coefficient, this makes its multiplying power and cycle performance poor.The existing pole piece technology of preparing of electrode material is as follows at present：By phosphorus
Ferrous silicate lithium dusty material carries out mixing system with binder (such as PVDF), conductive agent (such as graphite) and solvent (such as NMP)
For at the electrode slurry with certain viscosity and mobility.Then electrode plates are prepared by coating, and then are assembled into battery
It is used.
Sputter coating refers to the splash effect generated using particle bombardment target so that target atom or molecule are from solid table
Face is projected, and the process of film is formed in deposition on substrate.Magnetron sputtering technology rate of film build is high, and the consistency of film forming is good,
It forms a film comparatively dense, and film/base junction is closed preferably；It can realize that the film of nanoscale closely deposits in material or workpiece surface,
To change material or workpiece surface performance, there is very high economic value.
Invention content
It is an object of the invention to overcome the shortcomings of existing electrode material performance, a kind of scientific and effective, making side is provided
Just, the lithium ion battery electrode material nano surface metal-modified side with preferable high rate performance and good cycle performance
Method.
The present invention is achieved by the following technical solutions：A kind of lithium ion battery electrode material nano surface metal-modified
Method includes the following steps：
It is (1) with slurry as raw material electric stirring using lithium ion battery electrode material, conductive agent, binder and secondary solvent NMP,
Electric or hand coating prepares electrode plates；
(2) vacuum magnetron sputtering coating film technology is used, using the good metal of electric conductivity as target, by regulating and controlling vacuum
Magnetron sputtering membrane process parameter realizes even metal-modified on the electrode plates surface of above-mentioned preparation.
One of preferred embodiment as the present invention, the step (2) is middle to use metallic tin, aluminium, gold, silver and titanium as target
Material.
One of preferred embodiment as the present invention, phosphorus is prepared in the step (2) by vacuum magnetron sputtering coating film technology
When ferrous silicate lithium electrode plates, for the method used for radio-frequency magnetron sputter method, equipment is high vacuum magnetic-controlled sputtering coating equipment.
One of preferred embodiment as the present invention, vacuum magnetron sputtering coating film technology carries out electrode material in the step (2)
Expect surface modification.
One of preferred embodiment as the present invention, the vacuum magnetron sputtering coating film technique ginseng of tin target in the step (2)
Number is specially：Base vacuum (0.5-1.5) × 10-5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, work temperature
Degree：200-260 DEG C, working air current：Ar, 50-100sccm, sputtering power 30-80W.
One of preferred embodiment as the present invention, the vacuum magnetron sputtering coating film technique ginseng of aluminium target in the step (2)
Number is specially：Base vacuum (0.5-1.5) × 10-5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, work temperature
Degree：200-260 DEG C, working air current：Ar, 50-100sccm, sputtering power 60-120W.
One of preferred embodiment as the present invention, the vacuum magnetron sputtering coating film technique ginseng of silver-colored target in the step (2)
Number is specially：Base vacuum (0.5-1.5) × 10-5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, work temperature
Degree：200-260 DEG C, working air current：Ar, 50-100sccm, sputtering power 30-90W.
One of preferred embodiment as the present invention, the vacuum magnetron sputtering coating film technique ginseng of gold target material in the step (2)
Number is specially：Base vacuum (0.5-1.5) × 10-5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, work temperature
Degree：200-260 DEG C, working air current：Ar, 50-100sccm, sputtering power 50-120W.
One of preferred embodiment as the present invention, the vacuum magnetron sputtering coating film technique ginseng of titanium target material in the step (2)
Number is specially：Base vacuum (0.5-1.5) × 10-5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, work temperature
Degree：200-260 DEG C, working air current：Ar, 50-100sccm, sputtering power 60-120W.
One of preferred embodiment as the present invention, the step (2) is middle to use vacuum magnetic-control sputtering technology in ferrous phosphate
The material electrodes surfaces such as lithium material, cobalt acid lithium material, ternary material, phosphoric acid vanadium lithium carry out nano surface metal-modified.
The present invention compared with prior art the advantages of be：
(1) scientific and effective, preparation is conveniently；
(2) there is good high rate performance and cyclicity using the lithium ion battery electrode material pole piece that this method is produced
Energy；
(3) not only environmental protection and saving energy consumption, but also can be easier to realize that nano metal controllably be modified.
Description of the drawings
Fig. 1 is that a kind of flow of lithium ion battery electrode material nano surface metal-modified method in embodiment 1-4 is shown
It is intended to.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
As shown in Figure 1, a kind of lithium iron phosphate cathode material pole piece nano metal tin method of modifying of the present embodiment,
Include the following steps：
It is (1) with slurry as raw material electric stirring using lithium iron phosphate cathode material, conductive agent, binder and secondary solvent NMP,
Electric or hand coating prepares electrode plates；
(2) vacuum magnetron sputtering coating film technology is used, it is true by regulating and controlling using the good metallic tin of electric conductivity as target
Empty magnetron sputtering membrane process parameter realizes even on the lithium iron phosphate cathode material electrode plates surface of above-mentioned preparation
Metallic tin is modified.
Wherein, the vacuum magnetron sputtering coating film technological parameter of tin target is specially：Base vacuum (0.5-1.5) × 10-5Pa,
Starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 30-80W.
Embodiment 2
As shown in Figure 1, a kind of nickel cobalt aluminium tertiary cathode material pole piece nano metal tin method of modifying of the present embodiment,
Include the following steps：
It is (1) with slurry as raw material electric stirring using nickel cobalt aluminium tertiary cathode material, conductive agent, binder and secondary solvent NMP,
Electric or hand coating prepares electrode plates；
(2) vacuum magnetron sputtering coating film technology is used, it is true by regulating and controlling using the good metallic tin of electric conductivity as target
Empty magnetron sputtering membrane process parameter realizes even on the nickel cobalt aluminium tertiary cathode material electrode plates surface of above-mentioned preparation
Metallic tin is modified.
Wherein, the vacuum magnetron sputtering coating film technological parameter of tin target is specially：Base vacuum (0.5-1.5) × 10-5Pa,
Starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 30-80W.
Embodiment 3
As shown in Figure 1, a kind of lithium iron phosphate cathode material pole piece nano metal aluminium method of modifying of the present embodiment,
Include the following steps：
It is (1) with slurry as raw material electric stirring using lithium iron phosphate cathode material, conductive agent, binder and secondary solvent NMP,
Electric or hand coating prepares electrode plates；
(2) vacuum magnetron sputtering coating film technology is used, it is true by regulating and controlling using the good metallic aluminium of electric conductivity as target
Empty magnetron sputtering membrane process parameter realizes even on the lithium iron phosphate cathode material electrode plates surface of above-mentioned preparation
Metallic aluminium is modified.
Wherein, the vacuum magnetron sputtering coating film technological parameter of aluminium target is specially：Base vacuum (0.5-1.5) × 10-5Pa,
Starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 60-120W.
Embodiment 4
As shown in Figure 1, a kind of nickel cobalt aluminium tertiary cathode material pole piece nano metal aluminium method of modifying of the present embodiment,
Include the following steps：
It is (1) with slurry as raw material electric stirring using nickel cobalt aluminium tertiary cathode material, conductive agent, binder and secondary solvent NMP,
Electric or hand coating prepares electrode plates；
(2) vacuum magnetron sputtering coating film technology is used, it is true by regulating and controlling using the good metallic aluminium of electric conductivity as target
Empty magnetron sputtering membrane process parameter realizes even on the nickel cobalt aluminium tertiary cathode material electrode plates surface of above-mentioned preparation
Metallic tin is modified.
Wherein, the vacuum magnetron sputtering coating film technological parameter of aluminium target is specially：Base vacuum (0.5-1.5) × 10-5Pa,
Starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 60-120W.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of lithium ion battery electrode material nano surface metal-modified method, which is characterized in that include the following steps：
(1) with slurry as raw material electric stirring using lithium ion battery electrode material, conductive agent, binder and secondary solvent NMP, it is electronic
Or hand coatings prepare electrode plates；
(2) vacuum magnetron sputtering coating film technology is used, using the good metal of electric conductivity as target, by regulating and controlling vacuum magnetic control
Sputter coating process parameter realizes even metal-modified on the electrode plates surface of above-mentioned preparation.
2. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In the step (2) is middle to be used using metallic tin, aluminium, gold, silver and titanium as target.
3. the preparation method of lithium iron phosphate cathode material pole piece according to claim 1, which is characterized in that the step
(2) when preparing LiFePO 4 electrode plates by vacuum magnetron sputtering coating film technology in, the method used is splashed for radio frequency magnetron
Method is penetrated, equipment is high vacuum magnetic-controlled sputtering coating equipment.
4. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In vacuum magnetron sputtering coating film technology carries out electrode material surface modification in the step (2).
5. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In the vacuum magnetron sputtering coating film technological parameter of tin target is specially in the step (2)：Base vacuum (0.5-1.5) × 10- 5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 30-80W.
6. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In the vacuum magnetron sputtering coating film technological parameter of aluminium target is specially in the step (2)：Base vacuum (0.5-1.5) × 10- 5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 60-120W.
7. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In the vacuum magnetron sputtering coating film technological parameter of silver-colored target is specially in the step (2)：Base vacuum (0.5-1.5) × 10- 5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 30-90W.
8. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In the vacuum magnetron sputtering coating film technological parameter of gold target material is specially in the step (2)：Base vacuum (0.5-1.5) × 10- 5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 50-120W.
9. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In the vacuum magnetron sputtering coating film technological parameter of titanium target material is specially in the step (2)：Base vacuum (0.5-1.5) × 10- 5Pa, starter pressure 0.5-3Pa, operating air pressure 0.14-0.16Pa, operating temperature：200-260 DEG C, working air current：Ar, 50-
100sccm, sputtering power 60-120W.
10. a kind of lithium ion battery electrode material nano surface metal-modified method according to claim 1, feature exist
In using vacuum magnetic-control sputtering technology in ferrousphosphate lithium material, cobalt acid lithium material, ternary material, phosphoric acid in the step (2)
The material electrodes such as vanadium lithium surface carries out nano surface metal-modified.
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| CN201810342654.0A CN108390013A (en) | 2018-04-17 | 2018-04-17 | A kind of lithium ion battery electrode material nano surface metal-modified method |
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| CN201810342654.0A CN108390013A (en) | 2018-04-17 | 2018-04-17 | A kind of lithium ion battery electrode material nano surface metal-modified method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346714A (en) * | 2018-10-15 | 2019-02-15 | 安庆师范大学 | A kind of novel storage hydrogen, storage lithium magnesium base alloy preparation method and applications |
| CN111313003A (en) * | 2020-02-28 | 2020-06-19 | 桂林电子科技大学 | Fast-charging modified nickel-cobalt-manganese ternary cathode material and preparation method and application thereof |
| CN114665067A (en) * | 2022-03-18 | 2022-06-24 | 江西安驰新能源科技有限公司 | Thick pole piece processing method |
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| CN101692493A (en) * | 2009-10-16 | 2010-04-07 | 中国科学院上海微***与信息技术研究所 | Metallic film capable of improving stability of anode of lithium ion battery and manufacturing method |
| CN103219492A (en) * | 2013-04-09 | 2013-07-24 | 中南大学 | Manganese positive pole of modified lithium ion battery, and preparation method of manganese positive pole |
| CN106898733A (en) * | 2017-03-24 | 2017-06-27 | 安庆师范大学 | A kind of preparation method of lithium iron phosphate cathode material pole piece |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101162774A (en) * | 2007-07-31 | 2008-04-16 | 北京理工大学 | Surface film coating modify method for improving lithium ionic cell positive pole safety |
| CN101692493A (en) * | 2009-10-16 | 2010-04-07 | 中国科学院上海微***与信息技术研究所 | Metallic film capable of improving stability of anode of lithium ion battery and manufacturing method |
| CN103219492A (en) * | 2013-04-09 | 2013-07-24 | 中南大学 | Manganese positive pole of modified lithium ion battery, and preparation method of manganese positive pole |
| CN106898733A (en) * | 2017-03-24 | 2017-06-27 | 安庆师范大学 | A kind of preparation method of lithium iron phosphate cathode material pole piece |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346714A (en) * | 2018-10-15 | 2019-02-15 | 安庆师范大学 | A kind of novel storage hydrogen, storage lithium magnesium base alloy preparation method and applications |
| CN111313003A (en) * | 2020-02-28 | 2020-06-19 | 桂林电子科技大学 | Fast-charging modified nickel-cobalt-manganese ternary cathode material and preparation method and application thereof |
| CN111313003B (en) * | 2020-02-28 | 2022-02-08 | 桂林电子科技大学 | Fast-charging modified nickel-cobalt-manganese ternary cathode material and preparation method and application thereof |
| CN114665067A (en) * | 2022-03-18 | 2022-06-24 | 江西安驰新能源科技有限公司 | Thick pole piece processing method |
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