CN104409692A - Modification method for electrode material for lithium ion battery - Google Patents

Modification method for electrode material for lithium ion battery Download PDF

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Publication number
CN104409692A
CN104409692A CN201410661331.XA CN201410661331A CN104409692A CN 104409692 A CN104409692 A CN 104409692A CN 201410661331 A CN201410661331 A CN 201410661331A CN 104409692 A CN104409692 A CN 104409692A
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China
Prior art keywords
electrode material
precursor
ion battery
lithium ion
reaction chamber
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CN201410661331.XA
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Chinese (zh)
Inventor
何丹农
王丹
吴晓燕
严鹏
杨扬
张春明
黄昭
贺旷驰
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a modification method for an electrode material for a lithium ion battery. The modification method comprises the following steps: putting a pretreated electrode plate in a reaction cavity for atomic layer deposition equipment, closing the cavity, and washing the reaction cavity with high-purity nitrogen; under the condition of low vacuum of lower than 20 hPa, heating to 80-150 DEG C, introducing a precursor into the reaction cavity with the pulse time of 0.1-1 s under the carrier gas flow condition of 1-100 ml/min, completing once pulsing, washing with high-purity nitrogen for 1-10 s, washing unnecessary precursor, then introducing water vapor to enable the precursor to hydrolyze with the pulse time of 0.1-1 s, and finally washing with high-purity nitrogen again for 1-20 s; in the process of the precursor, washing with the high-purity nitrogen, water vapor and washing with the high-purity nitrogen, and after 1-1000 times of cycles for deposition, obtaining the modified electrode material for the lithium ion battery. The method can greatly improve the electrical conductivity of the electrode material, and thus the rate capacity of the electrode material is improved.

Description

A kind of method of modifying of lithium ion battery electrode material
Technical field
The present invention relates to a kind of method of modifying of lithium ion battery electrode material, belong to electrochemical field.
Background technology
Ald (Atomic Layer Deposition, ALD) be a kind of can by material with the monatomic form membrane method being plated in substrate surface from level to level.By vaporous precursors pulse alternately being passed into reactor chemisorbed also reaction formation deposited film on depositing base.Technique for atomic layer deposition is due to the height controllable type (thickness, composition and structure) of its deposition parameter, and excellent deposition uniformity and consistency make it have a wide range of applications potentiality in fields such as micro-nano electronics and nano materials.The material adopting ALD technology to deposit comprises: oxide, nitride, fluoride, metal, carbide, the compound etc. of sulfide and above material.ALD at present more is applied to the material preparations such as semiconductor.
The present invention utilizes ALD method to carry out modification to lithium ion battery electrode material, can greatly improve conductivity and the high rate performance of electrode material.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of method of modifying of lithium ion battery electrode material.A method of modifying for lithium ion battery electrode material, is characterized in that, concrete steps are:
(1) preliminary treatment of electrode material, is prepared into slurry coating on a current collector, dry for standby under 100 DEG C of vacuum conditions, forms electrode slice by electrode material, keep the electrode slice for modification to have clean surface;
(2) ald prepares modified electrode material, will be placed in the reaction chamber of atomic layer deposition apparatus through pretreated electrode slice, closes cavity, then is the High Purity Nitrogen cleaning reaction chamber of 99.999% by purity; With vacuum pump reaction chamber be extracted into the low vacuum of below 20hPa and be heated to 80 DEG C-150 DEG C, burst length precursor being passed into reaction chamber under 1-100ml/min carrier gas flux condition is 0.1-1s, complete pulsatile once, clean with high pure nitrogen, the burst length of high pure nitrogen cleaning precursor is 1-10s, wash unnecessary precursor, then passing into steam makes precursor be hydrolyzed, the burst length passing into water vapour is 0.1-1s, finally clean 1-20s with high pure nitrogen again, remove the steam do not reacted; Precursor-high pure nitrogen cleaning-steam-high pure nitrogen cleaning, this procedure definition is a deposition cycle; After depositing 1-1000 circulation, obtain the lithium ion battery electrode material of modification.
Described electrode material is the one in cobalt acid lithium, lithium nickel cobalt dioxide, nickel manganese cobalt, LiMn2O4, LiFePO4, lithium titanate.
Precursor described in step (2) is trimethyl aluminium, diethyl zinc, titanium tetrachloride, n-butyl titanium, titanium ethanolate; aluminum isopropylate, four (dimethylamino) titanium, four (dimethylamino) zirconium, two (hexafluoroacetylacetone) close one in copper, two (hexafluoro Dimethylpropanoyl acrylic acid) copper, trifluoroacetylacetone (TFA) copper or its combination, and the purity of precursor is greater than 98%.
The lithium ion battery electrode material of method modification of the present invention is adopted to show excellent large high rate performance.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve of the embodiment of the present invention 1 product under 1C multiplying power.
Fig. 2 is the first charge-discharge curve of the embodiment of the present invention 2 product under 2C multiplying power.
Embodiment
Below embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1: by active material Li 4ti 5o 12powder, acetylene black and binding agent Kynoar (PVDF) to mix in mass ratio at 85: 10: 5, take NMP as solvent, the uniform electrode slurry of furnishing.Then by its even application on collector Cu paper tinsel, in the vacuum drying oven of 100 DEG C, dry 12 h, make Li 4ti 5o 12electrode slice.The reaction chamber of atomic layer deposition apparatus will be placed in through pretreated electrode slice, close cavity, then be the High Purity Nitrogen cleaning reaction chamber of 99.999% by purity.With vacuum pump reaction chamber be extracted into the low vacuum of 10hPa and be heated to 120 DEG C, be, under the condition of 5ml/min, butyl titanate is passed into reaction chamber 0.1s at carrier gas flux, 5s is cleaned with high pure nitrogen, wash unnecessary butyl titanate, then passing into steam 0.2s makes butyl titanate be hydrolyzed, finally clean 10s with high pure nitrogen again, remove the steam do not reacted.So repeatedly complete 100 deposition cycle, obtain the Li of modification 4ti 5o 12electrode slice.
This electrode slice is placed on dry 12 h in the vacuum drying oven of 100 DEG C, with this electrode slice for positive pole, metal lithium sheet is negative pole, and Celgard3501 polypropylene perforated membrane is barrier film, with 1 mol/L LiPF 6the mixed solution of ethylene carbonate (EC)/diethyl carbonate (DEC) (volume ratio is 1: 1) be electrolyte, in the glove box being full of dry argon gas, be assembled into simulated battery.Fig. 1 is under 5C multiplying power, the first charge-discharge curve of this battery.
Embodiment 2: active compound lithium iron phosphate powder, acetylene black and binding agent Kynoar (PVDF) being mixed at 80: 10: 10 in mass ratio, take NMP as solvent, the uniform electrode slurry of furnishing.Then by its even application on collector Al paper tinsel, in the vacuum drying oven of 100 DEG C, dry 12 h, make iron phosphate lithium electrode sheet.The reaction chamber of atomic layer deposition apparatus will be placed in through pretreated electrode slice, close cavity, then be the High Purity Nitrogen cleaning reaction chamber of 99.999% by purity.With vacuum pump reaction chamber be extracted into the low vacuum of 10hPa and be heated to 100 DEG C, be, under the condition of 2ml/min, trimethyl aluminium is passed into reaction chamber 0.1s at carrier gas flux, 10s is cleaned with high pure nitrogen, wash unnecessary trimethyl aluminium, then passing into steam 0.2s makes trimethyl aluminium be hydrolyzed, finally clean 20s with high pure nitrogen again, remove the steam do not reacted.So repeatedly complete 50 deposition cycle, obtain the iron phosphate lithium electrode sheet of modification.
This electrode slice is placed on dry 12 h in the vacuum drying oven of 100 DEG C, with this electrode slice for positive pole, metal lithium sheet is negative pole, and Celgard3501 polypropylene perforated membrane is barrier film, with 1 mol/L LiPF 6the mixed solution of ethylene carbonate (EC)/diethyl carbonate (DEC) (volume ratio is 1: 1) be electrolyte, in the glove box being full of dry argon gas, be assembled into simulated battery.Fig. 2 is under 2C multiplying power, the first charge-discharge curve of this battery.
Embodiment 3: the acid of active material cobalt lithium powder, acetylene black and binding agent Kynoar (PVDF) being mixed at 80: 10: 10 in mass ratio, take NMP as solvent, the uniform electrode slurry of furnishing.Then by its even application on collector Al paper tinsel, dry 12 h in the vacuum drying oven of 100 DEG C, make cobalt acid lithium electrode sheet.The reaction chamber of atomic layer deposition apparatus will be placed in through pretreated electrode slice, close cavity, then be the High Purity Nitrogen cleaning reaction chamber of 99.999% by purity.With vacuum pump reaction chamber be extracted into the low vacuum of 20hPa and be heated to 140 DEG C, be, under the condition of 1ml/min, four (dimethylamino) zirconium is passed into reaction chamber 0.5s at carrier gas flux, 5s is cleaned with high pure nitrogen, wash unnecessary four (dimethylamino) zirconium, then passing into steam 1s makes four (dimethylamino) zirconium be hydrolyzed, finally clean 5s with high pure nitrogen again, remove the steam do not reacted.So repeatedly complete 500 deposition cycle, obtain the cobalt acid lithium electrode sheet of modification.
Embodiment 4: active material LiMn2O4 powder, acetylene black and binding agent Kynoar (PVDF) being mixed at 80: 10: 10 in mass ratio, take NMP as solvent, the uniform electrode slurry of furnishing.Then by its even application on collector Al paper tinsel, in the vacuum drying oven of 100 DEG C, dry 12 h, make LiMn2O4 electrode slice.The reaction chamber of atomic layer deposition apparatus will be placed in through pretreated electrode slice, close cavity, then be the High Purity Nitrogen cleaning reaction chamber of 99.999% by purity.With vacuum pump reaction chamber be extracted into the low vacuum of 20hPa and be heated to 80 DEG C, be, under the condition of 1ml/min, four (dimethylamino) titanium is passed into reaction chamber 0.5s at carrier gas flux, 5s is cleaned with high pure nitrogen, wash unnecessary four (dimethylamino) titanium, then passing into steam 1s makes four (dimethylamino) titanium be hydrolyzed, finally clean 5s with high pure nitrogen again, remove the steam do not reacted.So repeatedly complete 1000 deposition cycle, obtain the LiMn2O4 electrode slice of modification.

Claims (3)

1. a method of modifying for lithium ion battery electrode material, is characterized in that, concrete steps are:
(1) preliminary treatment of electrode material, is prepared into slurry coating on a current collector, dry for standby under 100 DEG C of vacuum conditions, forms electrode slice by electrode material, keep the electrode slice for modification to have clean surface;
(2) ald prepares modified electrode material, will be placed in the reaction chamber of atomic layer deposition apparatus through pretreated electrode slice, closes cavity, then is the High Purity Nitrogen cleaning reaction chamber of 99.999% by purity; With vacuum pump reaction chamber be extracted into the low vacuum of below 20hPa and be heated to 80 DEG C-150 DEG C, burst length precursor being passed into reaction chamber under 1-100ml/min carrier gas flux condition is 0.1-1s, complete pulsatile once, clean with high pure nitrogen, the burst length of high pure nitrogen cleaning precursor is 1-10s, wash unnecessary precursor, then passing into steam makes precursor be hydrolyzed, the burst length passing into water vapour is 0.1-1s, finally clean 1-20s with high pure nitrogen again, remove the steam do not reacted; Precursor-high pure nitrogen cleaning-steam-high pure nitrogen cleaning, this procedure definition is a deposition cycle; After depositing 1-1000 circulation, obtain the lithium ion battery electrode material of modification.
2. the method for modifying of a kind of lithium ion battery electrode material according to claim 1, is characterized in that, described electrode material is the one in cobalt acid lithium, lithium nickel cobalt dioxide, nickel manganese cobalt, LiMn2O4, LiFePO4, lithium titanate.
3. the method for modifying of a kind of lithium ion battery electrode material according to claim 1; it is characterized in that; precursor described in step (2) is trimethyl aluminium, diethyl zinc, titanium tetrachloride, n-butyl titanium, titanium ethanolate; aluminum isopropylate, four (dimethylamino) titanium, four (dimethylamino) zirconium, two (hexafluoroacetylacetone) close one in copper, two (hexafluoro Dimethylpropanoyl acrylic acid) copper, trifluoroacetylacetone (TFA) copper or its combination, and the purity of precursor is greater than 98%.
CN201410661331.XA 2014-11-19 2014-11-19 Modification method for electrode material for lithium ion battery Pending CN104409692A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108862230A (en) * 2018-09-18 2018-11-23 天津先众新能源科技股份有限公司 A kind of processing method of the ultra-fine powder material of LiFePO4
CN109860545A (en) * 2019-01-03 2019-06-07 欣旺达电子股份有限公司 A kind of atomic layer deposition coating modification method of ternary cathode material of lithium ion battery
CN113488643A (en) * 2021-06-30 2021-10-08 陕西科技大学 Surface coating modification method for ternary cathode material of lithium ion battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102244231A (en) * 2010-05-14 2011-11-16 中国科学院物理研究所 Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery
CN103928704A (en) * 2014-04-14 2014-07-16 南京安普瑞斯有限公司 Lithium ion battery and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102244231A (en) * 2010-05-14 2011-11-16 中国科学院物理研究所 Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery
CN103928704A (en) * 2014-04-14 2014-07-16 南京安普瑞斯有限公司 Lithium ion battery and manufacturing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARK Q. SNYDER ET AL: ""Synthesis and characterization of atomic layer deposited titanium nitride thin films on lithium titanate spinel powder as a lithium-ion battery anode"", 《JOURNAL OF POWER SOURCES》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108862230A (en) * 2018-09-18 2018-11-23 天津先众新能源科技股份有限公司 A kind of processing method of the ultra-fine powder material of LiFePO4
CN108862230B (en) * 2018-09-18 2021-10-08 天津先众新能源科技股份有限公司 Treatment method of lithium iron phosphate superfine powder material
CN109860545A (en) * 2019-01-03 2019-06-07 欣旺达电子股份有限公司 A kind of atomic layer deposition coating modification method of ternary cathode material of lithium ion battery
CN113488643A (en) * 2021-06-30 2021-10-08 陕西科技大学 Surface coating modification method for ternary cathode material of lithium ion battery

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