CN101393984A - Positive electrode material of Lithium ion battery and producing process thereof - Google Patents

Positive electrode material of Lithium ion battery and producing process thereof Download PDF

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Publication number
CN101393984A
CN101393984A CNA2008102023182A CN200810202318A CN101393984A CN 101393984 A CN101393984 A CN 101393984A CN A2008102023182 A CNA2008102023182 A CN A2008102023182A CN 200810202318 A CN200810202318 A CN 200810202318A CN 101393984 A CN101393984 A CN 101393984A
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China
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lithium
anode material
ion batteries
preparation
parts
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CNA2008102023182A
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杨晓伟
马紫峰
何雨石
廖小珍
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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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

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Abstract

The invention discloses a positive material of a lithium ion battery and a preparation method thereof. The positive material is a coating-type positive material, namely LiFeO2 coated with metallic nanometer ions, and the conductivity of electrons and the ions is improved; the reversible ratio capacity reaches 155mAh/g during charging and discharging at the multiplying power of 25mA/g, and is improved by 35mAh/g than the positive material, namely LiFeO2 without being coated with the metallic nanometer ions; and the stable circulation performance is shown. The method for coating LiFeO2 with the metallic nanometer ions has simple and practicable process, cleanness and no pollution, and is suitable for industrialized production.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The present invention relates to a kind of battery electrode material and preparation method thereof, particularly a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
LiFeO 2With characteristics such as its abundant iron resource, cheap price, good thermal stability and environmental friendliness, be considered to a kind of very potential anode material for lithium-ion batteries.
USP5863512 and JP10233212 disclose a kind of stratiform LiFeO 2Anode material for lithium-ion batteries and preparation method thereof.But this material is proved to be unsettled in the practical application of anode material for lithium-ion batteries, can not support long-term charge and discharge cycles.
J.Power Sources 1997 (68) 145 and J.Power Sources 1997 (68) 711 have described a kind of corrugated LiFeO 2Anode material for lithium-ion batteries and preparation method thereof.But the discharge capacity of this material has only 100mAhg -1
J.Am.Chem.Soc.2008 (130) 3554 has described a kind of tetrahedral LiFeO 2Anode material for lithium-ion batteries and preparation method thereof, this product has higher charge/discharge capacity (120mAhg -1) and can support long-term charge and discharge cycles, so have higher using value.Yet the electronic conductivity that this product is extremely low (about 10 -9Scm -1) cause actual charge/discharge capacity far below theoretical capacity.
Summary of the invention
The object of the invention provides a kind of anode material for lithium-ion batteries and preparation method thereof, is a kind of cladded type positive electrode.
A kind of anode material for lithium-ion batteries of the present invention composed as follows:
Be a kind of cladded type positive electrode, promptly metal nanoparticle coats LiFeO 2, metal nanoparticle and LiFeO 2Mass ratio be 1:99-1:1, metal nanoparticle is Nano silver grain, copper nano-particle or aluminium nano particle.
The concrete preparation method of a kind of anode material for lithium-ion batteries of the present invention is as follows, below all represents with mass parts:
1 part of natrium carbonicum calcinatum and 1.5-1.8 parts of di-iron trioxides are fully mixed, grind, are heated to 900-1100 ℃ of insulations 12-18 hours, pulverize, under 120-160 ℃, carry out 6-12 hours backflow displacement reaction with 1-10 parts lithium salts, filtration washing is placed in the aqueous solution, stir the high-conductive metal salt that adds 0.018-1.8 parts down, the reducing agent that adds 0.05-2 parts then, continue to stir after 1-4 hours and filter, wash, dry, obtain a kind of anode material for lithium-ion batteries.
The lithium salts that the present invention uses is lithium chloride, lithium nitrate, lithium acetate, lithium phosphate, lithium carbonate or lithium hydroxide.
The high-conductive metal salt that the present invention uses is silver nitrate, copper nitrate or aluminum nitrate.
The reducing agent that the present invention uses is sodium borohydride, potassium borohydride, ascorbic acid, formaldehyde, hydrazine hydrate, polymeric alcohol or sodium dithionite.
A kind of anode material for lithium-ion batteries of the present invention is a kind of cladded type positive electrode, and promptly metal nanoparticle coats LiFeO 2LiFeO 2Itself has lower electronic conductivity, seriously influenced its electrochemical kinetics, in the charge and discharge cycles process, electronics must be accompanied by lithium ion and shift, if electronics can not import and derive timely in the material, then the diffusion of lithium ion is inevitable be replaced by the transition speed of electronics, the electronics of enrichment will by polarity effect conversely limiting lithium ion insertion and deviate to make material electrochemical performance to worsen.The present invention adopts metal nanoparticle to coat LiFeO 2After, improve the electronic conductivity of positive electrode, thereby improved the electrochemical impedance in the conduction velocity of lithium ion in positive electrode and the reduction charge and discharge process, help improving charge/discharge capacity.
A kind of anode material for lithium-ion batteries of the present invention is that metal nanoparticle coats LiFeO 2Be assembled into lithium ion battery with metal lithium sheet, with 25mAg -1Electric current discharge and recharge, reversible specific capacity reaches 155mAhg -1, than the LiFeO of clad metal nano particle not among the J.Am.Chem.Soc.2008 (130) 3554 2Positive electrode has improved 35mAhg -1, and show stable cycle performance.This method is simple, can realize the suitability for industrialized production that cleans.
Description of drawings
Fig. 1 is the sem photograph of the prepared anode material for lithium-ion batteries of example 1.
Fig. 2 is the charging and discharging curve of the prepared anode material for lithium-ion batteries of example 1.
Embodiment
Embodiment 1:
1.06 gram natrium carbonicum calcinatums and 1.6 gram di-iron trioxides are fully mixed, grind, are heated to 900 ℃ of insulations 12 hours, pulverize, under 160 ℃, carry out 8 hours backflow displacement reaction with 10 grams lithium chlorides, filtration washing is placed in the aqueous solution, stir the silver nitrate that adds 0.09 gram down, the ascorbic acid that adds 0.4 gram then, continue to stir after 2 hours and filter, wash, dry, obtain a kind of anode material for lithium-ion batteries.
Fig. 1 is that the anode material for lithium-ion batteries Nano silver grain that example 1 obtains coats LiFeO 2Amplify 30000 times sem photograph.Granule among the figure is exactly a Nano silver grain, and they evenly are coated on LiFeO 2Outer surface on, particle diameter is greatly between 20-50nm.
Take by weighing 0.225 restrain Nano silver grain coat LiFeO 2, add 0.045 gram carbon black conductive agent and 0.03 and restrain the polyvinylidene fluoride binding agent that is dissolved in the N-N ' dimethyl pyrrolidone solution, mix the uniform slurry of furnishing, slurry is coated in makes positive plate on the aluminium foil.In being full of the glove box of argon gas, be negative pole with the metal lithium sheet, Celgard2700 is a barrier film, 1molL -1LiPF 6/ EC+DMC is electrolyte (EC, DMC volume ratio are 1: 1), is assembled into button cell.
In 1.5-4.95V voltage range, at room temperature with 25mAg -1Electric current battery is carried out charge and discharge cycles test.Fig. 2 is this battery charging and discharging curve.As seen from the figure, the Nano silver grain that makes of the present invention coats LiFeO 2Reversible specific capacity reaches 155mAhg -1, battery is not obviously decay of capacity after 30 circulations.
Embodiment 2:
1.06 gram natrium carbonicum calcinatums and 1.6 gram di-iron trioxides are fully mixed, grind, are heated to 900 ℃ of insulations 12 hours, pulverize, under 160 ℃, carry out 8 hours backflow displacement reaction with 10 grams lithium chlorides, filtration washing is placed in the aqueous solution, stirs to add 0.265 gram Cu (NO down 3) 26H 2O adds 0.5 ascorbic acid that restrains then, continues to stir after 2 hours and filters, washs, dries, and obtains a kind of anode material for lithium-ion batteries.The products therefrom copper nano-particle coats LiFeO 2With 25mAg -1The electric current specific capacity of carrying out charge-discharge test be 148mAhg -1
Embodiment 3:
1.06 gram natrium carbonicum calcinatums and 1.6 gram di-iron trioxides are fully mixed, grind, are heated to 900 ℃ of insulations 12 hours, pulverize, under 160 ℃, carry out 8 hours backflow displacement reaction with 10 grams lithium chlorides, filtration washing is placed in the aqueous solution, stirs to add 0.816 gram Al (NO down 3) 39H 2O adds 0.7 ascorbic acid that restrains then, continues to stir after 2 hours and filters, washs, dries, and obtains a kind of anode material for lithium-ion batteries.Products therefrom aluminium nano particle coats LiFeO 2With 25mAg -1The electric current specific capacity of carrying out charge-discharge test be 146mAhg -1

Claims (5)

1. anode material for lithium-ion batteries is characterized in that it is composed as follows:
Be a kind of cladded type positive electrode, promptly metal nanoparticle coats LiFeO 2, metal nanoparticle and LiFeO 2Mass ratio be 1:99-1:1, metal nanoparticle is Nano silver grain, copper nano-particle or aluminium nano particle.
2. the preparation method of a kind of anode material for lithium-ion batteries as claimed in claim 1 is characterized in that the preparation method is as follows, below all represents with mass parts:
1 part of natrium carbonicum calcinatum and 1.5-1.8 parts of di-iron trioxides are fully mixed, grind, are heated to 900-1100 ℃ of insulations 12-18 hours, pulverize, under 120-160 ℃, carry out 6-12 hours backflow displacement reaction with 1-10 parts lithium salts, filtration washing is placed in the aqueous solution, stir the high-conductive metal salt that adds 0.018-1.8 parts down, the reducing agent that adds 0.05-2 parts then, continue to stir after 1-4 hours and filter, wash, dry, obtain a kind of anode material for lithium-ion batteries.
3. the preparation method of a kind of anode material for lithium-ion batteries according to claim 2 is characterized in that lithium salts is lithium chloride, lithium nitrate, lithium acetate, lithium phosphate, lithium carbonate or lithium hydroxide.
4. the preparation method of a kind of anode material for lithium-ion batteries according to claim 2 is characterized in that high-conductive metal salt is silver nitrate, copper nitrate and aluminum nitrate.
5. the preparation method of a kind of anode material for lithium-ion batteries according to claim 2 is characterized in that reducing agent is sodium borohydride, potassium borohydride, ascorbic acid, formaldehyde, hydrazine hydrate, polymeric alcohol or sodium dithionite.
CNA2008102023182A 2008-11-06 2008-11-06 Positive electrode material of Lithium ion battery and producing process thereof Pending CN101393984A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807716A (en) * 2010-03-22 2010-08-18 庄安中 Lithium oxide power battery
CN101891179A (en) * 2010-06-23 2010-11-24 万星光电子(东莞)有限公司 Preparation method of LiFePO material, lithium ion battery and positive plate thereof
CN102034980A (en) * 2010-11-22 2011-04-27 湖南杉杉新材料有限公司 Lithium iron phosphate-aluminum-carbon composite cathode material and preparation method thereof
CN102983329A (en) * 2012-11-28 2013-03-20 浙江工业大学 Preparation method of lithium iron phosphate anode material co-coated by conducting polymer/nanometer metal particles
CN104692465A (en) * 2015-02-04 2015-06-10 天津大学 Preparation method of alpha-LiFeO2 nano powder for positive pole material of lithium-ion battery
CN106601489A (en) * 2016-12-28 2017-04-26 宁波中车新能源科技有限公司 Pre-embedding-free lithium-type lithium-ion capacitor and manufacturing method thereof
CN106611846A (en) * 2017-01-17 2017-05-03 扬州大学 Synthesis method of alpha-LiFeO2/porous carbon composite material of lithium-ion battery anode
US9985294B2 (en) * 2015-05-29 2018-05-29 Pacesetter, Inc. High energy density and high rate Li battery
CN108649179A (en) * 2018-04-28 2018-10-12 北京航空航天大学 A kind of method of modification lithium-ion battery anode material
WO2024012481A1 (en) * 2022-07-13 2024-01-18 深圳市德方创域新能源科技有限公司 Iron-based lithium supplementing material for positive electrode, and preparation method therefor and use thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807716B (en) * 2010-03-22 2013-03-20 庄安中 Lithium oxide power battery
CN101807716A (en) * 2010-03-22 2010-08-18 庄安中 Lithium oxide power battery
CN101891179A (en) * 2010-06-23 2010-11-24 万星光电子(东莞)有限公司 Preparation method of LiFePO material, lithium ion battery and positive plate thereof
CN101891179B (en) * 2010-06-23 2012-08-29 万星光电子(东莞)有限公司 Preparation method of LiFePO material, lithium ion battery and positive plate thereof
CN102034980A (en) * 2010-11-22 2011-04-27 湖南杉杉新材料有限公司 Lithium iron phosphate-aluminum-carbon composite cathode material and preparation method thereof
CN102034980B (en) * 2010-11-22 2012-10-31 湖南杉杉新材料有限公司 Lithium iron phosphate-aluminum-carbon composite cathode material and preparation method thereof
CN102983329B (en) * 2012-11-28 2015-10-07 浙江工业大学 The preparation method of the lithium iron phosphate positive material that conducting polymer/nano metal particles is coated altogether
CN102983329A (en) * 2012-11-28 2013-03-20 浙江工业大学 Preparation method of lithium iron phosphate anode material co-coated by conducting polymer/nanometer metal particles
CN104692465A (en) * 2015-02-04 2015-06-10 天津大学 Preparation method of alpha-LiFeO2 nano powder for positive pole material of lithium-ion battery
US9985294B2 (en) * 2015-05-29 2018-05-29 Pacesetter, Inc. High energy density and high rate Li battery
CN106601489A (en) * 2016-12-28 2017-04-26 宁波中车新能源科技有限公司 Pre-embedding-free lithium-type lithium-ion capacitor and manufacturing method thereof
CN106601489B (en) * 2016-12-28 2019-06-21 宁波中车新能源科技有限公司 One kind is without pre- embedding lithium type lithium-ion capacitor and preparation method thereof
CN106611846A (en) * 2017-01-17 2017-05-03 扬州大学 Synthesis method of alpha-LiFeO2/porous carbon composite material of lithium-ion battery anode
CN108649179A (en) * 2018-04-28 2018-10-12 北京航空航天大学 A kind of method of modification lithium-ion battery anode material
WO2019205263A1 (en) * 2018-04-28 2019-10-31 北京航空航天大学 Method for modifying cathode material of lithium-ion battery and obtained cathode material
WO2024012481A1 (en) * 2022-07-13 2024-01-18 深圳市德方创域新能源科技有限公司 Iron-based lithium supplementing material for positive electrode, and preparation method therefor and use thereof

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