CN1585168A - Modified ferrous lithium phosphate as anode material for lithium ion batteries and its production - Google Patents

Modified ferrous lithium phosphate as anode material for lithium ion batteries and its production Download PDF

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Publication number
CN1585168A
CN1585168A CNA2004100102938A CN200410010293A CN1585168A CN 1585168 A CN1585168 A CN 1585168A CN A2004100102938 A CNA2004100102938 A CN A2004100102938A CN 200410010293 A CN200410010293 A CN 200410010293A CN 1585168 A CN1585168 A CN 1585168A
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CN
China
Prior art keywords
lithium
anode material
ion batteries
inert atmosphere
ferrous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2004100102938A
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Chinese (zh)
Inventor
赵丽
崔成伟
孙科
王涛
杨书廷
赵娜红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinxiang Green New Energy Material Co Ltd
HENAN JINLONG PRECISE COPPER PIPE CO Ltd
Original Assignee
Xinxiang Green New Energy Material Co Ltd
HENAN JINLONG PRECISE COPPER PIPE CO Ltd
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Application filed by Xinxiang Green New Energy Material Co Ltd, HENAN JINLONG PRECISE COPPER PIPE CO Ltd filed Critical Xinxiang Green New Energy Material Co Ltd
Priority to CNA2004100102938A priority Critical patent/CN1585168A/en
Publication of CN1585168A publication Critical patent/CN1585168A/en
Pending legal-status Critical Current

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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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention is to supply a positive pole material for the lithium ion battery with the property of excellent performance and low cost, apply the olivine type modification lithium ferrous phosphate as positive material, its molecular formula is presented as LiFl-xMxPO4, in which the M is one or two of the elements as below: Cr, Co Mn, Mg, Ni, La. The producing method mixes the lithium iron modification element M with the phosphor after warming-up and igloss processing in the inert gases, the modification lithium ferrous phosphate with stable structure is produced.

Description

Lithium ion battery ferrous lithium anode material of modified phosphate and production method thereof
Technical field:
The present invention relates to a kind of battery, particularly a kind of lithium ion battery ferrous lithium anode material of modified phosphate and production method thereof.
Background technology:
The superior function of lithium ion battery and pollution-free having obtained are used widely.The positive electrode of lithium ion battery is the bottleneck of restriction lithium ion battery development, and it is determining performance, price and the development thereof of lithium ion battery.Commercial LiCoO 2With the LiNiO that is subjected to broad research 2With LiMn 2O 4Each tool advantage of positive electrode, but the synthetic difficulty of LiNiO2 is difficult for suitability for industrialized production, the LiMn2O4 actual specific capacity is low, and cycle performance is poor, and the cobalt of LiCoO2 is more expensive and resource is few, and its development is restricted.Existing bibliographical information synthesizes lithium iron phosphate cathode material with high temperature solid-state, and its advantage is that Fe aboundresources price is low, but its discharge capacity and cycle performance are relatively poor.
Summary of the invention:
The technical issues that need to address of the present invention provide low anode material for lithium-ion batteries and the production method thereof of the good cost of a kind of performance.Technical scheme of the present invention is, a kind of anode material for lithium-ion batteries, it is characterized in that: positive electrode is the ferrous lithium of olivine-type modified phosphate, and molecular formula is LiFe1-xMxPO4, and wherein M is any one or two kinds of element: Cr, Co in the following column element, Mn, Mg, Ni, La.Following atoms of elements ratio is: Li/Fe+M=1-1.1, Fe/P=1, Fe/M=32-99.The production method of anode material for lithium-ion batteries, it is characterized in that: operation (1): lithium, iron, modifying element M and phosphorus source mix by following atomic ratio, Li/Fe+M=1.0-1.1, Fe/P=1, Fe/M=32-99, operation (2): in the mixed material of operation (1), add conductive agent, operation (3): it is even that the material of operation (2) is put into stirrer for mixing, operation (4): with operation (3) mixed material in inert atmosphere and under 300-400 ℃ of condition after The pre-heat treatment 10-18 hour, then in inert atmosphere and under 650-750 ℃ of condition, carry out calcination in 20-24 hour processing, operation (5): the material after above-mentioned calcination is handled carries out ball milling after cooling, crosses 300 mesh sieves and promptly makes the ferrous lithium anode material of modified phosphate.The present invention is owing to having adopted the ferrous reason of modified phosphate to make positive electrode and having adopted middle temperature solid phase synthesis and the technology of the interior doping surfaces coating of body, synthesize the ferrous lithium of modified phosphate (LiFe-xMxPO4) material, has discharge capacity compared with the prior art up to 135mAh/g, the remarkable advantage that cycle performance height and cost are low.
The ferrous lithium of modified phosphate of the present invention is adopted material modifiedly is constitutionally stable element, i.e. any one among Cr, Co, Mn, Mg, Ni, the La or two kinds.Adopted the low-temperature prewarming processing, make the lithium source, source of iron and phosphorus source are molten to together, allow oxygen, iron, phosphonium ion keeps superperformance, this not only can guarantee the atomic ratio coordination, constant and reactant atom obtains good diffusion, make lithium take place to mix in the level of atom level with modifier Mx, behind high temperature sintering, make good crystallinity, constitutionally stable olivine-type LiFeI-xMxPO4 positive electrode, its uniform properties that has can make lithium ion battery show significant fail safe and thermal stability, the charging and discharging capacity height, the advantage that reversibility is good, particularly high rate during charging-discharging significantly improves.
Embodiment:
Embodiment 1
The atomic ratio of lithium and iron and M be Li/ (Fe+M)=1.02 mixing of materials such as lithium carbonate, ferrous salt, chromic salts (chromium-containing oxide), conductive agent 2 hours evenly.
2. will in inert atmosphere, be incubated 15 hours, natural cooling under lower temperature 400 degree at the powder material that described first treatment step obtains.
3. will batch mixing be even once more at the powder thing of the described second treatment step pre-burning, insulation 24 hours under higher temperatures 650 degree in inert atmosphere again, it is stand-by that the cooling ball milling is crossed 300 mesh sieves.
Embodiment 2
The atomic ratio of lithium and iron and M be Li/ (Fe+M)=1.04 mixing of materials such as lithium carbonate, ferrous salt, chromic salts (chromium-containing oxide), conductive agent 2 hours evenly.
2. will in inert atmosphere, be incubated 14 hours, natural cooling under lower temperature 400 degree at the powder material that described first treatment step obtains.
3. will batch mixing be even once more at the powder thing of the described second treatment step pre-burning, insulation 24 hours under higher temperatures 650 degree in inert atmosphere again, it is stand-by that the cooling ball milling is crossed 300 mesh sieves.
Embodiment 3
The atomic ratio of lithium and iron and M be Li/ (Fe+M)=1.06 mixing of materials such as lithium carbonate, ferrous salt, chromic salts (chromium-containing oxide), conductive agent 2 hours evenly.
2. will in inert atmosphere, be incubated 18 hours, natural cooling under lower temperature 400 degree at the powder material that described first treatment step obtains.
3. will batch mixing be even once more at the powder thing of the described second treatment step pre-burning, insulation 24 hours under higher temperatures 650 degree in inert atmosphere again, it is stand-by that the cooling ball milling is crossed 300 mesh sieves.
Embodiment 4
The atomic ratio of lithium and iron and M be Li/ (Fe+M)=1.04 mixing of materials such as lithium carbonate, ferrous salt, chromic salts (chromium-containing oxide), conductive agent 2 hours evenly.
2. will in inert atmosphere, be incubated 10 hours, natural cooling under lower temperature 400 degree at the powder material that described first treatment step obtains.
3. will batch mixing be even once more at the powder thing of the described second treatment step pre-burning, insulation 20 hours under higher temperatures 750 degree in inert atmosphere again, it is stand-by that the cooling ball milling is crossed 300 mesh sieves.
Embodiment 5
The atomic ratio of lithium and iron and M be Li/ (Fe+M)=1.05 mixing of materials such as lithium carbonate, ferrous salt, chromic salts (chromium-containing oxide), conductive agent 2 hours evenly.
2. will in inert atmosphere, be incubated 10 hours, natural cooling under lower temperature 400 degree at the powder material that described first treatment step obtains.
3. will batch mixing be even once more at the powder thing of the described second treatment step pre-burning, insulation 20 hours under higher temperatures 750 degree in inert atmosphere again, it is stand-by that the cooling ball milling is crossed 300 mesh sieves.
Embodiment 6
The atomic ratio of lithium and iron and M be Li/ (Fe+M)=1.04 mixing of materials such as lithium carbonate, ferrous salt, chromic salts (chromium-containing oxide), conductive agent 2 hours evenly.
2. will in inert atmosphere, be incubated 18 hours, natural cooling under lower temperature 350 degree at the powder material that described first treatment step obtains.
3. will batch mixing be even once more at the powder thing of the described second treatment step pre-burning, insulation 24 hours under higher temperatures 650 degree in inert atmosphere again, it is stand-by that the cooling ball milling is crossed 300 mesh sieves.
Embodiment 7
The atomic ratio of lithium and iron and M be Li/ (Fe+M)=1.05 mixing of materials such as lithium carbonate, ferrous salt, chromic salts (chromium-containing oxide), conductive agent 2 hours evenly.
2. will in inert atmosphere, be incubated 20 hours, natural cooling under lower temperature 350 degree at the powder material that described first treatment step obtains.
3. will batch mixing be even once more at the powder thing of the described second treatment step pre-burning, insulation 24 hours under higher temperatures 700 degree in inert atmosphere again, it is stand-by that the cooling ball milling is crossed 300 mesh sieves.
Anode material for lithium-ion batteries and lithium ion battery negative material graphite with method for preparing, with the vinylidene is the pole plate binding agent, make the positive plate and the negative plate of lithium ion battery respectively, with the microporous polypropylene membrane is electrode diaphragm, is dimethyl carbonate with the volume ratio: diethyl carbonate: the 1M lithium hexafluoro phosphate of ethylene carbonate=1: 1: 1 is that electrolyte is assembled into lithium ion battery.
The performance table of the lithium ion battery of each embodiment preparation

Claims (3)

1. anode material for lithium-ion batteries, it is characterized in that: positive electrode is the ferrous lithium of olivine-type modified phosphate, and molecular formula is LiFe1-xMxPO4, wherein M is any one or two kinds of element: Cr, Co in the column element down, Mn, Mg, Ni, La.
2. anode material for lithium-ion batteries according to claim 1 is characterized in that: following atoms of elements ratio is: Li/Fe+M=1-1.1, Fe/P=1, Fe/M=32-99.
3. the production method of anode material for lithium-ion batteries, it is characterized in that: operation (1): lithium, iron, modifying element M and phosphorus source mix by following atomic ratio, Li/Fe+M=1.0-1.1, Fe/P=1, Fe/M=32-99, operation (2): in the mixed material of operation (1), add conductive agent, operation (3): it is even that the material of operation (2) is put into stirrer for mixing, operation (4): with operation (3) mixed material in inert atmosphere and under 300-400 ℃ of condition after The pre-heat treatment 10-18 hour, then in inert atmosphere and under 650-750 ℃ of condition, carry out calcination in 20-24 hour processing, operation (5): the material after above-mentioned calcination is handled carries out ball milling after cooling, crosses 300 mesh sieves and promptly makes the ferrous lithium anode material of modified phosphate.
CNA2004100102938A 2004-05-21 2004-05-21 Modified ferrous lithium phosphate as anode material for lithium ion batteries and its production Pending CN1585168A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009012669A1 (en) * 2007-07-20 2009-01-29 Byd Company Limited Cathode active material for a lithium ion battery and method for preparing the same
WO2009124431A1 (en) 2008-04-07 2009-10-15 Byd Company Limited A method for preparing iron source used for preparing lithium ferrous phosphate, and a method for preparing lithium ferrous phosphate
CN101327921B (en) * 2007-06-20 2010-05-26 中南大学 Preparation of ferric phosphate lithium composite material
CN102104148A (en) * 2010-12-31 2011-06-22 北京中科浩运科技有限公司 Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof
CN101401230B (en) * 2006-03-08 2011-09-07 张惇杰 Cathode material for li-ion battery applications
CN101617422B (en) * 2007-02-19 2012-01-11 丰田自动车株式会社 Electrode active material and manufacturing method of the same
CN109980295A (en) * 2019-03-26 2019-07-05 陈林龙 The preparation process of new energy resource power battery

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101401230B (en) * 2006-03-08 2011-09-07 张惇杰 Cathode material for li-ion battery applications
CN101617422B (en) * 2007-02-19 2012-01-11 丰田自动车株式会社 Electrode active material and manufacturing method of the same
US8951667B2 (en) 2007-02-19 2015-02-10 Toyota Jidosha Kabushiki Kaisha Electrode active material and manufacturing method of same
CN101327921B (en) * 2007-06-20 2010-05-26 中南大学 Preparation of ferric phosphate lithium composite material
WO2009012669A1 (en) * 2007-07-20 2009-01-29 Byd Company Limited Cathode active material for a lithium ion battery and method for preparing the same
WO2009124431A1 (en) 2008-04-07 2009-10-15 Byd Company Limited A method for preparing iron source used for preparing lithium ferrous phosphate, and a method for preparing lithium ferrous phosphate
CN102104148A (en) * 2010-12-31 2011-06-22 北京中科浩运科技有限公司 Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof
CN109980295A (en) * 2019-03-26 2019-07-05 陈林龙 The preparation process of new energy resource power battery

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