CN103985869A - Preparation method for positive electrode material of lithium ion battery - Google Patents

Preparation method for positive electrode material of lithium ion battery Download PDF

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Publication number
CN103985869A
CN103985869A CN201410233392.6A CN201410233392A CN103985869A CN 103985869 A CN103985869 A CN 103985869A CN 201410233392 A CN201410233392 A CN 201410233392A CN 103985869 A CN103985869 A CN 103985869A
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China
Prior art keywords
preparation
raw material
positive electrode
lithium
tio
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CN201410233392.6A
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Chinese (zh)
Inventor
傅汝毅
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Guangxi Doctor Hai Yi Information Technology Co Ltd
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Guangxi Doctor Hai Yi Information Technology Co Ltd
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Priority to CN201410233392.6A priority Critical patent/CN103985869A/en
Publication of CN103985869A publication Critical patent/CN103985869A/en
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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
    • H01M4/58—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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 preparation method for a positive electrode material of a lithium ion battery. The LiFePO4 positive electrode material is prepared from the raw materials including Li2CO3, NH4H2PO4, TiO2 and saccharose, and is doped with Ti. The LiFePO4 belongs to a multi-anion positive electrode material and has an olivine-type structure; as the positive electrode material of the lithium ion battery, the LiFePO4 is high in electrochemical performance; charging and discharging platforms are very steady; furthermore, in charging and discharging processes, the structure is stable, toxicity and pollution are avoided, the temperature range is large, and raw materials are easily available and low in cost; due to Ti doping modification, the particle sizes of the materials are uniformly distributed, and the conductivity is effectively improved.

Description

The preparation method of anode material for lithium-ion batteries
Technical field
The present invention relates to the preparation method in lithium ion battery field, particularly a kind of anode material for lithium-ion batteries.
Technical background
Lithium ion battery has unique advantages such as specific energy is high, operating voltage is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, pollution-free, security performance is good, now be widely used as pocket valuable household electrical appliance as the power supply of mobile phone, portable computer, video camera, camera etc., and in Aeronautics and Astronautics, navigation, artificial satellite, small medical and military domain of communication equipment, progressively substituted traditional power supply.
Can be used as in the positive electrode of lithium ion battery LiFePO 4have regular olivine-type structure, stable olivine structural makes positive electrode have following advantage: theoretical specific capacity (170 mAhg that (1) is higher -1) and operating voltage (3.4 V); (2) good cycle performance, particularly high temperature cyclic performance; (3) good security performance.But due to olivine-type LiFePO 4design feature cause its conductivity low, electrochemical process is diffusion control, thus there is electronic conductivity and the extremely low problem of ion diffusion rate, become restriction its application bottleneck.Cause it to commercially produce.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery LiFePO 4the preparation method of positive electrode, carries out Ti doping vario-property to material, and the positive electrode crystal formation of preparation is good, and impurity is few, effectively improves electric conductivity.
For achieving the above object, adopt following technical scheme:
A preparation method for anode material for lithium-ion batteries, positive electrode comprises following raw material: Li 2cO 3, NH 4h 2pO 4, TiO 2and sucrose, it is characterized in that: preparation process is as follows,
(1) get Li 2cO 3, NH 4h 2pO 4, TiO 2put into beaker with sucrose, add distilled water to make described raw material fully dissolve mixing;
(2) add Fe 2o 3powder, continues 8-10 hours;
(3) heated constant temperature to 80 DEG C, stirs in heating process, is stirred to moisture evaporation and obtains mixture;
(4) mixture is placed in tube furnace to 700 DEG C of roastings of constant temperature 24 hours under flowing nitrogen atmosphere;
(5) by after cooling roasting afterproduct grinding, cross 400 order sub-sieves, obtain positive electrode.
The mol ratio Li of described raw material 2cO 3: Fe 2o 3: NH 4h 2pO 4: sucrose=12:12:24:1.
Described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:99.
Described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:98.
Described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:97.
Described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:96.
Described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:95.
Substantive distinguishing features of the present invention and progress are: LiFePO 4belong to polyanionic type positive electrode, have olivine-type structure.There is good chemical property as the positive electrode of lithium ion battery, charge and discharge platform Stability Analysis of Structures, nontoxic pollution-free very steadily and in charge and discharge process, temperature range is wide, raw material are extensively with low cost, utilize carbothermic method preparation, and through Ti doping vario-property, material particle size is evenly distributed, effectively improves electric conductivity.
Brief description of the drawings
Fig. 1 is the XRD collection of illustrative plates of positive electrode in embodiment.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention will be further described.
Embodiment
(1) get Li 2cO 3, NH 4h 2pO 4, TiO 2put into beaker with sucrose, add distilled water to make described raw material fully dissolve mixing;
(2) add Fe 2o 3powder, continues 8-10 hours,
(3) heated constant temperature to 80 DEG C, stirs in heating process, is stirred to moisture evaporation and obtains mixture;
(4) mixture is placed in tube furnace to 700 DEG C of roastings of constant temperature 24 hours under flowing nitrogen atmosphere;
(5) by after cooling roasting afterproduct grinding, cross 400 order sub-sieves, obtain positive electrode Li 1-xti xfePO 4.
The mol ratio Li of raw material 2cO 3: Fe 2o 3: NH 4h 2pO 4: sucrose=12:12:24:1.
Wherein, according to raw material TiO 2with Li 2cO 3mol ratio be respectively Ti:Li=1:99,1:98,1:97,1:96,1:95, the positive electrode of gained is Li 1-xti xfePO 4(x=0.01,0.02,0.03,0.04,0.05).
Reaction principle is:
Sucrose decomposes and generates water and simple substance carbon is heated to 700 DEG C under nitrogen or argon gas atmosphere protection time, and reaction equation is:
C 12H 22O 11→12C+11H 2O
The simple substance carbon that sucrose decomposition generates is reduced into ferrous iron by ferric iron in reactant under experiment condition, and the ferrous iron of generation obtains target product with other raw material reactions again, and equation is as follows:
Li 2CO 3+2NH 4H 2PO 4+C+Fe 2O 3→2LiFePO 4+2NH 3+CO 2+3H 2O+CO
By gained positive electrode Li 1-xti xfePO 4(x=0.01,0.02,0.03,0.04,0.05) and the LiFePO that does not carry out Ti doping 4carry out X-ray diffractogram analysis of spectrum, obtain Fig. 1, in the XRD collection of illustrative plates by Fig. 1, can find out the Li synthetic by carbothermic method 1-xti xfePO 4with LiFePO 4position and the peak intensity of the diffraction maximum of material are almost identical, and hence one can see that: the LiFePO adulterating after a small amount of different proportion titanic 4material still keeps the structure of olivine-type, and titanic introducing does not cause LiFePO 4crystal formation change.The titanium ion of doping is at LiFePO 4in exist in the mode of solid solution.Because mixing of titanium occupies the position of lithium, lithium ion is+1 valency, titanium ion is+4 valencys, the lithium ion room of 4 mol produces when adulterating 1 mol titanium ion, titanium ion should not adulterate too much, because too much doping ratio can cause the loss of lithium ion, reduce for lithium that can deintercalation, the specific capacity of material is reduced.
Gained positive electrode particle diameter is evenly distributed, and effectively improves electric conductivity.

Claims (7)

1. a preparation method for anode material for lithium-ion batteries, positive electrode comprises following raw material: Li 2cO 3, NH 4h 2pO 4, TiO 2and sucrose, it is characterized in that: preparation process is as follows,
(1) get Li 2cO 3, NH 4h 2pO 4, TiO 2put into beaker with sucrose, add distilled water to make described raw material fully dissolve mixing;
(2) add Fe 2o 3powder, continues 8-10 hours;
(3) heated constant temperature to 80 DEG C, stirs in heating process, is stirred to moisture evaporation and obtains mixture;
(4) mixture is placed in tube furnace to 700 DEG C of roastings of constant temperature 24 hours under flowing nitrogen atmosphere;
(5) by after cooling roasting afterproduct grinding, cross 400 order sub-sieves, obtain positive electrode.
2. the preparation method of anode material for lithium-ion batteries according to claim 1, is characterized in that: the mol ratio Li of described raw material 2cO 3: Fe 2o 3: NH 4h 2pO 4: sucrose=12:12:24:1.
3. the preparation method of anode material for lithium-ion batteries according to claim 1, is characterized in that: described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:99.
4. the preparation method who wants the anode material for lithium-ion batteries described in 1 according to right, is characterized in that: described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:98.
5. the preparation method who wants the anode material for lithium-ion batteries described in 1 according to right, is characterized in that: described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:97.
6. the preparation method who wants the anode material for lithium-ion batteries described in 1 according to right, is characterized in that: described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:96.
7. the preparation method who wants the anode material for lithium-ion batteries described in 1 according to right, is characterized in that: described raw material TiO 2with Li 2cO 3mol ratio be, Ti:Li=1:95.
CN201410233392.6A 2014-05-29 2014-05-29 Preparation method for positive electrode material of lithium ion battery Pending CN103985869A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004036671A1 (en) * 2002-10-18 2004-04-29 Japan As Represented By President Of The University Of Kyusyu Method for preparing positive electrode material for secondary cell, and secondary cell
CN101314463A (en) * 2007-05-28 2008-12-03 上海比亚迪有限公司 Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode
CN101714658A (en) * 2009-11-05 2010-05-26 湖南维邦新能源有限公司 Preparation method of lithium iron phosphate for lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004036671A1 (en) * 2002-10-18 2004-04-29 Japan As Represented By President Of The University Of Kyusyu Method for preparing positive electrode material for secondary cell, and secondary cell
CN101314463A (en) * 2007-05-28 2008-12-03 上海比亚迪有限公司 Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode
CN101714658A (en) * 2009-11-05 2010-05-26 湖南维邦新能源有限公司 Preparation method of lithium iron phosphate for lithium ion battery

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Application publication date: 20140813