CN107834030A - One kind addition nano titanium oxide prepares combination electrode material and technique - Google Patents

One kind addition nano titanium oxide prepares combination electrode material and technique Download PDF

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Publication number
CN107834030A
CN107834030A CN201710582777.7A CN201710582777A CN107834030A CN 107834030 A CN107834030 A CN 107834030A CN 201710582777 A CN201710582777 A CN 201710582777A CN 107834030 A CN107834030 A CN 107834030A
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electrode material
combination electrode
powder
ball
source
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CN201710582777.7A
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郑观情
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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 one kind addition nano titanium oxide to prepare combination electrode material and technique.The material is the Fe (PO using LiOH as lithium source4)3As source of iron, (NH4)2HPO4For source of phosphoric acid, doped raw material of the Nd powder as doping Nd, doped raw material of the nano titanium dioxide powder as doping Ti, according to Li1‑xNd xFe1‑yTiyPO4Atom ratio prepare a kind of combination electrode material.First according to atom ratio dispensing, slurry is then prepared by ball-milling technology ball milling, will be heat-treated after slurry drying under inert atmosphere protection, cooled down and can prepare target product.The method technique is simple, and combination electrode material powder property is good.

Description

One kind addition nano titanium oxide prepares combination electrode material and technique
Technical field
The present invention relates to a kind of lithium ion combination electrode material and its preparation technology, more particularly to a kind of doping titanium elements Lithium ion combination electrode material and preparation method, belong to electrode material manufacture field.
Background technology
Lithium ion battery is a kind of secondary cell（Rechargeable battery）, it relies primarily on lithium ion between a positive electrode and a negative electrode Movement carrys out work.In charge and discharge process, Li+ comes and goes insertion and deintercalation between two electrodes：During charging, Li+ takes off from positive pole It is embedding, negative pole is embedded in by electrolyte, negative pole is in rich lithium state, then opposite during electric discharge.With LiFePO4For representative it is poly- it is cloudy from Minor structure phosphate material, its protrude security, overlength cycle life, it is inexpensive the features such as lithium-ion electric subdomains by Extensive concern.
LiFePO4With the hexagonal closs packing arrangement architecture somewhat distorted, belong to rhombic system, where lithium atom In a-c planes, include PO4Tetrahedron, which limits the mobile space of lithium ion, causes lithium ion mobility speed and electricity Electron conductivity is relatively low, constrains LiFePO4The application of lithium battery.
There is document（Rare earth ion is adulterated to LiFePO4The influence of structure and performance,《Rare Metals Materials and work Journey》,2011,40 (11):1936-1940）Point out：By rare earth ion to LiFePO4Li atoms position be doped, lead to Cross X-ray diffraction（XRD）, constant current charge-discharge and electrochemical impedance（EIS）Genealogy of law system analysis shows：The property of sample after doping It can be greatly improved.Therefore rare earth element is often added in actual fabrication process, improves LiFePO4Electrode material Performance.But single addition rare earth element, to LiFePO4Conductance performance improvement it is single, LiFePO4Electrode material is applied Less than further lifting.
The content of the invention
The present invention prepares a kind of Li by ball-milling technology and high temperature solid-state method1-xNdxFe1-yTiyPO4Combination electrode material, and Rare earth Nd powder and nano titanium dioxide powder are added in preparation process, so as to adulterate Nd and Ti atoms, prepares Li1-xNdxFe1- yTiyPO4Combination electrode material, improve LiFePO4Conduction and charge-discharge performance.The method technique is simple, presoma mixing journey Degree is good, and production cost is low, and the electrode material circulation of preparation and volumetric properties are good.The preparation technology bag of the electrode material powder Include following steps：
(1) using LiOH as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Nd powder is as doping Nd's Doped raw material, doped raw material of the nano titanium dioxide powder as doping Ti, each composition is according to Li1-xNd xFe1-yTiyPO4 （0.02≤x≤0.1, 0.2≤y≤0.4）Atomic ratio dispensing, then take a certain amount of raw material prepared to be carried out with ball grinder Ball milling；
(2) obtained slurry mix after ball milling is dried, precursor powder is obtained after drying；
By the precursor powder of preparation under inert atmosphere protection in being heat-treated；
(4) after Technology for Heating Processing, products therefrom is naturally cooled into room temperature under inert atmosphere protection, powder is collected and produces To a kind of Li1-xNd xFe1-yTiyPO4Combination electrode material powder.
Above-mentioned electrode material powder step of preparation process (1) in, the mechanical milling process need add ball-milling medium it is anhydrous Alcohol or acetone, mechanical ball mill time are 10-15 hours.Above-mentioned electrode material powder step of preparation process (2) in, institute It is using spray drying to state to mixed slurry drying.Above-mentioned electrode material powder step of preparation process (3) in, it is described to preceding It is under the conditions of the mixed gas of nitrogen, argon gas or both, first in 500-600 DEG C of bar to drive body powder and carry out Technology for Heating Processing Heat treatment 5-8h is carried out under part, temperature is then increased to 700-800 DEG C, is heat-treated 10-15h.In above-mentioned electrode material powder Step of preparation process (4) in, be under the conditions of the mixed gas of nitrogen, argon gas or both under the inert atmosphere protection.
Embodiment one：
Using LiOH as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Nd powder is mixed as doping Nd's Miscellaneous raw material, doped raw material of the nano titanium dioxide powder as doping Ti, according to Li0.98Nd0.02Fe0.8Ti0.2PO4Atom match somebody with somebody Mixture than dispensing 5g, the mixture material prepared pour into ball grinder together after tentatively mixing, then toward ball grinder It is middle to add appropriate steel ball and absolute alcohol as ball-milling medium, then cover ball grinder lid and tighten screw, again will after tightening It, which is put into planetary ball mill, carries out ball milling 10 hours, ball milling removes ball grinder standing a period of time after terminating after, opens ball Grinding jar, alloy powder slurry in ball grinder is taken out and be spray-dried to obtain precursor powder, then by powder nitrogen protection Under the conditions of be heated at high temperature to 500 DEG C, constant temperature 5 hours, then raise temperature to 700 DEG C, constant temperature 10 hours, products therefrom exists Room temperature is naturally cooled under nitrogen atmosphere protection, powder is collected and produces product.
Embodiment two：
Using LiOH as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Nd powder is mixed as doping Nd's Miscellaneous raw material, doped raw material of the nano titanium dioxide powder as doping Ti, according to Li0.95Nd0.05Fe0.7Ti0.3PO4Atom match somebody with somebody Mixture than dispensing 20g, the mixture material prepared pour into ball grinder together after tentatively mixing, then toward ball grinder It is middle to add appropriate steel ball and absolute alcohol ball-milling medium, then cover ball grinder lid and tighten screw, put again after tightening Enter to carry out ball milling in planetary ball mill 12 hours, ball milling removes ball grinder standing a period of time after terminating after, open ball grinder, Alloy powder slurry in ball grinder is taken out and carries out being spray-dried to obtain precursor powder, then by powder under the protective condition of nitrogen Carry out being heated at high temperature to 550 DEG C, constant temperature 6 hours, then raise temperature to 750 DEG C, constant temperature 12 hours, products therefrom is in nitrogen gas Room temperature is naturally cooled under atmosphere protection, powder is collected and produces product.
Embodiment three：
Using LiOH as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Nd powder is mixed as doping Nd's Miscellaneous raw material, doped raw material of the nano titanium dioxide powder as doping Ti, according to Li0.9Nd0.1Fe0.6Ti0.4PO4Atom ratio Dispensing 50g mixture, the mixture material prepared pour into ball grinder together after tentatively mixing, then toward in ball grinder Appropriate steel ball and acetone ball-milling medium is added, ball grinder lid is then covered and tightens screw, put it into planet after tightening again Ball milling is carried out in formula ball mill 15 hours, ball milling removes ball grinder standing a period of time after terminating after, ball grinder is opened, by ball milling Alloy powder slurry, which takes out, in tank is carried out being spray-dried to obtain precursor powder, then precursor powder is loaded to the quartz of an end closure In glass tube, inside full of appropriate nitrogen, then with the thermal-flame vitreous silica tube opening other end make its sealing, by the stone of sealing English glass tube input water in verify air-tightness, if bubble-free, can assert that its sealing is good, by powder nitrogen protection Under the conditions of be heated at high temperature to 600 DEG C, constant temperature 8 hours, then raise temperature to 800 DEG C, constant temperature 15 hours, products therefrom exists Room temperature is naturally cooled under nitrogen atmosphere protection, powder is collected and produces product.

Claims (5)

  1. A kind of 1. Li1-xNdxFe1-yTiyPO4Combination electrode material, it is characterised in that the preparation method of the combination electrode material is by such as Lower step is carried out：
    (1) using LiOH as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Nd powder is mixed as doping Nd's Miscellaneous raw material, doped raw material of the nano titanium dioxide powder as doping Ti, each composition is according to Li1-xNd xFe1-yTiyPO4（0.02 ≤x≤0.1, 0.2≤y≤0.4）Atomic ratio dispensing, then take a certain amount of raw material prepared to carry out ball milling with ball grinder；
    (2) obtained slurry mix after ball milling is dried, precursor powder is obtained after drying；
    By the precursor powder of preparation under inert atmosphere protection in being heat-treated；
    (4) after Technology for Heating Processing, products therefrom is naturally cooled into room temperature under inert atmosphere protection, powder is collected and produces To a kind of Li1-xNd xFe1-yTiyPO4Combination electrode material powder.
  2. A kind of 2. Li as claimed in claim 11-xNdxFe1-yTiyPO4Combination electrode material, it is characterised in that in preparation technology Step (1) in, the mechanical milling process needs to add ball-milling medium absolute alcohol or acetone, and the mechanical ball mill time is that 10-15 is small When.
  3. A kind of 3. Li as described in claim 1 or 21-xNdxFe1-yTiyPO4Combination electrode material, it is characterised in that in material Material prepare the step of (2) in, it is described to mixed slurry dry be using spray drying.
  4. A kind of 4. Li as described in claim 1 or 21-xNdxFe1-yTiyPO4Combination electrode material, it is characterised in that making Standby processing step (3) in, the Technology for Heating Processing that carried out to precursor powder is the mixed gas in nitrogen, argon gas or both Under the conditions of, heat treatment 5-8h is first carried out under conditions of 500-600 DEG C, temperature is then increased to 700-800 DEG C, heat treatment 10-15h。
  5. A kind of 5. Li as described in claim 1 or 21-xNdxFe1-yTiyPO4Combination electrode material, it is characterised in that making Standby processing step (4) in, be under the conditions of the mixed gas of nitrogen, argon gas or both under the inert atmosphere protection.
CN201710582777.7A 2017-07-17 2017-07-17 One kind addition nano titanium oxide prepares combination electrode material and technique Withdrawn CN107834030A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837033A (en) * 2006-03-24 2006-09-27 山东科技大学 Process for synthesizing LiFePO4 as positive electrode materials of lithium ion cell
CN101339994A (en) * 2008-09-01 2009-01-07 罗绍华 Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof
CN101800315A (en) * 2010-04-09 2010-08-11 曲阜毅威能源股份有限公司 Multielement-doped lithium iron phosphate positive electrode material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837033A (en) * 2006-03-24 2006-09-27 山东科技大学 Process for synthesizing LiFePO4 as positive electrode materials of lithium ion cell
CN101339994A (en) * 2008-09-01 2009-01-07 罗绍华 Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof
CN101800315A (en) * 2010-04-09 2010-08-11 曲阜毅威能源股份有限公司 Multielement-doped lithium iron phosphate positive electrode material and preparation method thereof

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Application publication date: 20180323