CN107834028A - A kind of combination electrode material for adulterating vanadium - Google Patents

A kind of combination electrode material for adulterating vanadium Download PDF

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Publication number
CN107834028A
CN107834028A CN201710578304.XA CN201710578304A CN107834028A CN 107834028 A CN107834028 A CN 107834028A CN 201710578304 A CN201710578304 A CN 201710578304A CN 107834028 A CN107834028 A CN 107834028A
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electrode material
powder
combination electrode
adulterating
vanadium
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CN201710578304.XA
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郑观情
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of combination electrode material for adulterating vanadium.The combination electrode material is using LiOH as lithium source, with FeC2O4・2H2O is as source of iron, NH4H2PO4As source of phosphoric acid, with Nd powder and NH4VO3Powder prepares Li as foreign atom raw material1‑xNd xFe1‑yVyPO4Combination electrode material.First raw material is mixed by atom ratio; slurry mix is prepared using mechanical ball mill after mixing, is then dried under inert atmosphere protection, obtains precursor powder; again by precursor powder under inert atmosphere protection, a kind of combination electrode material powder-product is produced by being cooled down after Technology for Heating Processing.

Description

A kind of combination electrode material for adulterating vanadium
Technical field
The present invention relates to a kind of li-ion electrode materials and its preparation technology, more particularly to a kind of addition rare earth and v element Li-ion electrode materials and preparation method thereof, belong to battery electrode material manufacture field.
Background technology
With developing rapidly for the field such as mobile phone, notebook, electric car and telecommunications is standby, lithium ion battery has obtained widely Using.Lithium ion battery is a kind of secondary cell(Rechargeable battery), it relies primarily on lithium ion and moved between a positive electrode and a negative electrode Move and carry 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 A-c planes in, include PO4Tetrahedron, which limits the mobile space of lithium ion, causes lithium ion mobility speed It is relatively low with electronic conductivity, constrain 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 show:Rare earth ion It is dissolved into well in olivine structural, the performance for adulterating sample is greatly improved.Therefore in order to improve LiFePO4's Performance, rare earth element is often added in actual fabrication process, rare earth element is metal material " vitamin ", to improving metal It is special that the performance of material plays the role of.But rare earth element is only added, to LiFePO4Conductance performance improvement it is single, LiFePO4The application of electrode material cannot be lifted further.
The content of the invention
The present invention prepares a kind of Li by ball-milling technology and high temperature solid-state method1-xNdxFe1-yVyPO4Combination electrode material, lead to Cross and add rare earth Nd powder and NH during tradition is using ball-milling technology and high temperature solid-state method4VO3Powder, adulterate Nd and V atoms, system Standby Li1-xNdxFe1-yVyPO4Combination electrode material, make up LiFePO4Deficiency, improve LiFePO4Conduction and charge-discharge performance. The method technique is simple, and presoma mixability is good, and production cost is low.The preparation technology of the electrode material powder includes as follows Step:
(1) using LiOH as lithium source, with FeC2O4・2H2O is as source of iron, NH4H2PO4As source of phosphoric acid, and Nd powder and NH4VO3Powder End is used as doped raw material, according to Li1-xNd xFe1-yVyPO4(0.02≤x≤0.1, 0. 2≤y≤0.4)Atomic ratio dispensing, Then take a certain amount of raw material prepared to pour into ball grinder, and add appropriate steel ball and ball-milling medium progress mechanical ball mill 10-15 obtains slurry mix after hour;
(2) slurry mix obtained above is taken out, it is dried, precursor powder is obtained after drying;
(3) the precursor powder of preparation is subjected to heat treatment 5-8h under inert atmosphere protection under conditions of 500 DEG C;
(4) temperature is increased to 700 DEG C again, constant temperature heat treatment 10-15h;
(5) products therefrom naturally cools to room temperature under inert atmosphere protection, collects powder and obtains a kind of Li1-xNd xFe1- yVyPO4Combination electrode material powder.
Preferentially, step (1) in, ball-milling medium is absolute alcohol or acetone.
Preferentially, step (2) in, the drying means of the presoma is spray drying.
Preferentially, step (3) in, described inert gas is the mixed gas of nitrogen, argon gas or both.
Preferentially, step (5) in, described inert gas is the mixed gas of nitrogen, argon gas or both.
Embodiment one:
Using LiOH as lithium source, with FeC2O4・2H2O is as source of iron, NH4H2PO4As source of phosphoric acid, and Nd powder and NH4VO3Powder As doped raw material, according to Li0.98Nd0.02Fe0.8V0.2PO4Atom ratio dispensing 5g mixture, the mixture prepared is former Material poured into together in ball grinder after tentatively mixing, then toward adding appropriate steel ball and absolute alcohol in ball grinder as ball milling Jie Matter, then covers ball grinder lid and tightens screw, is put it into again after tightening in planetary ball mill and carries out ball milling 10 hours, Ball milling removes ball grinder standing a period of time after terminating after, ball grinder is opened, alloy powder slurry in ball grinder is taken out and carried out It is spray-dried to obtain precursor powder, then powder is carried out under the protective condition of nitrogen to being heated at high temperature to 500 DEG C, constant temperature 5 hours, Then temperature is raised to 700 DEG C, and constant temperature 10 hours, products therefrom naturally cools to room temperature under nitrogen atmosphere protection, collects powder End produces product.
Embodiment two:
Using LiOH as lithium source, with FeC2O4・2H2O is as source of iron, NH4H2PO4As source of phosphoric acid, and Nd powder and NH4VO3Powder As doped raw material, according to Li0.95Nd0.05Fe0.7V0.3PO4Atom ratio dispensing 20g mixture, the mixture that will be prepared Raw material poured into together in ball grinder after tentatively mixing, then is situated between toward appropriate steel ball and absolute alcohol ball milling is added in ball grinder Matter, then covers ball grinder lid and tightens screw, is put it into again after tightening in planetary ball mill and carries out ball milling 12 hours, Ball milling removes ball grinder standing a period of time after terminating after, ball grinder is opened, alloy powder slurry in ball grinder is taken out and carried out It is spray-dried to obtain precursor powder, then powder is carried out under the protective condition of nitrogen to being heated at high temperature to 500 DEG C, constant temperature 6 hours, Then temperature is raised to 700 DEG C, and constant temperature 12 hours, products therefrom naturally cools to room temperature under nitrogen atmosphere protection, collects powder End produces product.
Embodiment three:
Using LiOH as lithium source, with FeC2O4・2H2O is as source of iron, NH4H2PO4As source of phosphoric acid, and Nd powder and NH4VO3Powder As doped raw material, according to Li0.9Nd0.1Fe0.6V0.4PO4Atom ratio dispensing 50g mixture, the mixture prepared is former Material poured into together in ball grinder after tentatively mixing, then toward adding appropriate steel ball and absolute alcohol ball-milling medium in ball grinder, Then cover ball grinder lid and tighten screw, put it into again after tightening in planetary ball mill and carry out ball milling 15 hours, ball Mill removes ball grinder standing a period of time after terminating after, ball grinder is opened, alloy powder slurry in ball grinder is taken out and sprayed Mist it is dry precursor powder, then precursor powder is fitted into the quartz glass tube of an end closure, inside full of appropriate nitrogen, Make its sealing with the thermal-flame vitreous silica tube opening other end again, it is airtight by being verified in the quartz glass tube input water of sealing Property, it if bubble-free, can assert that its sealing is good, will carry out being heated at high temperature to 500 under protective condition of the powder in nitrogen DEG C, constant temperature 8 hours, temperature is then raised to 700 DEG C, constant temperature 15 hours, products therefrom natural cooling under nitrogen atmosphere protection To room temperature, collect powder and produce product.

Claims (5)

  1. A kind of 1. Li for adulterating vanadium1-xNdxFe1-yVyPO4Combination electrode material, it is characterised in that the preparation of the combination electrode material Method is carried out as follows:
    (1) using LiOH as lithium source, with FeC2O4・2H2O is as source of iron, NH4H2PO4As source of phosphoric acid, and Nd powder and NH4VO3Powder As doped raw material, according to Li1-xNd xFe1-yVyPO4(0.02≤x≤0.1, 0. 2≤y≤0.4)Atomic ratio dispensing, so Take a certain amount of raw material prepared to pour into ball grinder afterwards, and add appropriate steel ball and ball-milling medium progress mechanical ball mill 10- Slurry mix is obtained after 15 hours;
    (2) slurry mix obtained above is taken out, it is dried, precursor powder is obtained after drying;
    (3) the precursor powder of preparation is subjected to heat treatment 5-8h under inert atmosphere protection under conditions of 500 DEG C;
    (4) temperature is increased to 700 DEG C again, constant temperature heat treatment 10-15h;
    (5) products therefrom naturally cools to room temperature under inert atmosphere protection, collects powder and obtains a kind of Li1-xNd xFe1- yVyPO4Combination electrode material powder.
  2. A kind of 2. Li for adulterating vanadium as claimed in claim 11-xNdxFe1-yVyPO4Combination electrode material, it is characterised in that Step (1) in, ball-milling medium is absolute alcohol or acetone.
  3. A kind of 3. Li for adulterating vanadium as described in claim 1 or 21-xNdxFe1-yVyPO4Combination electrode material, its feature exist In, prepared by material the step of (2) in, the drying means of the presoma is spray drying.
  4. A kind of 4. Li for adulterating vanadium as described in claim 1 or 21-xNdxFe1-yVyPO4Combination electrode material, its feature exist In, prepared by material the step of (3) in, described inert gas is the mixed gas of nitrogen, argon gas or both.
  5. A kind of 5. Li for adulterating vanadium as described in claim 1 or 21-xNdxFe1-yVyPO4Combination electrode material, its feature exist In, material prepare step (5) in, described inert gas is the mixed gas of nitrogen, argon gas or both.
CN201710578304.XA 2017-07-16 2017-07-16 A kind of combination electrode material for adulterating vanadium Withdrawn CN107834028A (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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