CN107834029A - A kind of doping Cr combination electrode material and its preparation technology - Google Patents
A kind of doping Cr combination electrode material and its preparation technology Download PDFInfo
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- CN107834029A CN107834029A CN201710582758.4A CN201710582758A CN107834029A CN 107834029 A CN107834029 A CN 107834029A CN 201710582758 A CN201710582758 A CN 201710582758A CN 107834029 A CN107834029 A CN 107834029A
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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
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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
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of doping Cr combination electrode material and its preparation technology.The combination electrode material is with LiOH, Fe (PO4)3, (NH4)2HPO4, Rare-Earth Ce powder and metal Cr powder are as raw material, according to Li1‑xCe xFe1‑yCryPO4Atomic ratio dispensing prepare a kind of Li1‑xCe xFe1‑yCryPO4Combination electrode material.First by raw material atomic ratio dispensing; the raw material prepared is subjected to mechanical ball mill with ball grinder again and prepares uniform slurry mix; then it is dried under inert atmosphere protection, obtains precursor powder, will be finally heat-treated under precursor powder, cools down and can obtain combination electrode material product.Particle size uniformity is obtained due to being handled by ball-milling technology, preparation technology is simple using high temperature solid-state method, easily operated, and the sample of preparation has excellent charge-discharge performance.
Description
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 Cr 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-xCexFe1-yCryPO4Combination electrode material.
Rare-Earth Ce powder and metal Cr powder are added in preparation process, prepares a kind of Li1-xCexFe1-yCryPO4Combination electrode material, by mixing
Miscellaneous Cr ions enter LiFePO4Substitute a part of Fe atoms in structure cell, the result is that so that the faint distortion of lattice generation, widens
Li+ ion diffusion admittances.The preparation technology of the electrode material powder comprises the following steps：
(1) LiOH is as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Rare-Earth Ce powder is as doping Ce
Atomic raw material, doped raw material of the metal Cr powder as doping Cr atoms, each composition is according to Li1-xCe xFe1-yCryPO4（0.02≤x
≤0.1, 0.2≤y≤0.4）Atomic ratio dispensing；
(2) take a certain amount of raw material prepared to carry out mechanical ball mill with ball grinder；
(3) 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；
(5) 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-xCe xFe1-yCryPO4Combination electrode material powder.
Above-mentioned electrode material powder step of preparation process (2) 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 (3) in, institute
It is using spray drying to state to mixed slurry drying.Above-mentioned electrode material powder step of preparation process (4) 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 800-900 DEG C, is heat-treated 10-15h.In above-mentioned electrode material powder
Step of preparation process (5) in, be under the conditions of the mixed gas of nitrogen, argon gas or both under the inert atmosphere protection.
The Li of preparation1-xCe xFe1-yCryPO4Combination electrode material powder has advantages below：
(I) particle size uniformity can be obtained by being handled by ball-milling technology.
(2) the high temperature solid-state method preparation technology used is simple, easily operated.
(3) Li after Ce and Cr is adulterated1-xCe xFe1-yCryPO4Sample has excellent charge-discharge performance.
Embodiment one：
Using LiOH as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Ce powder is mixed as doping Ce's
Miscellaneous raw material, doped raw material of the metal Cr powder as doping Cr atoms, according to Li0.98Ce0.02Fe0.8Cr0.2PO4Atom ratio match somebody with somebody
Expect 5g mixture, the mixture material prepared poured into together in ball grinder after tentatively mixing, then toward adding in ball grinder
Appropriate steel ball and absolute alcohol is added then to cover ball grinder lid as ball-milling medium and tighten screw, put again after tightening
Enter to carry out ball milling in planetary ball mill 10 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 500 DEG C, constant temperature 5 hours, then raise temperature to 800 DEG C, constant temperature 10 hours, products therefrom is in nitrogen gas
Room temperature is naturally cooled under 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, Ce powder is mixed as doping Ce's
Miscellaneous raw material, doped raw material of the metal Cr powder as doping Cr atoms, according to Li0.95Ce0.05Fe0.7Cr0.3PO4Atom ratio match somebody with somebody
Expect 20g mixture, the mixture material prepared poured into together in ball grinder after tentatively mixing, then toward adding in ball grinder
Add appropriate steel ball and absolute alcohol ball-milling medium, then cover ball grinder lid and tighten screw, put it into row after tightening again
Ball milling is carried out in planetary ball mill 12 hours, ball milling removes ball grinder standing a period of time after terminating after, ball grinder is opened, by ball
Alloy powder slurry is taken out and carries out being spray-dried to obtain precursor powder in grinding jar, then powder is carried out under the protective condition of nitrogen
It is heated at high temperature to 550 DEG C, constant temperature 6 hours, then raises temperature to 850 DEG C, constant temperature 12 hours, products therefrom is protected in nitrogen atmosphere
Room temperature is naturally cooled under shield, 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, Ce powder is mixed as doping Ce's
Miscellaneous raw material, doped raw material of the metal Cr powder as doping Cr atoms, according to Li0.9Ce0.1Fe0.6Cr0.4PO4Atom ratio dispensing
50g mixture, the mixture material prepared pour into ball grinder together after tentatively mixing, then toward adding in ball grinder
Appropriate steel ball and acetone ball-milling medium, then cover ball grinder lid and tighten screw, put it into planetary ball after tightening again
Ball milling is carried out in grinding machine 15 hours, ball milling removes ball grinder standing a period of time after terminating after, ball grinder is opened, by ball grinder
Alloy powder slurry, which takes out, to be carried out being spray-dried to obtain precursor powder, then precursor powder is loaded to the quartz glass of an end closure
Guan Zhong, inside full of appropriate nitrogen, then with the thermal-flame vitreous silica tube opening other end make its sealing, by the quartzy glass of sealing
Glass pipe input water in verify air-tightness, if bubble-free, can assert that its sealing is good, by powder nitrogen protective condition
Under be heated at high temperature to 600 DEG C, constant temperature 8 hours, then raise temperature to 900 DEG C, constant temperature 15 hours, products therefrom is in nitrogen
Room temperature is naturally cooled under atmosphere protection, powder is collected and produces product.
Claims (5)
1. a kind of doping Cr combination electrode material, it is characterised in that the preparation method of the combination electrode material is entered as follows
OK：
LiOH is as lithium source, with Fe (PO4)3As source of iron, (NH4)2HPO4As source of phosphoric acid, Rare-Earth Ce powder is as doping Ce atoms
Raw material, doped raw material of the metal Cr powder as doping Cr atoms, each composition is according to Li1-xCe xFe1-yCryPO4（0.02≤x≤
0.1, 0.2≤y≤0.4）Atomic ratio dispensing；
(2) take a certain amount of raw material prepared to carry out mechanical ball mill with ball grinder；
(3) 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；
(5) 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-xCe xFe1-yCryPO4Combination electrode material powder.
A kind of 2. doping Cr combination electrode material as claimed in claim 1, it is characterised in that step (2) in, the ball
It is 10-15 hours that honed journey, which needs to add ball-milling medium absolute alcohol or acetone, mechanical ball mill time,.
3. a kind of doping Cr combination electrode material as claimed in claim 1, it is characterised in that prepared by material the step of (3)
In, described dried to mixed slurry is using spray drying.
4. a kind of doping Cr combination electrode material as claimed in claim 1, it is characterised in that in step of preparation process (4)
In, the Technology for Heating Processing that carried out to precursor powder is under the conditions of the mixed gas of nitrogen, argon gas or both, is first existed
Heat treatment 5-8h is carried out under conditions of 500-600 DEG C, temperature is then increased to 800-900 DEG C, is heat-treated 10-15h.
5. the combination electrode material of a kind of doping Cr as described in claim any one of 1-4, it is characterised in that in preparation technology
Step (5) in, be under the conditions of the mixed gas of nitrogen, argon gas or both under the inert atmosphere protection.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710582758.4A CN107834029A (en) | 2017-07-17 | 2017-07-17 | A kind of doping Cr combination electrode material and its preparation technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710582758.4A CN107834029A (en) | 2017-07-17 | 2017-07-17 | A kind of doping Cr combination electrode material and its preparation technology |
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| CN107834029A true CN107834029A (en) | 2018-03-23 |
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| CN201710582758.4A Withdrawn CN107834029A (en) | 2017-07-17 | 2017-07-17 | A kind of doping Cr combination electrode material and its preparation technology |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112909157A (en) * | 2021-03-06 | 2021-06-04 | 西北工业大学 | Preparation method of AMTEC high-temperature-resistant TiN/Mo electrode |
Citations (3)
| 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 |
-
2017
- 2017-07-17 CN CN201710582758.4A patent/CN107834029A/en not_active Withdrawn
Patent Citations (3)
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112909157A (en) * | 2021-03-06 | 2021-06-04 | 西北工业大学 | Preparation method of AMTEC high-temperature-resistant TiN/Mo electrode |
| CN112909157B (en) * | 2021-03-06 | 2022-03-15 | 西北工业大学 | Preparation method of AMTEC high-temperature-resistant TiN/Mo electrode |
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