CN108206273A - A kind of LiMn for adulterating Tb2O4Electrode material - Google Patents
A kind of LiMn for adulterating Tb2O4Electrode material Download PDFInfo
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- CN108206273A CN108206273A CN201611172284.8A CN201611172284A CN108206273A CN 108206273 A CN108206273 A CN 108206273A CN 201611172284 A CN201611172284 A CN 201611172284A CN 108206273 A CN108206273 A CN 108206273A
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- Prior art keywords
- limn
- adulterating
- ball
- electrode material
- ball milling
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Classifications
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of LiMn for adulterating Tb2O4Electrode material and preparation method thereof.First by raw material gadolinium acetate, lithium carbonate, manganese dioxide according to LiGdxMn2‑xO4Atomic ratio dispensing, the raw mixture prepared is poured into ball grinder together and carries out ball milling, is dried alloy powder, then high-temperature calcination after ball milling, up to product after calcining.Its preparation process is simple, easy to operate.
Description
Technical field
The present invention relates to a kind of LiMn2O4Li-ion electrode materials, more particularly to a kind of li-ion electrode material for adding rare earth
Material and preparation method thereof, belongs to battery electrode material field.
Background technology
With being widely used for portable digital product, special mobile phone, laptop etc., lithium ion battery is just with excellent
Performance be used widely in this kind of product.Initial lithium battery be it is a kind of by lithium metal or lithium alloy be negative material,
Use the battery of non-aqueous electrolytic solution.Since the chemical characteristic of lithium metal is very active so that the processing of lithium metal, preservation,
It uses, it is very high to environmental requirement, so lithium battery production will carry out under special environmental condition.Later, Sony was public
The lithium battery for making anode with the compound containing lithium using Carbon Materials as cathode has been invented by department, in charge and discharge process, without lithium metal
In the presence of only lithium ion, here it is lithium ion batteries.
Anode material for lithium-ion batteries common at present mainly has the phosphoric acid of the cobalt acid lithium and olivine structural of layer structure
Iron lithium etc..Wherein LiCoO2The overcharge resistant ability of material is poor, declines rapidly in higher charging voltage specific capacity;LiFePO4
There are discharge voltage is low, tap density is low etc., shortcomings all constrain the further application of itself, LiMn2O4Material has as electrode
There is good performance.There is document to point out, to LiMn2O4The rare earth doped element of ingredient, can effectively improve cycle performance, slows down electricity
The increase of pole impedance.It is micro- that the present invention using lithium carbonate, electrolytic manganese dioxide, acetic acid terbium as raw material is worn into alloy through ball-milling technology
Powder, then pass through calcine technology Solid phase synthesis LiTbxMn2-xO4 Material, the LiTb after dopingxMn2-xO4 The synthesis of electrode material
Performance will further improve.
Invention content
The object of the present invention is to provide a kind of LiMn for adulterating Tb2O4Electrode material and preparation method thereof.The preparation process packet
Include following steps:
(1) appropriate chemical pure acetic acid terbium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiTbxMn2-xO4(0.01≤
X≤0.1)Atomic ratio dispensing;
(2) a ball grinder is taken, the raw mixture prepared is poured into its tank, and add suitable steel ball, ball is carried out with ball mill
Mill;
(3) the alloy powder of ball milling is dried;
(4) the high-temperature calcination under the conditions of starvation by the alloy powder after drying;
(5) after calcining, powder is collected up to product.
Preferentially, step (1) in, according to LiTbxMn2-xO4(0.03≤X≤0.05)Atomic ratio dispensing.
Preferentially, step (2) in, ratio of grinding media to material 15-20.
Preferentially, step (2) in, ball mill carry out ball milling time be 20-40h.
Step (2) in, acetone can also be changed into gasoline or alcohol.
Preferentially, step (4) in, high-temperature calcination temperature be 800-900 DEG C, time control is in 10-20h.
The present invention has following advantages and characteristic:
(1) the electrode material conductivity prepared is high;
(2) preparation process is simple, and flow is short.
Specific embodiment
Embodiment one:
Appropriate chemical pure acetic acid terbium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiTb0.01Mn1.99O4Atom
Ratio dispensing 5g, the mixture material prepared is poured into ball grinder together, and puts into the steel ball of 100g, then to pour into acetone molten
After submerging ball grinder, cover is covered tightly for liquid, is put into planetary ball mill and is carried out ball milling, after ball milling 40h, alloy powder is taken out,
It is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube, in the case of continuous pumping, carry out
Vacuum sealing will verify air-tightness in the quartz glass tube input water of sealing, if bubble-free, can assert that its leakproofness is good,
Quartz glass tube is taken out again, dries to be put into 800 DEG C of high temperature furnace after moisture and be calcined, after calcining 20h, processing will be passed through
Quartz glass tube take out, smash quartz glass tube after cooling, collect powder up to product.
Embodiment two:
Appropriate chemical pure acetic acid terbium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiTb0.1Mn1.9O4Atomic ratio
Example dispensing 10g, the mixture material prepared is poured into ball grinder together, and put into the steel ball of 150g, then pour into acetone soln,
After submerging ball grinder, cover is covered tightly, planetary ball mill is put into and carries out ball milling, after ball milling 30h, alloy powder is taken out, is put
Enter and dried in a smooth container, then the powder dried is fitted into quartz glass tube, in the case of continuous pumping, carry out true
Sky sealing will verify air-tightness in the quartz glass tube input water of sealing, if bubble-free, can assert that its leakproofness is good, then
Quartz glass tube is taken out, dries to be put into 800 DEG C of high temperature furnace after moisture and be calcined, it, will be treated after calcining 15h
Quartz glass tube takes out, and quartz glass tube is smashed after cooling, collects powder up to product.
Embodiment three:
Appropriate chemical pure acetic acid terbium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiTb0.05Mn1.95O4Atom
Ratio dispensing 20g, the mixture material prepared is poured into ball grinder together, and puts into the steel ball of 300g, then to pour into acetone molten
After submerging ball grinder, cover is covered tightly for liquid, is put into planetary ball mill and is carried out ball milling, after ball milling 20h, alloy powder is taken out,
It is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube, in the case of continuous pumping, carry out
Vacuum sealing will verify air-tightness in the quartz glass tube input water of sealing, if bubble-free, can assert that its leakproofness is good,
Quartz glass tube is taken out again, dries to be put into 900 DEG C of high temperature furnace after moisture and be calcined, after calcining 10h, processing will be passed through
Quartz glass tube take out, smash quartz glass tube after cooling, collect powder up to product.
Claims (6)
1. a kind of LiMn for adulterating Tb2O4Electrode material, it is characterised in that the preparation method of the material carries out as follows:
(1) appropriate chemical pure acetic acid terbium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiTbxMn2-xO4(0.01≤X
≤0.1)Atomic ratio dispensing;
(2) a ball grinder is taken, the raw mixture prepared is poured into its tank, and add suitable steel ball, ball is carried out with ball mill
Mill;
(3) the alloy powder of ball milling is dried;
(4) the high-temperature calcination under the conditions of starvation by the alloy powder after drying;
(5) after calcining, powder is collected up to product.
2. a kind of LiMn for adulterating Tb as shown in claim 12O4Electrode material, which is characterized in that step (1) in, according to
LiTbxMn2-xO4(0.03≤X≤0.05)Atomic ratio dispensing.
3. a kind of LiMn for adulterating Tb as shown in claim 12O4Electrode material, which is characterized in that step (2) in, ball material
Than for 15-20.
4. a kind of LiMn for adulterating Tb as shown in claim 12O4Electrode material, which is characterized in that step (2) in, ball milling
The time that machine carries out ball milling is 20-40h.
5. a kind of LiMn for adulterating Tb as shown in claim 12O4Electrode material, which is characterized in that step (2) in, also may be used
To change acetone into gasoline or alcohol.
6. a kind of LiMn for adulterating Tb as shown in claim 12O4Electrode material, which is characterized in that step (4) in, high temperature
Calcination temperature is 800-900 DEG C, and time control is in 10-20h.
Priority Applications (1)
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CN201611172284.8A CN108206273A (en) | 2016-12-17 | 2016-12-17 | A kind of LiMn for adulterating Tb2O4Electrode material |
Applications Claiming Priority (1)
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CN201611172284.8A CN108206273A (en) | 2016-12-17 | 2016-12-17 | A kind of LiMn for adulterating Tb2O4Electrode material |
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CN108206273A true CN108206273A (en) | 2018-06-26 |
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CN201611172284.8A Pending CN108206273A (en) | 2016-12-17 | 2016-12-17 | A kind of LiMn for adulterating Tb2O4Electrode material |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1447466A (en) * | 2003-04-04 | 2003-10-08 | 清华大学 | Method for preparing anode material of spherical lithium manganate applicable to lithium ion batteries |
CN101780983A (en) * | 2009-01-16 | 2010-07-21 | 比亚迪股份有限公司 | Spinel Li1+xMyMn2-x-yO4, preparation method thereof and lithium-ion secondary battery |
CN102195042A (en) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | High performance lithium ion battery anode material lithium manganate and preparation method thereof |
CN105591103A (en) * | 2015-12-21 | 2016-05-18 | 李梦思 | Modification process of lithium ion battery cathode material |
-
2016
- 2016-12-17 CN CN201611172284.8A patent/CN108206273A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1447466A (en) * | 2003-04-04 | 2003-10-08 | 清华大学 | Method for preparing anode material of spherical lithium manganate applicable to lithium ion batteries |
CN101780983A (en) * | 2009-01-16 | 2010-07-21 | 比亚迪股份有限公司 | Spinel Li1+xMyMn2-x-yO4, preparation method thereof and lithium-ion secondary battery |
CN102195042A (en) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | High performance lithium ion battery anode material lithium manganate and preparation method thereof |
CN105591103A (en) * | 2015-12-21 | 2016-05-18 | 李梦思 | Modification process of lithium ion battery cathode material |
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