CN108206273A - A kind of LiMn for adulterating Tb2O4Electrode material - Google Patents

A kind of LiMn for adulterating Tb2O4Electrode material Download PDF

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Publication number
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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CN
China
Prior art keywords
limn
adulterating
ball
electrode material
ball milling
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CN201611172284.8A
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Chinese (zh)
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赖愉文
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Individual
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Individual
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Priority to CN201611172284.8A priority Critical patent/CN108206273A/en
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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
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00Compounds of manganese
    • C01G45/12Manganates manganites or permanganates
    • 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
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/30Batteries in portable systems, e.g. mobile phone, laptop
    • 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)
  • 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

A kind of LiMn for adulterating Tb2O4Electrode material
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.
CN201611172284.8A 2016-12-17 2016-12-17 A kind of LiMn for adulterating Tb2O4Electrode material Pending CN108206273A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611172284.8A CN108206273A (en) 2016-12-17 2016-12-17 A kind of LiMn for adulterating Tb2O4Electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611172284.8A CN108206273A (en) 2016-12-17 2016-12-17 A kind of LiMn for adulterating Tb2O4Electrode material

Publications (1)

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CN108206273A true CN108206273A (en) 2018-06-26

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Citations (4)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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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