CN108258233A - A kind of rare earth doped novel manganic acid lithium electrode material and preparation method thereof - Google Patents
A kind of rare earth doped novel manganic acid lithium electrode material and preparation method thereof Download PDFInfo
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- CN108258233A CN108258233A CN201611241520.7A CN201611241520A CN108258233A CN 108258233 A CN108258233 A CN 108258233A CN 201611241520 A CN201611241520 A CN 201611241520A CN 108258233 A CN108258233 A CN 108258233A
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- electrode material
- rare earth
- earth doped
- acid lithium
- lithium electrode
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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
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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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of rare earth doped novel manganic acid lithium electrode materials and preparation method thereof.The electrode material is a kind of LiPr of rare earth doped Pr, NdxNdyMn2‑(x+y)O4Electrode material.The preparation method of the electrode material is：Suitable praseodymium acetate, acetic acid neodymium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, with LiPrxNdyMn2‑(x+y)O4（0.01≤x+y≤0.2）Atomic ratio dispensing, be mixed, it then prepared into alloy powder through ball milling, again through high-temperature calcination after drying, the electrode material can be obtained after calcining fully.
Description
Technical field
The present invention relates to a kind of li-ion electrode materials and its preparation process, more particularly to a kind of LiMn2O4 for adding rare earth
Electrode material and its preparation process belong to lithium battery material field.
Background technology
With the high-tech development such as mobile phone, battery is applied in daily life, especially lithium ion battery because
With operating voltage is high, higher than energy, capacity is big, self discharge is small, good cycle, service life are long, light-weight, small etc.
Outstanding advantages are favored by people.The most important component part of lithium ion battery is anode and cathode.To lithium ion cell positive
The research of material is current hot spot of concern.The quality of positive electrode will directly determine the property of final lithium ion battery
Energy.Positive electrode proportion in battery cost may be up to 40% or so, and research anode material for lithium-ion batteries is that have very much must
It wants.
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 is as a new generation
Li-ion electrode materials be just widely studied, there is document to point out, to LiMn2O4The rare earth doped element of ingredient, can effectively improve and follow
Ring performance slows down the increase of electrode impedance, but single component is rare earth doped, and effect is often not satisfactory, the present invention
Alloy powder is worn into, then by forging through ball-milling technology as raw material using lithium carbonate, electrolytic manganese dioxide, lanthanum acetate, acetic acid Cerium
A kind of novel LiMn of rare earth doped Pr and Nd of firing technique Solid phase synthesis2O4Electrode composite material, after rare earth doped
LiLaxCeyMn2-(x+y)O4The comprehensive performance of electrode material will further improve.
Invention content
The object of the present invention is to provide a kind of novel LiMn of rare earth doped Pr and Nd2O4Electrode composite material and its preparation
Technique, the preparation process include the following steps：
(1) suitable praseodymium acetate, acetic acid neodymium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiPrxNdyMn2-(x+y)O4
（0.01≤x+y≤0.2）Atomic ratio prepare suitable raw material, be mixed；
(2) the raw mixture prepared is poured into a ball grinder, and add suitable steel ball, and liquid feeding body carries out protection progress
Ball milling；
(3) after ball milling, ball milling micro mist is taken out, and 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 LiPrxNdyMn2-(x+y)O4（0.03≤x+y≤0.6）Atomic ratio dispensing.
Embodiment as priority, step (2) in, ratio of grinding media to material 10-20, ball mill carry out ball milling time be 30-
50h。
Embodiment as priority, step (2) in, liquid protection is acetone, gasoline or alcohol.
Embodiment as priority, step (3) in, dry for naturally dry.
Embodiment as priority, step (4) in, high-temperature calcination temperature be 700-900 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.
Embodiment one：
The praseodymium acetate that takes appropriate chemistry pure, acetic acid neodymium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiPr0.1Nd0.2Mn1.7O4Atomic ratio dispensing 5g, the mixture material prepared is poured into ball grinder together, and is put into
The steel ball of 100g, then acetone is poured into, after submerging ball grinder, cover is covered tightly, planetary ball mill is put into and carries out ball milling, ball milling
After 50h, alloy powder is taken out, is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube,
Constantly in the case of pumping, vacuum sealing is carried out, will verify air-tightness in the quartz glass tube input water of sealing, if bubble-free,
It can then assert that its leakproofness is good, then quartz glass tube is taken out, dry to be put into 700 DEG C of high temperature furnace after moisture and be forged
It burns, after calcining 20h, treated quartz glass tube is taken out, quartz glass tube is smashed after cooling, collect powder up to producing
Product.
Embodiment two：
The praseodymium acetate that takes appropriate chemistry pure, acetic acid neodymium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiPr0.2Nd0.2Mn1.6O4Atomic ratio dispensing 10g, the mixture material prepared is poured into ball grinder together, and is put into
The steel ball of 150g, then acetone is poured into, after submerging ball grinder, cover is covered tightly, planetary ball mill is put into and carries out ball milling, ball milling
After 40h, alloy powder is taken out, is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube,
Constantly in the case of pumping, vacuum sealing is carried out, will verify air-tightness in the quartz glass tube input water of sealing, if bubble-free,
It can then assert that its leakproofness is good, then quartz glass tube is taken out, dry to be put into 800 DEG C of high temperature furnace after moisture and be forged
It burns, after calcining 15h, treated quartz glass tube is taken out, quartz glass tube is smashed after cooling, collect powder up to producing
Product.
Embodiment three：
The praseodymium acetate that takes appropriate chemistry pure, acetic acid neodymium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiPr0.4Nd0.2Mn1.4O4Atomic ratio dispensing 20g, the mixture material prepared is poured into ball grinder together, and is put into
The steel ball of 200g, then gasoline is poured into, after submerging ball grinder, cover is covered tightly, planetary ball mill is put into and carries out ball milling, ball milling
After 30h, alloy powder is taken out, is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube,
Constantly in the case of pumping, vacuum sealing is carried out, will verify air-tightness in the quartz glass tube input water of sealing, if bubble-free,
It can then assert that its leakproofness is good, then quartz glass tube is taken out, dry to be put into 900 DEG C of high temperature furnace after moisture and be forged
It burns, after calcining 10h, treated quartz glass tube is taken out, quartz glass tube is smashed after cooling, collect powder up to producing
Product.
Claims (6)
1. a kind of rare earth doped novel manganic acid lithium electrode material, it is characterised in that the preparation method of the electrode material is by following step
It is rapid to carry out：
(1) suitable praseodymium acetate, acetic acid neodymium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiPrxNdyMn2-(x+y)O4
（0.01≤x+y≤0.2）Atomic ratio prepare suitable raw material, be mixed；
(2) the raw mixture prepared is poured into a ball grinder, and add suitable steel ball, and liquid feeding body carries out protection progress
Ball milling；
(3) after ball milling, ball milling micro mist is taken out, and 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 rare earth doped novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that in step (1)
In, according to LiPrxNdyMn2-(x+y)O4（0.03≤x+y≤0.6）Atomic ratio dispensing.
3. a kind of rare earth doped novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that in step (2)
In, ratio of grinding media to material 10-20, the time that ball mill carries out ball milling is 30-50h.
4. a kind of rare earth doped novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that in step (2)
In, liquid protection is acetone, gasoline or alcohol.
5. a kind of rare earth doped novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that in step (3)
In, it dries for naturally dry.
6. a kind of rare earth doped novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that in step (4)
In, high-temperature calcination temperature is 700-900 DEG C, and time control is in 10-20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611241520.7A CN108258233A (en) | 2016-12-29 | 2016-12-29 | A kind of rare earth doped novel manganic acid lithium electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611241520.7A CN108258233A (en) | 2016-12-29 | 2016-12-29 | A kind of rare earth doped novel manganic acid lithium electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108258233A true CN108258233A (en) | 2018-07-06 |
Family
ID=62719633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611241520.7A Withdrawn CN108258233A (en) | 2016-12-29 | 2016-12-29 | A kind of rare earth doped novel manganic acid lithium electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108258233A (en) |
-
2016
- 2016-12-29 CN CN201611241520.7A patent/CN108258233A/en not_active Withdrawn
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| SE01 | Entry into force of request for substantive examination | ||
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| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180706 |
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| WW01 | Invention patent application withdrawn after publication |