CN108258232A - A kind of novel manganic acid lithium electrode material - Google Patents
A kind of novel manganic acid lithium electrode material Download PDFInfo
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- CN108258232A CN108258232A CN201611241349.XA CN201611241349A CN108258232A CN 108258232 A CN108258232 A CN 108258232A CN 201611241349 A CN201611241349 A CN 201611241349A CN 108258232 A CN108258232 A CN 108258232A
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- Prior art keywords
- electrode material
- novel
- acid lithium
- lithium electrode
- manganic acid
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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
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- 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 present invention relates to a kind of novel manganic acid lithium electrode materials.The electrode material is a kind of rare earth doped LiLaxCeyMn2‑(x+y)O4Electrode material.The preparation method of the electrode material is：Using lithium carbonate, electrolytic manganese dioxide, lanthanum acetate, acetic acid Cerium as raw material, according to LiLaxCeyMn2‑(x+y)O4（0.01≤x+y≤0.2）Atomic ratio dispensing, be then mixed object and worn into alloy powder through ball-milling technology, after drying again by calcine technology carry out high-temperature calcination, the electrode material can be obtained after calcining.
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 being widely used for portable digital product, the use of special mobile phone, laptop, portable, capacitance
The lithium ion battery of high, recyclable charging is just used widely with excellent performance in this kind of product.Initial lithium electricity
Pond be it is a kind of by lithium metal or lithium alloy be negative material, the battery using non-aqueous electrolytic solution.Due to the chemistry of lithium metal
Characteristic is very active so that processing, preservation, the use of lithium metal, it is very high to environmental requirement, and so lithium battery production will be in spy
It is carried out under different environmental condition, use condition is very harsh.Later, Sony Corporation of Japan had been invented using Carbon Materials as cathode, with
Compound containing lithium makees the lithium battery of anode, in charge and discharge process, exists without lithium metal, only lithium ion, here it is lithiums
Ion battery.
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 La and Ce 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 for adulterating La and Ce2O4Electrode composite material and its preparation process,
The preparation process includes the following steps：
(1) first using lanthanum acetate, acetic acid Cerium, lithium carbonate, electrolytic manganese dioxide as raw material, according to LiLaxCeyMn2-(x+y)O4
（0.01≤x+y≤0.2）Atomic ratio prepare suitable raw material, be mixed；
(2) the raw mixture of mixing is poured into a ball grinder, and add suitable steel ball, and liquid feeding body carries out protection and carries out ball
Mill；
(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 LiLaxCeyMn2-(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-
40h。
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 lanthanum acetate that takes appropriate chemistry pure, acetic acid Cerium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiLa0.1Ce0.2Mn1.7O4Atomic ratio dispensing 5g, the mixture material prepared is poured into ball grinder together, and is put into
The steel ball of 100g, then acetone soln is poured into, after submerging ball grinder, cover is covered tightly, planetary ball mill is put into and carries out ball milling, ball
After grinding 40h, alloy powder is taken out, is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube,
In the case of continuous pumping, vacuum sealing is carried out, air-tightness will be verified in the quartz glass tube input water of sealing, if without gas
Bubble, then can assert that its leakproofness is good, then quartz glass tube is taken out, and dry to be put into 700 DEG C of high temperature furnace after moisture and carry out
After calcining 20h, treated quartz glass tube is taken out for calcining, and quartz glass tube is smashed after cooling, collects powder up to producing
Product.
Embodiment two：
The lanthanum acetate that takes appropriate chemistry pure, acetic acid Cerium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiLa0.2Ce0.2Mn1.6O4Atomic ratio dispensing 10g, the mixture material prepared is poured into ball grinder together, and is put into
The steel ball of 150g, then acetone soln is poured into, after submerging ball grinder, cover is covered tightly, planetary ball mill is put into and carries out ball milling, ball
After grinding 30h, alloy powder is taken out, is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube,
In the case of continuous pumping, vacuum sealing is carried out, air-tightness will be verified in the quartz glass tube input water of sealing, if without gas
Bubble, then can assert that its leakproofness is good, then quartz glass tube is taken out, and dry to be put into 800 DEG C of high temperature furnace after moisture and carry out
After calcining 15h, treated quartz glass tube is taken out for calcining, and quartz glass tube is smashed after cooling, collects powder up to producing
Product.
Embodiment three：
The lanthanum acetate that takes appropriate chemistry pure, acetic acid Cerium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiLa0.4Ce0.2Mn1.4O4Atomic ratio dispensing 20g, the mixture material prepared is poured into ball grinder together, and is put into
The steel ball of 200g, then acetone soln is poured into, after submerging ball grinder, cover is covered tightly, planetary ball mill is put into and carries out ball milling, ball
After grinding 30h, alloy powder is taken out, is put into a smooth container and dries, then the powder dried is fitted into quartz glass tube,
In the case of continuous pumping, vacuum sealing is carried out, air-tightness will be verified in the quartz glass tube input water of sealing, if without gas
Bubble, then can assert that its leakproofness is good, then quartz glass tube is taken out, and dry to be put into 900 DEG C of high temperature furnace after moisture and carry out
After calcining 10h, treated quartz glass tube is taken out for calcining, and quartz glass tube is smashed after cooling, collects powder up to producing
Product.
Claims (6)
1. a kind of novel manganic acid lithium electrode material, it is characterised in that the preparation method of the electrode material carries out as follows：
(1) first using lanthanum acetate, acetic acid Cerium, lithium carbonate, electrolytic manganese dioxide as raw material, according to LiLaxCeyMn2-(x+y)O4
（0.01≤x+y≤0.2）Atomic ratio prepare suitable raw material, be mixed；
(2) the raw mixture of mixing is poured into a ball grinder, and add suitable steel ball, and liquid feeding body carries out protection and carries out ball
Mill；
(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 novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that step (1) in, according to
LiLaxCeyMn2-(x+y)O4（0.03≤x+y≤0.6）Atomic ratio dispensing.
3. a kind of novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that step (2) in, ratio of grinding media to material is
10-20, the time that ball mill carries out ball milling are 30-40h.
4. a kind of novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that step (2) in, liquid protection
For acetone, gasoline or alcohol.
5. a kind of novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that step (3) in, dry for from
So dry.
6. a kind of novel manganic acid lithium electrode material as shown in claim 1, which is characterized in that 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 |
|---|---|---|---|
| CN201611241349.XA CN108258232A (en) | 2016-12-29 | 2016-12-29 | A kind of novel manganic acid lithium electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611241349.XA CN108258232A (en) | 2016-12-29 | 2016-12-29 | A kind of novel manganic acid lithium electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108258232A true CN108258232A (en) | 2018-07-06 |
Family
ID=62720481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611241349.XA Withdrawn CN108258232A (en) | 2016-12-29 | 2016-12-29 | A kind of novel manganic acid lithium electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108258232A (en) |
-
2016
- 2016-12-29 CN CN201611241349.XA patent/CN108258232A/en not_active Withdrawn
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Application publication date: 20180706 |
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