CN108258234A - A kind of manganic acid lithium electrode material for adding rare earth Ho, Er - Google Patents
A kind of manganic acid lithium electrode material for adding rare earth Ho, Er Download PDFInfo
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- CN108258234A CN108258234A CN201611242198.XA CN201611242198A CN108258234A CN 108258234 A CN108258234 A CN 108258234A CN 201611242198 A CN201611242198 A CN 201611242198A CN 108258234 A CN108258234 A CN 108258234A
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- electrode material
- rare earth
- acid lithium
- adding rare
- 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
- 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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- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of manganic acid lithium electrode materials for adding rare earth Ho, Er.The preparation method of the electrode material is：With raw materials such as acetic acid holmium, acetic acid erbium, lithium carbonate, manganese dioxide, by LiHoxEryMn2‑(x+y)O4（0.01≤x+y≤0.2）Atomic ratio prepare appropriate amount of sample, then by sample mixture wet ball grinding, micro mist is dried after ball milling, the micro mist vacuum high-temperature dried calcining finally can be obtained into the electrode material.The electrode material powdered conductive rate of preparation is high, good cycle and preparation process are simple.
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 addition rare earth Ho, Er's
Manganic acid lithium electrode material and its preparation process belong to lithium battery material field.
Background technology
With the extensive use of the portable equipments such as mobile phone, battery is applied in daily life, especially lithium ion
Battery is because with operating voltage is high, higher than energy, capacity is big, self discharge is small, good cycle, service life are long, light-weight, body
Outstanding advantages of product is small is favored by people.The most important component part of lithium ion battery is anode and cathode.Positive electrode
Quality, will directly determine the performance of final lithium ion battery, and positive electrode proportion in battery cost may be up to 40% left side
The right side, research anode material for lithium-ion batteries are necessary.
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, acetic acid holmium, acetic acid erbium
A kind of novel LiMn of rare earth doped Ho and Er of firing technique Solid phase synthesis2O4Electrode composite material, after rare earth doped
LiHoxEryMn2-(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 Ho and Er2O4Electrode composite material and its preparation
Technique, the preparation process include the following steps：
(1) suitable acetic acid holmium, acetic acid erbium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiHoxEryMn2-(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 a kind of manganic acid lithium electrode material for adding rare earth Ho, Er.
Preferentially, step (1) in, according to LiHoxEryMn2-(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) the electrode material good cycle prepared；
(3) preparation process is simple, and flow is short.
Embodiment one：
The acetic acid holmium that takes appropriate chemistry pure, acetic acid erbium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiHo0.1Er0.2Mn1.7O4Atomic 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 a kind of
Add the manganic acid lithium electrode material of rare earth Ho, Er.
Embodiment two：
The acetic acid holmium that takes appropriate chemistry pure, acetic acid erbium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiHo0.2Er0.2Mn1.6O4Atomic 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 a kind of
Add the manganic acid lithium electrode material of rare earth Ho, Er.
Embodiment three：
The acetic acid holmium that takes appropriate chemistry pure, acetic acid erbium, lithium carbonate, electrolytic manganese dioxide as raw material, according to
LiHo0.4Er0.2Mn1.4O4Atomic 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 a kind of
Add the manganic acid lithium electrode material of rare earth Ho, Er.
Claims (6)
1. a kind of manganic acid lithium electrode material for adding rare earth Ho, Er, it is characterised in that the preparation method of the electrode material is by as follows
Step carries out：
(1) suitable acetic acid holmium, acetic acid erbium, lithium carbonate, electrolytic manganese dioxide are taken as raw material, according to LiHoxEryMn2-(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 a kind of manganic acid lithium electrode material for adding rare earth Ho, Er.
2. a kind of manganic acid lithium electrode material for adding rare earth Ho, Er 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 manganic acid lithium electrode material for adding rare earth Ho, Er 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 manganic acid lithium electrode material for adding rare earth Ho, Er 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 manganic acid lithium electrode material for adding rare earth Ho, Er as shown in claim 1, which is characterized in that in step (3)
In, it dries for naturally dry.
6. a kind of manganic acid lithium electrode material for adding rare earth Ho, Er 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 |
|---|---|---|---|
| CN201611242198.XA CN108258234A (en) | 2016-12-29 | 2016-12-29 | A kind of manganic acid lithium electrode material for adding rare earth Ho, Er |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611242198.XA CN108258234A (en) | 2016-12-29 | 2016-12-29 | A kind of manganic acid lithium electrode material for adding rare earth Ho, Er |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108258234A true CN108258234A (en) | 2018-07-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611242198.XA Withdrawn CN108258234A (en) | 2016-12-29 | 2016-12-29 | A kind of manganic acid lithium electrode material for adding rare earth Ho, Er |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108258234A (en) |
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2016
- 2016-12-29 CN CN201611242198.XA patent/CN108258234A/en not_active Withdrawn
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| PB01 | Publication | ||
| PB01 | Publication | ||
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| WW01 | Invention patent application withdrawn after publication | ||
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Application publication date: 20180706 |