CN103606670A - Lithium manganate positive electrode material of power lithium ion battery and preparation method thereof - Google Patents
Lithium manganate positive electrode material of power lithium ion battery and preparation method thereof Download PDFInfo
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- CN103606670A CN103606670A CN201310636291.9A CN201310636291A CN103606670A CN 103606670 A CN103606670 A CN 103606670A CN 201310636291 A CN201310636291 A CN 201310636291A CN 103606670 A CN103606670 A CN 103606670A
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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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- 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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Abstract
The invention relates to a preparation and improvement method for a lithium manganate positive electrode material of a power lithium ion battery. The method comprises the following process steps (1) uniformly mixing a manganese salt, a lithium salt and a small amount of a solvent for calcining; (2) heating an obtained mixture in the air so as to obtain a precursor; (3) subjecting the precursor to natural cooling, adding a doping element and carrying out uniform grinding; (4) uniformly mixing and grinding an obtained precursor and a proper amount of a clad material; (5) calcining obtained powder so as to obtain a powder material, naturally cooling the powder material to room temperature and grinding the cooled powder material in a ball mill so as to obtain the lithium manganate positive electrode material of the power lithium ion battery. The positive electrode material prepared in the invention has uniform particles and good crystallization performance; the spinel type positive electrode material has good electrochemical properties like high specific capacity and good cycle performance and is suitable for large scale production and applicable to positive electrode materials of power lithium ion batteries.
Description
Technical field
The present invention relates to a kind of power lithium-ion battery manganate cathode material for lithium and preparation method thereof, belong to technical field of lithium ion.
Background technology
Lithium ion battery has the features such as high-energy, environmental friendliness due to it and occupies rapidly consumption market, is widely used in the fields such as portable type electronic product, electric automobile.Make a general survey of main several positive electrodes at present, LiMn2O4 LiMn
2o
4positive electrode shows unique advantage, i.e. high-energy, and high discharge voltage plateau, high security and environmental protection and inexpensive etc., be considered to most possible substituting cobalt acid lithium and one of business-like positive electrode.But, this material also exists in weak point, the high-energy that can't meet the need of market completely, the high power density such as high temperature cyclic performance is not good.
For the above LiMn2O4 LiMn
2o
4the shortcoming that positive electrode exists, need to provide a kind of low price, and cycle performance is good, the synthetic method of low and high temperature better performances and the coated and doped chemical of having found.
The method of synthesis of anode material of lithium-ion battery mainly contains solid phase method, coprecipitation and sol-gel process etc. at present.The defects such as solid phase method is simple to operate, and batch mixing is uneven but easily cause, and particle is larger.Coprecipitation is current the most general method, but building-up process is complicated, and process adjustments control ratio is stricter, needs through precipitation, and a plurality of steps such as washing, easily cause nickel in product, cobalt, manganese out of proportion.And the synthetic product of sol-gel process, uniform particles, advantages of good crystallization, purity is high; But the size of final particle is not easy to control, and production cost is high.The present invention is the improvement to existing solid state process.
?
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of lithium ion power electricity manganate cathode material for lithium and preparation thereof are provided and improve one's methods, this positive electrode uniform particles, crystal property is good, have specific capacity high, good cycle etc. are chemical property preferably.
According to technical scheme provided by the invention, described lithium ion battery manganate cathode material for lithium, feature is: the chemical general formula of described positive electrode is LiMn
2o
4;
The present invention also protects a kind of preparation method of ternary cathode material of lithium ion battery, and feature is to adopt following processing step:
(1) by manganese salt, lithium salts and a small amount of solvent, after mixing, prepare calcining; Described manganese salt, lithium salts, mol ratio be 2:1;
(2) mixture step (1) being obtained heats in the air atmosphere of 50～400 ℃, and be 3～18 hours heating time,, obtain precursor;
(3) by precursor in naturally cooling, add doped chemical, then grind evenly;
(4) the front body obtaining and appropriate clad material mixed grinding are even;
(5) above-mentioned powder is calcined, calcining heat is 500～900 ℃, and calcination time is 3～30 hours, obtains dusty material; Naturally cool to after room temperature in grinding in ball grinder 0.5～2 hour, obtain described power lithium-ion battery manganate cathode material for lithium.
Described manganese salt is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese dioxide, manganese carbonate, manganese chloride, and described lithium salts is one or more in lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide; Described clad material is aluminium oxide, iron oxide, titanium oxide, one or more in nickel oxide; Described doped chemical is magnesium, iron, calcium, cobalt, copper, one or more in caesium.
Described assistant research fellow's agent be water and/ethanol.
Advantage of the present invention:
(1) the prepared positive electrode uniform particles of the present invention, degree of crystallinity is high;
(2) to have specific capacity high for the positive electrode of spinel structure provided by the present invention, and good cycle etc. are chemical property preferably; Be applicable to large-scale production, can use for anode material for lithium-ion batteries.
Accompanying drawing explanation
Fig. 1 is the prepared positive electrode Li of the embodiment of the present invention one
1.03ce
xmn
1.97-xo
4the XRD collection of illustrative plates of (x=0.01,0.02,0.03).
Fig. 2 is the prepared positive electrode Li of the embodiment of the present invention one
1.03ce
xmn
1.97-xo
4the first charge-discharge capacity curve figure of (x=0.01,0.02,0.03).
Fig. 3 is the prepared positive electrode Li of the embodiment of the present invention one
1.03ce
xmn
1.97-xo
4the charge and discharge cycles figure of (x=0.01,0.02,0.03).
Below in conjunction with concrete drawings and Examples, the invention will be further described.
Embodiment mono-: a kind of power lithium-ion battery manganate cathode material for lithium and preparation method thereof, adopts following processing step:
(1) manganese dioxide and lithium carbonate be take to mol ratio as 2:1, after mixing, add 1% ethanol, grind;
(2) mixture step (1) being obtained is 100-400 ℃ of heating, and be 12 hours heating time, then naturally cooling, obtains dry precursor, grinds evenly;
(3) dry precursor is mixed with MgO and Ce2O3, calcining, calcining heat is 700 ℃, calcination time is 20 hours, after naturally cooling to room temperature after calcining, again on ball mill, grind 0.5 hour, obtain described power lithium-ion battery manganate cathode material for lithium Li
1.03ce
xmn
1.97-xo
4(x=0.01,0.02,0.03);
Embodiment bis-: a kind of power lithium-ion battery manganate cathode material for lithium and preparation method thereof, adopts following processing step:
(1) manganese acetate, with lithium acetate in molar ratio for 2:1 mixes, adds 1% ethanol after mixing, and grinds;
(2) mixture step (1) being obtained is 100-400 ℃ of heating, and be 12 hours heating time, then naturally cooling, obtains dry precursor, grinds evenly;
(3) dry precursor is mixed with MgO and Al2O3, calcining, calcining heat is 700 ℃, calcination time is 20 hours, after naturally cooling to room temperature after calcining, again on ball mill, grind 0.5 hour, obtain described power lithium-ion battery manganate cathode material for lithium Li
1.03al
xmn
1.97-xo
4(x=0.01,0.02,0.03);
Embodiment tri-: a kind of power lithium-ion battery manganate cathode material for lithium and preparation method thereof, adopts following processing step:
(1) by carbonic acid acid manganese and lithium acetate in molar ratio for 2:1 mixes, after mixing, add 1% ethanol, grinding;
(2) mixture step (1) being obtained is 100-400 ℃ of heating, and be 12 hours heating time, then naturally cooling, obtains dry precursor, grinds evenly;
(3) dry precursor is mixed with CaO; calcining, calcining heat is 750 ℃, calcination time is 20 hours; after naturally cooling to room temperature after calcining, again on ball mill, grind 0.5 hour, obtain described power lithium-ion battery manganate cathode material for lithium LiMn2O4;
The positive electrode that embodiment mono-is obtained carries out XRD detection, and as shown in Figure 1, the abscissa of Fig. 1 is sweep limits 2 θ (10～90 °) to result, and the intensity that ordinate is peak, can be as seen from Figure 1, and positive electrode is the spinel structure of high-sequential; Material is assembled into button cell, and it is carried out to charge-discharge test, charging/discharging voltage scope is 3.0 ~ 4.5V, as shown in Figure 2, first discharge specific capacity is 123.3mAh/g to the maximum, and Fig. 3 is that the abscissa that discharges and recharges fantasy curve is cycle-index, ordinate is specific capacity, and unit is mAh/g.
Claims (4)
1. power lithium-ion battery manganate cathode material for lithium and preparation method thereof, is characterized in that: the chemical general formula of described positive electrode is LiMn
2o
4.
2. power lithium-ion battery manganate cathode material for lithium and preparation method thereof,, it is characterized in that, adopt following processing step:
(1) by manganese salt, lithium salts and a small amount of solvent, after mixing, prepare calcining; Described manganese salt, lithium salts, mol ratio be 2:1;
(2) mixture step (1) being obtained heats in the air atmosphere of 50～400 ℃, and be 3～18 hours heating time, obtains precursor;
(3) by precursor in naturally cooling, add doped chemical, then grind evenly;
(4) the front body obtaining and appropriate clad material mixed grinding are even;
(5) above-mentioned powder is calcined, calcining heat is 500～900 ℃, and calcination time is 3～30 hours, obtains dusty material; Naturally cool to after room temperature in grinding in ball grinder 0.5～2 hour, obtain described power lithium-ion battery manganate cathode material for lithium.
3. the preparation method of power lithium-ion battery manganate cathode material for lithium as claimed in claim 2, it is characterized in that: described manganese salt is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese dioxide, manganese carbonate, manganese chloride, and described lithium salts is one or more in lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide; Described clad material is aluminium oxide, iron oxide, titanium oxide, one or more in nickel oxide; Described doped chemical is magnesium, iron, calcium, cobalt, copper, one or more in caesium.
4. a kind of power lithium-ion battery manganate cathode material for lithium as claimed in claim 2 and preparation method thereof, is characterized in that: described assistant research fellow's agent be water and/ethanol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104143626A (en) * | 2014-07-25 | 2014-11-12 | 江南大学 | Cation-anion co-doping lithium manganite positive electrode material and preparation method thereof |
| CN105895866A (en) * | 2014-12-25 | 2016-08-24 | 江南大学 | Light metal doping lithium manganate positive electrode material of lithium ion battery and preparation method of positive electrode material |
| CN108091855A (en) * | 2017-12-13 | 2018-05-29 | 江南大学 | A kind of preparation of light metal codope lithium ion battery mangaic acid lithium anode material and improved method |
| CN108336327A (en) * | 2017-12-30 | 2018-07-27 | 宁夏科捷锂电池股份有限公司 | A method of doping AL ion coated lithium tetraborates prepare LiMn2O4 |
| CN113307307A (en) * | 2021-05-17 | 2021-08-27 | 北京工业大学 | Method for preparing lithium-rich iron manganese of lithium ion battery anode material by dry method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556552A (en) * | 2004-01-10 | 2004-12-22 | 昆明理工大学 | Manufacturing method of lithium ion battery positive electrode material |
| CN101807682A (en) * | 2010-04-09 | 2010-08-18 | 曲阜毅威能源股份有限公司 | Power spinel lithium manganese oxide anode material and preparation method thereof |
| KR20130053171A (en) * | 2011-11-15 | 2013-05-23 | 경북대학교 산학협력단 | A positive active for a lithium secondary battery and preparation method thereof |
-
2013
- 2013-12-03 CN CN201310636291.9A patent/CN103606670A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556552A (en) * | 2004-01-10 | 2004-12-22 | 昆明理工大学 | Manufacturing method of lithium ion battery positive electrode material |
| CN101807682A (en) * | 2010-04-09 | 2010-08-18 | 曲阜毅威能源股份有限公司 | Power spinel lithium manganese oxide anode material and preparation method thereof |
| KR20130053171A (en) * | 2011-11-15 | 2013-05-23 | 경북대학교 산학협력단 | A positive active for a lithium secondary battery and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104143626A (en) * | 2014-07-25 | 2014-11-12 | 江南大学 | Cation-anion co-doping lithium manganite positive electrode material and preparation method thereof |
| CN105895866A (en) * | 2014-12-25 | 2016-08-24 | 江南大学 | Light metal doping lithium manganate positive electrode material of lithium ion battery and preparation method of positive electrode material |
| CN108091855A (en) * | 2017-12-13 | 2018-05-29 | 江南大学 | A kind of preparation of light metal codope lithium ion battery mangaic acid lithium anode material and improved method |
| CN108336327A (en) * | 2017-12-30 | 2018-07-27 | 宁夏科捷锂电池股份有限公司 | A method of doping AL ion coated lithium tetraborates prepare LiMn2O4 |
| CN113307307A (en) * | 2021-05-17 | 2021-08-27 | 北京工业大学 | Method for preparing lithium-rich iron manganese of lithium ion battery anode material by dry method |
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Application publication date: 20140226 |