CN105895866A - Light metal doping lithium manganate positive electrode material of lithium ion battery and preparation method of positive electrode material - Google Patents
Light metal doping lithium manganate positive electrode material of lithium ion battery and preparation method of positive electrode material Download PDFInfo
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- CN105895866A CN105895866A CN201410840727.0A CN201410840727A CN105895866A CN 105895866 A CN105895866 A CN 105895866A CN 201410840727 A CN201410840727 A CN 201410840727A CN 105895866 A CN105895866 A CN 105895866A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to preparation and improvement methods for a light metal doping lithium manganate positive electrode material of a lithium ion battery. The preparation method comprises the following steps of (1) uniformly mixing a manganate salt, a lithium salt and a small amount of solvent, and preparing for calcination; (2) heating the obtained mixture in an air atmosphere to obtain a precursor; (3) naturally cooling the precursor, adding a doping element, and uniformly grinding the precursor and the doping element; (4) uniformly mixing and grinding the obtained precursor and an appropriate amount of coating material; and (5) roasting the above powder to obtain a powder material, naturally cooling the powder material to a room temperature and grinding the powder material in a ball-milling machine, thereby obtaining the lithium manganate positive electrode material of the power lithium ion battery. The positive electrode material prepared according to the method is uniform in particle and high in crystallization property; and the spinel-shaped positive electrode material provided by the invention has high specific capacitance and relatively high electrochemical performance such as favorable cycle performance, is suitable for mass production, and can be applied to the positive electrode material of the power lithium ion battery.
Description
Technical field
The present invention relates to a kind of lithium manganate positive electrode material of power lithium ion and preparation method thereof, belong to technical field of lithium ion.
Background technology
Lithium ion battery occupies rapidly consumption market owing to it has the feature such as high-energy, environmental friendliness, be widely used in portable type electronic product,
The fields such as electric automobile.Make a general survey of several positive electrodes currently mainly, LiMn2O4 LiMn2O4The advantage that positive electrode display is unique, i.e. high-energy,
High discharge voltage plateau, high security and environmental protection with inexpensive etc. it is considered to be most possible substituting cobalt acid lithium and one of business-like positive electrode.No
Crossing, this material there is also in the weak point such as high temperature cyclic performance is the best, can't fully meet the high-energy of the market demand, high power density.
For the above LiMn2O4 LiMn2O4The shortcoming that positive electrode exists, it is desirable to provide a kind of low price, cycle performance is good, low and high temperature
The synthetic method of better performances and the cladding found and doped chemical.
The method of synthesis of anode material of lithium-ion battery mainly has solid phase method, coprecipitation and sol-gel process etc. at present.Solid phase method operation letter
Single, but it is uneven to easily cause batch mixing, the defects such as granule is bigger.Coprecipitation is current most common method, but building-up process is complicated, work
Skill regulation controls relatively strict, needs through multiple steps such as precipitation, washings, is easily caused nickel in product, cobalt, manganese out of proportion.And sol-gel
The product of method synthesis, granule is uniform, advantages of good crystallization, and purity is high；But the size of final granule is not easily controlled, and production cost is high.The present invention is to existing
The improvement of solid state process.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of lithium ion power electricity manganate cathode material for lithium and preparation thereof and improvement
Method, the preferable chemical properties such as this positive electrode granule is uniform, and crystal property is good, has specific capacity high, good cycle.
The technical scheme provided according to the present invention, described lithium ion battery mangaic acid lithium anode material, feature is: the chemical general formula of described positive electrode is
LiMn2O4；
The present invention also protects the preparation method of a kind of lithium ion cell electrode material, and feature is, uses following processing step:
(1) by manganese salt, lithium salts and a small amount of solvent, after mix homogeneously, calcining is prepared；Described manganese salt, lithium salts, mol ratio be 2: 1；
(2) being heated in the air atmosphere of 100～500 DEG C by the mixture that step (1) obtains, heat time heating time is 5～21 hours, before obtaining
Body；
(3) by precursor in natural cooling, add doped chemical, then grind uniformly；
(4) the front body obtained is uniform with appropriate covering material mixed grinding；
(5) being calcined by above-mentioned powder, calcining heat is 600～900 DEG C, and calcination time is 6～36 hours, obtains dusty material；Natural
It is cooled to after room temperature in grinding in ball grinder 0.5～3 hours, i.e. obtains described lithium manganate positive electrode material of power lithium ion.
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 acetic acid
One or more in lithium, lithium nitrate, lithium carbonate, Lithium hydrate；Described covering material is aluminium oxide, ferrum oxide, and titanium oxide, in nickel oxide
One or more；Described doped chemical is magnesium, ferrum, calcium, cobalt, copper, one or more in caesium.
Described assistant research fellow's agent is water and/ethanol.
Advantages of the present invention:
(1) positive electrode granule prepared by the present invention is uniform, and degree of crystallinity is high；
(2) the preferable chemical properties such as the positive electrode of spinel structure provided by the present invention has specific capacity height, good cycle；It is suitable for
Large-scale production, may be used for anode material for lithium-ion batteries and uses.
Accompanying drawing explanation
Fig. 1 is the positive electrode Li prepared by the embodiment of the present invention one1.03AlxMn1.97-xO4The XRD figure spectrum of (x=0.025,0.05,0.10).
Fig. 2 is the positive electrode Li prepared by the embodiment of the present invention one1.03AlxMn1.97-xO4The first charge-discharge of (x=0.025,0.05,0.10) holds
Discharge curve figure.
Fig. 3 is the positive electrode Li prepared by the embodiment of the present invention one1.03AlxMn1.97-xO4The charge and discharge cycles figure of (x=0.025,0.05,0.10).
Below in conjunction with concrete drawings and Examples, the invention will be further described.
Embodiment one: the preparation method of a kind of lithium ion battery mangaic acid lithium anode material, uses following processing step:
(1) by manganese dioxide and lithium carbonate with mol ratio for 2: 1, the ethanol adding 1% after mix homogeneously, grind；
(2) mixture step (1) obtained is 150-500 DEG C of heating, and heat time heating time is 12 hours, then natural cooling, obtains being dried
Precursor, grinds uniformly；
(3) being mixed with Al (NO3) 3 by dry precursor, calcining, calcining heat is 700 DEG C, and calcination time is 20 hours, natural after calcining
Again grind 0.5 hour on ball mill after being cooled to room temperature, i.e. obtain described lithium manganate positive electrode material of power lithium ion
Li1.03AlxMn1.97-xO4(x=0.025,0.05,0.10).
Embodiment two: the preparation method of a kind of lithium ion battery mangaic acid lithium anode material, uses following processing step:
(1) manganese acetate is to mix at 2: 1 in molar ratio with Quilonorm (SKB), the ethanol adding 1% after mix homogeneously, grinds；
(2) mixture step (1) obtained is 100-400 DEG C of heating, and heat time heating time is 12 hours, then natural cooling, obtains being dried
Precursor, grinds uniformly；
(3) being mixed with Al (NO3) 3 by dry precursor, calcining, calcining heat is 650 DEG C, and calcination time is 25 hours, natural after calcining
Again grind 1.5 hours on ball mill after being cooled to room temperature, i.e. obtain described lithium manganate positive electrode material of power lithium ion
Li1.03AlxMn1.97-xO4(x=0.025,0.05,0.10)；
Embodiment three: the preparation method of a kind of lithium ion battery mangaic acid lithium anode material, uses following processing step:
(1) by carbonic acid acid manganese and Quilonorm (SKB) be in molar ratio 2: 1 mixing, the ethanol adding 1% after mix homogeneously, grind；
(2) mixture step (1) obtained is 100-400 DEG C of heating, and heat time heating time is 12 hours, then natural cooling, obtains being dried
Precursor, grinds uniformly；；
(3) being mixed with CaO by dry precursor, calcining, calcining heat is 750 DEG C, and calcination time is 20 hours, natural cooling after calcining
Again grind 0.5 hour on ball mill to room temperature, i.e. obtain described lithium manganate positive electrode material of power lithium ion LiMn2O4；
Positive electrode embodiment one obtained carries out XRD detection, result as it is shown in figure 1, the abscissa of Fig. 1 is sweep limits 2 θ (10～90 °),
Vertical coordinate is the intensity at peak, can be it is seen in fig. 1, that positive electrode is the spinel structure of high-sequential；Material is assembled into button cell, and
It is carried out charge-discharge test, and charging/discharging voltage scope is 3.0～4.5V, as in figure 2 it is shown, first discharge specific capacity is 122.9mAh/g to the maximum, and figure
3 is charge and discharge cycles curve；Abscissa be cycle-index, vertical coordinate is specific capacity, and unit is mAh/g.
Claims (4)
1. a light metal doped lithium ion battery manganate cathode material for lithium, is characterized in that: the chemical general formula of described positive electrode is
LiMn2-xMxO4, wherein x is between 0 to 0.1, and M is Cu, one or more in Al, Li, Mg, Zn, Fe.
2. a preparation method for light metal doped lithium ion battery manganate cathode material for lithium, is characterized in that, uses following processing step:
(1) by manganese salt, lithium salts and a small amount of solvent, after mix homogeneously, calcining is prepared；Described manganese salt, lithium salts, mol ratio be 2: 1.03；
(2) being heated in the air atmosphere of 50～400 DEG C by the mixture that step (1) obtains, heat time heating time is 3～18 hours, obtain front body
Body；
(3) by precursor in natural cooling, add doped chemical, then grind uniformly；
(4) the front body obtained is uniform with appropriate covering material mixed grinding；
(5) being calcined by above-mentioned powder, calcining heat is 600～950 DEG C, and calcination time is 6～36 hours, obtains dusty material；Natural
It is cooled to after room temperature in grinding in ball grinder 0.5～3 hours, i.e. obtains described lithium manganate positive electrode material of power lithium ion.
3. the preparation method of lithium manganate positive electrode material of power lithium ion as claimed in claim 2, is characterized in that: described manganese salt be manganese sulfate,
One or more in manganese nitrate, manganese acetate, manganese dioxide, manganese carbonate, manganese chloride, described lithium salts is Quilonorm (SKB), lithium nitrate, lithium carbonate, hydrogen
One or more in lithium oxide；Described covering material is aluminium oxide, ferrum oxide, titanium oxide, one or more in nickel oxide；Described doping unit
Element is lithium, aluminum, magnesium, ferrum, calcium, cobalt, copper, one or more in caesium.
4. the preparation method of lithium manganate positive electrode material of power lithium ion as claimed in claim 2, is characterized in that: described assistant research fellow's agent be water and/
Ethanol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265507A (en) * | 2017-06-20 | 2017-10-20 | 兰州理工大学 | The preparation method of manganate cathode material for lithium |
| CN108063247A (en) * | 2017-12-23 | 2018-05-22 | 清远佳致新材料研究院有限公司 | A kind of method that compound manganese ore prepares manganate cathode material for lithium |
| 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 |
| CN108493441A (en) * | 2018-02-11 | 2018-09-04 | 山东联星能源集团有限公司 | A kind of positive plate and preparation method thereof for lithium ion battery |
| CN108878832A (en) * | 2018-06-27 | 2018-11-23 | 天津赫维科技有限公司 | A kind of method of two steps lithiumation preparation lithium-rich manganese base material |
| CN111072068A (en) * | 2019-12-24 | 2020-04-28 | 江苏强劲新能源科技有限公司 | Preparation method of ion-doped spinel type lithium manganate positive electrode material |
| US20220223831A1 (en) * | 2021-01-08 | 2022-07-14 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and manufacturing method of positive electrode active material |
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| CN103606670A (en) * | 2013-12-03 | 2014-02-26 | 苏州科大微龙信息技术有限公司 | Lithium manganate positive electrode material of power lithium ion battery and preparation method thereof |
| CN104112849A (en) * | 2014-07-25 | 2014-10-22 | 江南大学 | Light metal element-doped ternary lithium ion battery positive electrode material and synthesis method thereof |
| 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 |
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| CN103606670A (en) * | 2013-12-03 | 2014-02-26 | 苏州科大微龙信息技术有限公司 | Lithium manganate positive electrode material of power lithium ion battery and preparation method thereof |
| CN104112849A (en) * | 2014-07-25 | 2014-10-22 | 江南大学 | Light metal element-doped ternary lithium ion battery positive electrode material and synthesis method thereof |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265507A (en) * | 2017-06-20 | 2017-10-20 | 兰州理工大学 | The preparation method of manganate cathode material for lithium |
| CN107265507B (en) * | 2017-06-20 | 2019-04-02 | 兰州理工大学 | The preparation method of manganate cathode material for lithium |
| 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 |
| CN108063247A (en) * | 2017-12-23 | 2018-05-22 | 清远佳致新材料研究院有限公司 | A kind of method that compound manganese ore prepares manganate cathode material for lithium |
| CN108493441A (en) * | 2018-02-11 | 2018-09-04 | 山东联星能源集团有限公司 | A kind of positive plate and preparation method thereof for lithium ion battery |
| CN108878832A (en) * | 2018-06-27 | 2018-11-23 | 天津赫维科技有限公司 | A kind of method of two steps lithiumation preparation lithium-rich manganese base material |
| CN111072068A (en) * | 2019-12-24 | 2020-04-28 | 江苏强劲新能源科技有限公司 | Preparation method of ion-doped spinel type lithium manganate positive electrode material |
| US20220223831A1 (en) * | 2021-01-08 | 2022-07-14 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and manufacturing method of positive electrode active material |
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Application publication date: 20160824 |