CN109888230A - A kind of synthetic method of manganate cathode material for lithium - Google Patents
A kind of synthetic method of manganate cathode material for lithium Download PDFInfo
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- CN109888230A CN109888230A CN201910159195.7A CN201910159195A CN109888230A CN 109888230 A CN109888230 A CN 109888230A CN 201910159195 A CN201910159195 A CN 201910159195A CN 109888230 A CN109888230 A CN 109888230A
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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
Abstract
The invention discloses a kind of synthetic methods of manganate cathode material for lithium, comprising the following steps: (1) prepared by manganate precursor for lithium；(2) nickel source is mixed；(3) it is pre-sintered；(4) high temperature sintering；(5) aluminium coats.The manganate cathode material for lithium that the present invention synthesizes can improve the theoretical capacity of lithium battery and performance is recycled.
Description
Technical field
The present invention relates to anode material of lithium battery field, in particular to a kind of synthetic method of manganate cathode material for lithium.
Background technique
Spinel lithium manganate have the advantages that it is resourceful, low in cost, environmentally friendly, especially because of its three-dimensional deintercalation
Lithium tunnel is able to bear high current charge-discharge, is acknowledged as one of the positive electrode of lithium ion battery most development prospect,
It is widely used in high-capacity dynamical lithium-ion battery.But the battery theoretical capacity of manganate cathode material for lithium is not high and is recycled
Performance, greatest problem in the application is that cycle performance is bad, the Manganic ion and big multiplying power especially under high temperature, in material
Mangaic acid is finally destroyed so that the dissolution of material in the electrolytic solution is obvious in the divalent manganesetion that particle surface is formed when electric discharge
The structure of lithium also reduces the cycle performance of material.
Summary of the invention
The purpose of the present invention is making improvement and innovation for shortcoming and defect present in background technique, a kind of manganese is provided
The manganate cathode material for lithium of the synthetic method of sour lithium anode material, this method synthesis can improve the theoretical capacity and circulation of lithium battery
Service performance.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of synthetic method of manganate cathode material for lithium, packet
Include following steps:
(1) prepared by manganate precursor for lithium: by Li:Mn molar ratio be 1:2 ingredient by lithium salts and manganese salt, be put into ball milling 3 in ball mill ~
5 hours, stirring and dissolving in distilled water is added after mixing, is reacted 20 ~ 24 hours in 180 ~ 200 DEG C of reaction kettles, reaction terminates cold
But it to after room temperature, is rinsed 3 ~ 5 times with dehydrated alcohol, is put into 40 ~ 50 DEG C of baking oven and dries, obtain manganate precursor for lithium；
(2) it mixes nickel source: taking nickel salt in the ratio of 0.56 ~ 0.8:1 of Le:Li molar ratio, nickel salt and manganate precursor for lithium are put into
Mixture is made in ball milling 2 ~ 3 hours in ball mill；
(3) it is pre-sintered: filling this blend into body, and in the sintering furnace that temperature is 350 ~ 450 DEG C, kept for constant temperature 3 ~ 5 hours,
Object must be pre-sintered；
(4) high temperature sintering: object will be pre-sintered and be packed into body, and in the sintering furnace that temperature is 800 ~ 900 DEG C, keep constant temperature 7 ~ 9
Hour, obtain high temperature sintering object；
(5) aluminium coats: by the broken sieving of high temperature sintering object, then successively high temperature sintering object, lithium aluminate being put into surfactant
Stirring 2 ~ 3 hours, finally by being filtered, washed, drying, obtains manganate cathode material for lithium.
Preferably, lithium salts described in step (1) is one of lithium carbonate, lithium acetate, lithium chloride or a variety of.
Preferably, manganese salt described in step (1) is manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, one in manganese carbonate
Kind is a variety of.
Preferably, nickel salt described in step (2) is one of nickel nitrate, nickel chloride, nickel sulfate or a variety of.
Preferably, surfactant described in step (5) is cetyl trimethylammonium bromide, dodecyl benzene sulfonic acid
One of sodium, disodium ethylene diamine tetraacetate, N-methyl pyrrole chlorine alkanone are a variety of.
Advantages of the present invention and the utility model has the advantages that
The present invention is using manganate precursor for lithium made from hydro-thermal method, and grain development is complete, and granularity is small, and is evenly distributed, electrochemistry
Function admirable.The present invention is adulterating nickel element raising potassium manganate positive electrode using high temperature solid-state method in manganate precursor for lithium
Activity and energy density, and the recycling performance of mangaic acid nickel is being improved by coating aluminium.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
A kind of synthetic method of manganate cathode material for lithium, comprising the following steps:
(1) prepared by manganate precursor for lithium: it is 1:2 ingredient that lithium carbonate and manganese dioxide, which are pressed Li:Mn molar ratio, is put into ball mill
Ball milling 3 ~ 5 hours, stirring and dissolving in distilled water is added after mixing, is reacted 20 ~ 24 hours in 180 ~ 200 DEG C of reaction kettles, reacts
After end is cooled to room temperature, is rinsed 3 ~ 5 times with dehydrated alcohol, be put into 40 ~ 50 DEG C of baking oven and dry, obtain LiMn2O4 forerunner
Body；
(2) it mixes nickel source: nickel nitrate is taken in the ratio of 0.56 ~ 0.8:1 of Le:Li molar ratio, by nickel nitrate and manganate precursor for lithium
Ball milling 2 ~ 3 hours in ball mill are put into, mixture is made；
(3) it is pre-sintered: filling this blend into body, and in the sintering furnace that temperature is 350 ~ 450 DEG C, kept for constant temperature 3 ~ 5 hours,
Object must be pre-sintered；
(4) high temperature sintering: object will be pre-sintered and be packed into body, and in the sintering furnace that temperature is 800 ~ 900 DEG C, keep constant temperature 7 ~ 9
Hour, obtain high temperature sintering object；
(5) aluminium coats: by the broken sieving of high temperature sintering object, then high temperature sintering object, lithium aluminate being successively put into cetyl front three
It is stirred 2 ~ 3 hours in base ammonium bromide, finally by being filtered, washed, drying, obtains manganate cathode material for lithium.
Embodiment 2
A kind of synthetic method of manganate cathode material for lithium, comprising the following steps:
(1) prepared by manganate precursor for lithium: it is 1:2 ingredient that lithium acetate and manganese sesquioxide managnic oxide, which are pressed Li:Mn molar ratio, is put into ball mill
Middle ball milling 3 ~ 5 hours is added stirring and dissolving in distilled water, reacts 20 ~ 24 hours in 180 ~ 200 DEG C of reaction kettles, instead after mixing
It should terminate after being cooled to room temperature, be rinsed 3 ~ 5 times with dehydrated alcohol, be put into 40 ~ 50 DEG C of baking oven and dry, before obtaining LiMn2O4
Drive body；
(2) it mixes nickel source: nickel chloride is taken in the ratio of 0.56 ~ 0.8:1 of Le:Li molar ratio, by nickel chloride and manganate precursor for lithium
Ball milling 2 ~ 3 hours in ball mill are put into, mixture is made；
(3) it is pre-sintered: filling this blend into body, and in the sintering furnace that temperature is 350 ~ 450 DEG C, kept for constant temperature 3 ~ 5 hours,
Object must be pre-sintered；
(4) high temperature sintering: object will be pre-sintered and be packed into body, and in the sintering furnace that temperature is 800 ~ 900 DEG C, keep constant temperature 7 ~ 9
Hour, obtain high temperature sintering object；
(5) aluminium coats: by the broken sieving of high temperature sintering object, then high temperature sintering object, lithium aluminate being successively put into detergent alkylate sulphur
It is stirred 2 ~ 3 hours in sour sodium, finally by being filtered, washed, drying, obtains manganate cathode material for lithium.
Embodiment 3
A kind of synthetic method of manganate cathode material for lithium, comprising the following steps:
(1) prepared by manganate precursor for lithium: it is 1:2 ingredient that lithium chloride and manganese carbonate, which are pressed Li:Mn molar ratio, is put into ball in ball mill
Mill 3 ~ 5 hours is added stirring and dissolving in distilled water, reacts 20 ~ 24 hours in 180 ~ 200 DEG C of reaction kettles after mixing, reaction knot
After beam is cooled to room temperature, is rinsed 3 ~ 5 times with dehydrated alcohol, be put into 40 ~ 50 DEG C of baking oven and dry, obtain LiMn2O4 forerunner
Body；
(2) it mixes nickel source: nickel sulfate is taken in the ratio of 0.56 ~ 0.8:1 of Le:Li molar ratio, by nickel sulfate and manganate precursor for lithium
Ball milling 2 ~ 3 hours in ball mill are put into, mixture is made；
(3) it is pre-sintered: filling this blend into body, and in the sintering furnace that temperature is 350 ~ 450 DEG C, kept for constant temperature 3 ~ 5 hours,
Object must be pre-sintered；
(4) high temperature sintering: object will be pre-sintered and be packed into body, and in the sintering furnace that temperature is 800 ~ 900 DEG C, keep constant temperature 7 ~ 9
Hour, obtain high temperature sintering object；
(5) aluminium coats: by the broken sieving of high temperature sintering object, then high temperature sintering object, lithium aluminate being successively put into ethylenediamine tetra-acetic acid
It is stirred 2 ~ 3 hours in disodium, finally by being filtered, washed, drying, obtains manganate cathode material for lithium.
The technical principle of the invention is described above in combination with a specific embodiment.These descriptions are intended merely to explain of the invention
Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, the technology of this field
Personnel can associate with other specific embodiments of the invention without creative labor, these modes are fallen within
Within protection scope of the present invention.
Claims (5)
1. a kind of synthetic method of manganate cathode material for lithium, it is characterised in that following steps:
(1) prepared by manganate precursor for lithium: by Li:Mn molar ratio be 1:2 ingredient by lithium salts and manganese salt, be put into ball milling 3 in ball mill ~
5 hours, stirring and dissolving in distilled water is added after mixing, is reacted 20 ~ 24 hours in 180 ~ 200 DEG C of reaction kettles, reaction terminates cold
But it to after room temperature, is rinsed 3 ~ 5 times with dehydrated alcohol, is put into 40 ~ 50 DEG C of baking oven and dries, obtain manganate precursor for lithium；
(2) it mixes nickel source: taking nickel salt in the ratio of 0.56 ~ 0.8:1 of Le:Li molar ratio, nickel salt and manganate precursor for lithium are put into
Mixture is made in ball milling 2 ~ 3 hours in ball mill；
(3) it is pre-sintered: filling this blend into body, and in the sintering furnace that temperature is 350 ~ 450 DEG C, kept for constant temperature 3 ~ 5 hours,
Object must be pre-sintered；
(4) high temperature sintering: object will be pre-sintered and be packed into body, and in the sintering furnace that temperature is 800 ~ 900 DEG C, keep constant temperature 7 ~ 9
Hour, obtain high temperature sintering object；
(5) aluminium coats: by the broken sieving of high temperature sintering object, then successively high temperature sintering object, lithium aluminate being put into surfactant
Stirring 2 ~ 3 hours, finally by being filtered, washed, drying, obtains manganate cathode material for lithium.
2. a kind of synthetic method of manganate cathode material for lithium according to claim 1, it is characterised in that described in step (1)
Lithium salts is one of lithium carbonate, lithium acetate, lithium chloride or a variety of.
3. a kind of synthetic method of manganate cathode material for lithium according to claim 1, it is characterised in that described in step (1)
Manganese salt is one of manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese carbonate or a variety of.
4. a kind of synthetic method of manganate cathode material for lithium according to claim 1, it is characterised in that described in step (2)
Nickel salt is one of nickel nitrate, nickel chloride, nickel sulfate or a variety of.
5. a kind of synthetic method of manganate cathode material for lithium according to claim 1, it is characterised in that described in step (5)
Surfactant is cetyl trimethylammonium bromide, neopelex, disodium ethylene diamine tetraacetate, N-methyl pyrrole chlorine
One of alkanone is a variety of.
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| CN103682315A (en) * | 2013-12-20 | 2014-03-26 | 哈尔滨工业大学 | Method for preparing high-capacity long-life lithium ion battery lithium manganate cathode material |
| CN104766960A (en) * | 2015-04-13 | 2015-07-08 | 河北工业大学 | Method for modifying lithium nickel manganese oxide positive electrode material for lithium ion battery |
| US20150270545A1 (en) * | 2014-03-20 | 2015-09-24 | Washington University | Doped Lithium-Rich Layered Composite Cathode Materials |
| CN105322150A (en) * | 2015-11-26 | 2016-02-10 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation technology of modified positive material lithium nickel manganese oxide for lithium-ion battery |
| CN105322151A (en) * | 2015-11-26 | 2016-02-10 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing modified lithium nickel manganese oxide which is anode material of lithium ion battery |
| CN105355905A (en) * | 2015-11-26 | 2016-02-24 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing high-voltage modified lithium ion cell cathode material lithium nickel manganese oxide |
| CN107093725A (en) * | 2017-04-29 | 2017-08-25 | 合肥国轩高科动力能源有限公司 | A kind of method of modifying of layered lithium manganate material |
| CN109244453A (en) * | 2018-10-31 | 2019-01-18 | 云南民族大学 | A kind of method of nickel doping preparation High-performance lithium manganate anode material |
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2019
- 2019-03-04 CN CN201910159195.7A patent/CN109888230B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880063A (en) * | 2010-07-16 | 2010-11-10 | 李运姣 | Preparation method of lithium manganate precursor for lithium ion battery anode material |
| CN102034977A (en) * | 2010-11-10 | 2011-04-27 | 湘西自治州兴湘科技开发有限责任公司 | Preparation method of positive-pole materials (lithium manganate and doped lithium manganate) of lithium ion battery |
| CN103682315A (en) * | 2013-12-20 | 2014-03-26 | 哈尔滨工业大学 | Method for preparing high-capacity long-life lithium ion battery lithium manganate cathode material |
| US20150270545A1 (en) * | 2014-03-20 | 2015-09-24 | Washington University | Doped Lithium-Rich Layered Composite Cathode Materials |
| CN104766960A (en) * | 2015-04-13 | 2015-07-08 | 河北工业大学 | Method for modifying lithium nickel manganese oxide positive electrode material for lithium ion battery |
| CN105322150A (en) * | 2015-11-26 | 2016-02-10 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation technology of modified positive material lithium nickel manganese oxide for lithium-ion battery |
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| CN107093725A (en) * | 2017-04-29 | 2017-08-25 | 合肥国轩高科动力能源有限公司 | A kind of method of modifying of layered lithium manganate material |
| CN109244453A (en) * | 2018-10-31 | 2019-01-18 | 云南民族大学 | A kind of method of nickel doping preparation High-performance lithium manganate anode material |
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