CN103094555A - Method for preparing manganese, cobalt, nickel, oxygen and lithium quinary lithium ion battery anode material with nanometer structure - Google Patents
Method for preparing manganese, cobalt, nickel, oxygen and lithium quinary lithium ion battery anode material with nanometer structure Download PDFInfo
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- CN103094555A CN103094555A CN2013100395336A CN201310039533A CN103094555A CN 103094555 A CN103094555 A CN 103094555A CN 2013100395336 A CN2013100395336 A CN 2013100395336A CN 201310039533 A CN201310039533 A CN 201310039533A CN 103094555 A CN103094555 A CN 103094555A
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Abstract
The invention discloses a method for preparing a manganese, cobalt, nickel, oxygen and lithium quinary lithium ion battery anode material with a nometer structure. The method comprises the following steps of: treating a reaction solution by utilizing a hydrothermal method so as to obtain a precursor of the required material; firing the precursor for a certain time to obtain the manganese, cobalt, nickel, oxygen and lithium quinary lithium ion battery anode material with the nanometer structure. The method has the advantages that the reaction is simple, the process cost is low, the product size controllability is high, and due to a special product structure, the specific surface area is large, the adsorption capacity is high, the size change is slight in the stress releasing process, the lithium ion storage capacity is improved, and the method has important significance for modifying the size change and improving the speed in the lithium adsorption and desorption process.
Description
Technical field
The invention belongs to technical field of novel materials, relate to the energy storage material technology of preparing, specifically refer to the preparation method of five yuan of anode material for lithium-ion batteries of a kind of nano-structure manganese cobalt nickel oxygen lithium.
Background technology
From the our times energy system, energy shortage and environmental problem are on the rise, so efficient, cleaning, safety, economically viable new forms of energy system become the active demand of current social.And ever-increasing energy demand makes energy conversion and storage become a worldwide important subject.Lithium ion battery have specific energy high, have extended cycle life, the characteristics of memory-less effect, and quick charged advantage is arranged, therefore can be widely used in portable type electronic product as mobile phone, notebook computer, Video Camera etc. and the required rechargeable battery of electric automobile.
In lithium ion battery, the performance of positive and negative pole material has directly determined the performance of lithium ion battery, therefore, cheap, high-performance just/exploitation of negative material is the research emphasis of lithium ion battery always.Theoretical specific capacity is high owing to having for the transition metal oxide of embedding lithium, environmental friendliness, low cost and other advantages, becomes the study hotspot of anode material for lithium-ion batteries.The present invention is directed to the preparation of anode material for lithium-ion batteries, proposed the preparation method of five yuan of anode material for lithium-ion batteries of a kind of nano-structure manganese cobalt nickel oxygen lithium.
In the process that lithium ion battery discharges and recharges, transition metal oxide has strong change in volume as electrode material, the positive electrode spherical particle surface of the present invention preparation is comprised of thin slice, and sheet thickness is tens nanoscale scopes, and toughness is better, and surface void is larger, therefore slowed down the variation of material volume in charge and discharge process, increased the material specific area, improved adsoptivity, and because sheet thickness is little, has improved lithium ion and inlayed the speed of taking off embedding.
Summary of the invention
A kind of method that the purpose of this invention is to provide five yuan of anode material for lithium-ion batteries of a kind of nano-structure manganese cobalt of preparation nickel oxygen lithium of simple possible, both considered the problem that promotes the lithium ion capacity storage, by its special structure, certain modification is carried out in the variation of volume in adsorption and desorption lithium ion process simultaneously, and the speed of attached desorption lithium process.
Method of the present invention is to obtain the precursor of product with hydro thermal method, and then the calcination regular hour obtains required product.The existing huge specific area of this class formation has certain patience to change in volume simultaneously in the process of adsorption/desorption lithium, and because laminated structure in this material structure is very thin, therefore the process of adsorption/desorption lithium is comparatively rapid.
The preparation method of five yuan of anode material for lithium-ion batteries of a kind of nano-structure manganese cobalt nickel oxygen lithium involved in the present invention comprises the steps:
At first, with Lithium hydroxide monohydrate, nickel sulfate hexahydrate, cobaltous sulfate hydrate, manganese sulfate monohydrate, hexa, P
123, inorganic acid take mol ratio as 1:(0.7~0.86): (0.1~0.2): (0.04~0.2): (0~2): (0~0.2): (0.5~9) is dissolved in certain deionized water, stirs, and forms reaction solution; Secondly, reactant liquor is added in reactor, reacted 4~6 hours under 100 ℃~150 ℃, obtain presoma; Then the presoma that obtains was obtained material requested in 4~6 hours 400 ℃~750 ℃ lower calcinations in crucible.
Described inorganic acid is hydrochloric acid, sulfuric acid, nitric acid.
Advantage of the present invention is: reaction is simple, process costs is low, handling strong to the product size, the special construction of product makes that its specific area is huge, high adsorption capacity and in the process that discharges stress change in volume less, the modification of the change in volume of the raising of lithium ion memory capacity and adsorption/desorption lithium process, the raising of speed are being had important meaning.
Description of drawings
Fig. 1: the scanning electron microscope diagram spectrum of five yuan of lithium ion anode materials of gained nano-structure manganese cobalt nickel oxygen lithium of the present invention.
Fig. 2: five yuan of lithium ion anode materials of gained nano-structure manganese cobalt nickel oxygen lithium of the present invention are applied in the energy dispersion X ray collection of illustrative plates of gained on silicon chip.
Fig. 3: the low power transmission electron microscope collection of illustrative plates of five yuan of lithium ion anode materials of gained nano-structure manganese cobalt nickel oxygen lithium of the present invention.
Embodiment:
Embodiment 1:
The 40ml deionized water is added in beaker, add 1mmolP
123, be stirred to dissolving fully, then add successively 4.3mmol nickel sulfate hexahydrate, 0.5mmol cobaltous sulfate hydrate, 0.2mmol manganese sulfate monohydrate, 5mmol Lithium hydroxide monohydrate, 10mmol hexa, 20mmol sulfuric acid to stir.Then pour in reactor, setting heating-up temperature is 120 ℃, and be 6 hours heating time.Heat complete after, take out reactor when naturally cooling to room temperature, centrifugal to the presoma that obtains, then use washed with de-ionized water, obtain required presoma.With the calcination of gained presoma, setting calcination temperature is 420 ℃ again, and calcination time is 6 hours, and calcination is complete, takes out when naturally cooling to room temperature, obtains end product.
Embodiment 2:
The 40ml deionized water is added in beaker, add 0.1mmolP
123, be stirred to dissolving fully, then add successively 3.5mmol nickel sulfate hexahydrate, 0.5mmol cobaltous sulfate hydrate, 1mmol manganese sulfate monohydrate, 5mmol Lithium hydroxide monohydrate, 10mmol hexa, 45mmol hydrochloric acid to stir.Then pour in reactor, setting heating-up temperature is 150 ℃, and be 4 hours heating time.Heat complete after, take out reactor when naturally cooling to room temperature, centrifugal to the presoma that obtains, then use washed with de-ionized water, obtain required presoma.With the calcination of gained presoma, setting calcination temperature is 750 ℃ again, and calcination time is 6 hours, and calcination is complete, takes out when naturally cooling to room temperature, obtains end product.
Embodiment 3:
The 40ml deionized water is added in beaker, add 0.5mmolP
123, be stirred to dissolving fully, then add successively 3.75mmol nickel sulfate hexahydrate, 1mmol cobaltous sulfate hydrate, 0.25mmol manganese sulfate monohydrate, 5mmol Lithium hydroxide monohydrate, 0mmol hexa, 2.5mmol sulfuric acid to stir.Then pour in reactor, setting heating-up temperature is 100 ℃, and be 5 hours heating time.Heat complete after, take out reactor when naturally cooling to room temperature, centrifugal to the presoma that obtains, then use washed with de-ionized water, obtain required presoma.With the calcination of gained presoma, setting calcination temperature is 400 ℃ again, and calcination time is 4 hours, and calcination is complete, takes out when naturally cooling to room temperature, obtains end product.
Embodiment 4:
The 20ml deionized water is added in beaker, add 0mmolP
123, be stirred to dissolving fully, then add successively 1.72mmol nickel sulfate hexahydrate, 0.2mmol cobaltous sulfate hydrate, 0.08mmol manganese sulfate monohydrate, 2mmol Lithium hydroxide monohydrate, 4mmol hexa, 18mmol nitric acid to stir.Then pour in reactor, setting heating-up temperature is 120 ℃, and be 6 hours heating time.Heat complete after, take out reactor when naturally cooling to room temperature, centrifugal to the presoma that obtains, then use washed with de-ionized water, obtain required presoma.With the calcination of gained presoma, setting calcination temperature is 450 ℃ again, and calcination time is 5 hours, and calcination is complete, takes out when naturally cooling to room temperature, obtains end product.
Embodiment 5:
The 40ml deionized water is added in beaker, add 1mmolP
123, be stirred to dissolving fully, then add successively 3.75mmol nickel sulfate hexahydrate, 0.75mmol cobaltous sulfate hydrate, 0.5mmol manganese sulfate monohydrate, 5mmol Lithium hydroxide monohydrate, 10mmol hexa, 22mmol sulfuric acid to stir.Then pour in reactor, setting heating-up temperature is 120 ℃, and be 6 hours heating time.Heat complete after, take out reactor when naturally cooling to room temperature, centrifugal to the presoma that obtains, then use washed with de-ionized water, obtain required presoma.With the calcination of gained presoma, setting calcination temperature is 420 ℃ again, and calcination time is 6 hours, and calcination is complete, takes out when naturally cooling to room temperature, obtains end product.
Claims (2)
1. the preparation method of five yuan of anode material for lithium-ion batteries of a nano-structure manganese cobalt nickel oxygen lithium, it comprises the steps:
At first, with Lithium hydroxide monohydrate, nickel sulfate hexahydrate, cobaltous sulfate hydrate, manganese sulfate monohydrate, hexa, P
123, inorganic acid take mol ratio as 1:(0.7~0.86): (0.1~0.2): (0.04~0.2): (0~2): (0~0.2): (0.5~9) is dissolved in certain deionized water, stirs, and forms reaction solution; Then, reactant liquor is added in reactor, reacted 4~6 hours under 100 ℃~150 ℃, obtain presoma; At last the presoma that obtains was obtained material requested in 4~6 hours 400 ℃~750 ℃ lower calcinations in crucible.
2. the preparation method of five yuan of anode material for lithium-ion batteries of a kind of nano-structure manganese cobalt nickel oxygen lithium according to claim 1, it is characterized in that: described inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
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Cited By (4)
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CN107946589A (en) * | 2017-11-28 | 2018-04-20 | 安徽零度新能源科技有限公司 | A kind of positive electrode that can reduce electrode of lithium cell polarization phenomena |
CN108232187A (en) * | 2018-01-03 | 2018-06-29 | 武汉科技大学 | High dispersive hexagonal nanosheet structure nickel-cobalt-manganternary ternary anode material and preparation method thereof |
CN109979761A (en) * | 2019-04-18 | 2019-07-05 | 桂林理工大学 | A kind of preparation method and applications of cobalt nickel bimetal hydroxide composite material |
CN111063882A (en) * | 2019-12-25 | 2020-04-24 | 中原工学院 | Ternary material for power type lithium ion battery and preparation method thereof |
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CN101869853A (en) * | 2010-05-28 | 2010-10-27 | 中山大学 | Ordered mesoporous carbon/tungsten carbide composite material and supported catalyst thereof and preparation method thereof |
US20110318249A1 (en) * | 2009-03-12 | 2011-12-29 | Mitsui Chemicals, Inc. | Novel porous metal oxide, method for producing the same, and use of the same |
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CN101355161A (en) * | 2008-09-17 | 2009-01-28 | 长沙矿冶研究院 | Method for preparing lithium ion battery anode material nickel cobalt lithium manganate |
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CN101869853A (en) * | 2010-05-28 | 2010-10-27 | 中山大学 | Ordered mesoporous carbon/tungsten carbide composite material and supported catalyst thereof and preparation method thereof |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107946589A (en) * | 2017-11-28 | 2018-04-20 | 安徽零度新能源科技有限公司 | A kind of positive electrode that can reduce electrode of lithium cell polarization phenomena |
CN108232187A (en) * | 2018-01-03 | 2018-06-29 | 武汉科技大学 | High dispersive hexagonal nanosheet structure nickel-cobalt-manganternary ternary anode material and preparation method thereof |
CN108232187B (en) * | 2018-01-03 | 2020-03-10 | 武汉科技大学 | High-dispersion hexagonal nanosheet structure nickel-cobalt-manganese ternary cathode material and preparation method thereof |
CN109979761A (en) * | 2019-04-18 | 2019-07-05 | 桂林理工大学 | A kind of preparation method and applications of cobalt nickel bimetal hydroxide composite material |
CN111063882A (en) * | 2019-12-25 | 2020-04-24 | 中原工学院 | Ternary material for power type lithium ion battery and preparation method thereof |
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Application publication date: 20130508 |