CN106450278A - Ternary positive electrode material with hollow microsphere structure, preparation method and application - Google Patents
Ternary positive electrode material with hollow microsphere structure, preparation method and application Download PDFInfo
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- CN106450278A CN106450278A CN201610953125.5A CN201610953125A CN106450278A CN 106450278 A CN106450278 A CN 106450278A CN 201610953125 A CN201610953125 A CN 201610953125A CN 106450278 A CN106450278 A CN 106450278A
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- hollow microsphere
- lithium
- microsphere structure
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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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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a ternary positive electrode material with a hollow microsphere structure, a preparation method and application. The preparation method comprises the steps that MnCO3 microspheres are calcined for 5-10 h at the temperature of 400 DEG C to 450 DEG C in a muffle furnace, and porous MnO2 is generated; lithium salt, nickel salt, cobalt salt and porous MnO2 are steeped in a homogeneous medium according to the molar weight ratio of 1:(1-x-y):x:y (0<x<1, 0<y<1), and the homogeneous medium is slowly evaporated under the room temperature condition in the magnetic stirring process; the mixture is ground for 10 min to 30 min and then calcined for 20-25 h at the temperature of 800 DEG C to 900 DEG C in the muffle furnace, and then the ternary positive electrode material with the hollow microsphere structure is obtained. The ternary positive electrode material with the hollow microsphere structure has the large specific surface area and can fully make contact with an electrolyte, and then the electrochemical performance of the material can be improved. The first-time specific discharge capacity is 170 mAh/g, the specific discharge capacity after 50 cycles is 152 mAh/g, and the capacity retention ratio is 89.4%. In addition, the preparation method is simple, the technological conditions are easy to achieve, energy consumption is low, and no pollution is generated in preparation.
Description
Technical field
The present invention relates to a kind of preparation method of lithium electricity positive electrode, more particularly to a kind of hollow microsphere structure ternary is just
Pole material and preparation method and application.
Background technology
With less, lighter and the electronics of higher performance and developing rapidly of communication apparatus, people carry to for these equipment
The battery performance of power supply source especially proposes higher and higher requirement to specific energy.But, the lithium-ion electric of commercialization at present
The specific capacity of pond and MH/Ni battery has been difficult to continue to improve.Therefore, the battery higher in the urgent need to developing specific energy.Lithium from
Sub- secondary cell has been widely used for mobile communication, notebook computer, video camera, photograph as high-energy-density electrochmical power source
The fields such as machine, portable instrument, develop rapidly and become one of currently the most important ones secondary cell.Lithium ion battery is as
The green high-capacity battery of a new generation, developed rapidly in early 1990s, and lithium ion battery is because its voltage is high, energy
Density is high, have extended cycle life, gain great popularity the advantages of environmental pollution is little.
Due to ternary material LiNi1-x-yCoxMnyO2（0<x<1, 0<y<1）Have better than LiFePO 4 and cobalt acid lithium
Characteristic, and according to adjusting the ratio of nickel, cobalt, manganese, the ternary electrode material of different performance can be prepared.With new forms of energy vapour
The rise of car and development, ternary material is the focus of research.
Content of the invention
For overcoming the deficiencies in the prior art, the present invention provides a kind of hollow microsphere structure tertiary cathode material and preparation method
And application.
A kind of preparation method of hollow microsphere structure tertiary cathode material is it is characterised in that the concretely comprising the following steps of the method：
（1）By MnCO3Microballoon 400 ~ 450 DEG C of calcining 5 ~ 10 h in Muffle furnace, form the MnO of porous2；
（2）Compare 1 by mole:1-x-y: x:y（0<x<1,0<y<1）By lithium salts, nickel salt, cobalt salt, porous MnO2It is immersed in uniformly
In medium, during magnetic agitation, slowly uniform dielectric is evaporated at ambient temperature；
（3）Above-mentioned gained mixture is ground 10 ~ 30 min, then 800 ~ 900 DEG C of calcining 20 ~ 25 h in Muffle furnace, obtain hollow
Micro-sphere structure tertiary cathode material.
Described lithium salts be one of lithium nitrate, lithium acetate, lithium citrate, lithium oxalate, lithium formate or lithium lactate or its
Combination.
Described nickel salt is one of nickel nitrate, nickel acetate or nickel oxalate or a combination thereof.
Described cobalt salt is one of cobalt nitrate, cobalt acetate or cobalt oxalate or a combination thereof.
Described uniform dielectric is acetone or absolute ethyl alcohol.
A kind of hollow microsphere structure tertiary cathode material is it is characterised in that prepare according to any of the above-described methods described.
A kind of hollow microsphere structure tertiary cathode material is as the application of lithium electricity positive electrode.
The present invention provides a kind of hollow microsphere structure tertiary cathode material（LiNi1-x-yCoxMnyO2（0<x<1, 0<y<1））
Preparation method, the present invention using " Kinkendal Effect " principle（Metallic atom nickel, cobalt, manganese faster external diffusion speed with
The oxygen atom hollow-core construction that more slowly interior diffusion rate is formed）, tiny balloon knot is prepared with infusion process assisted with high-temperature solid phase method
The ternary material of structure.The ternary material of hollow microsphere structure has larger specific surface area, can be fully contacted with electrolyte, enter
And the chemical property of material can be improved.And preparation method is simple, and process conditions are easily realized, and energy ezpenditure is low, and make
Standby pollution-free.
Brief description
Fig. 1 is embodiment 1 hollow microsphere structure LiNi1/3Co1/3Mn1/3O2The XRD of material.
Fig. 2 is embodiment 2 hollow microsphere structure LiNi0.5Co0.3Mn0.2O2The cycle life figure of material.
Specific embodiment
The present invention is described in detail by following instantiation, but protection scope of the present invention is not only restricted to these
Examples of implementation.
Embodiment one：
By MnCO3Microballoon 450 DEG C of calcining 10 h in Muffle furnace, form the MnO of porous2；By mole than 0.01 mol:
0.0033 mol :0.0033 mol :0.0033 mol is by lithium acetate, nickel acetate, cobalt acetate and porous MnO2It is immersed in anhydrous
In ethanol, during magnetic agitation, slowly absolute ethyl alcohol is evaporated at ambient temperature；Above-mentioned gained mixture is ground
10 min, then 800 DEG C of calcining 25 h in Muffle furnace, obtain the LiNi of hollow microsphere structure1/3Co1/3Mn1/3O2.Fig. 1 is hollow
Micro-sphere structure LiNi1/3Co1/3Mn1/3O2The XRD of material, through contrasting with document, this material is pure phase, and R(003)/(104)=1.7,
More than 1.2, illustrate there is no Li+With Ni2+Ion mix phenomenon,（006）/ (102) with（108）/（110）Division peak illustrative material
It is layer structure.
Embodiment two：
By MnCO3Microballoon 450 DEG C of calcining 5 h in Muffle furnace, form the MnO of porous2；By mole than 0.01 mol:
0.005 mol :0.003 mol :0.002 mol is by lithium nitrate, nickel nitrate, cobalt nitrate and porous MnO2It is immersed in anhydrous second
In alcohol, during magnetic agitation, slowly absolute ethyl alcohol is evaporated at ambient temperature；Above-mentioned gained mixture is ground 30
Min, then 850 DEG C of calcining 20 h in Muffle furnace, obtain the LiNi of hollow microsphere structure0.5Co0.3Mn0.2O2.Fig. 2 is tiny balloon
Structure LiNi0.5Co0.3Mn0.2O2The cycle life figure of material, first discharge specific capacity is 170 mAh/g, puts through 50 circulations
Electric specific capacity is 152 mAh/g, and capability retention is 89.4%.
Embodiment three：
By MnCO3Microballoon 400 DEG C of calcining 10 h in Muffle furnace, form the MnO of porous2；By mole than 0.01 mol:
0.008 mol :0.001 mol :0.001 mol is by lithium nitrate, nickel nitrate, cobalt nitrate and porous MnO2Impregnate in acetone,
During magnetic agitation, slowly acetone evaporated is fallen at ambient temperature；Above-mentioned gained mixture is ground 30 min, then
In Muffle furnace, 900 DEG C of calcining 20 h, obtain the LiNi of hollow microsphere structure0.8Co0.1Mn0.1O2.
Claims (7)
1. a kind of preparation method of hollow microsphere structure tertiary cathode material is it is characterised in that the concretely comprising the following steps of the method：
（1）By MnCO3Microballoon 400 ~ 450 DEG C of calcining 5 ~ 10 h in Muffle furnace, form the MnO of porous2；
（2）Compare 1 by mole:1-x-y: x:y（0<x<1,0<y<1）By lithium salts, nickel salt, cobalt salt, porous MnO2It is immersed in uniformly
In medium, during magnetic agitation, slowly uniform dielectric is evaporated at ambient temperature；
（3）Above-mentioned gained mixture is ground 10 ~ 30 min, then 800 ~ 900 DEG C of calcining 20 ~ 25 h in Muffle furnace, obtain hollow
Micro-sphere structure tertiary cathode material.
2. according to claim 1 a kind of preparation method of hollow microsphere structure tertiary cathode material it is characterised in that described
Lithium salts be one of lithium nitrate, lithium acetate, lithium citrate, lithium oxalate, lithium formate or lithium lactate or a combination thereof.
3. according to claim 1 a kind of preparation method of hollow microsphere structure tertiary cathode material it is characterised in that described
Nickel salt be one of nickel nitrate, nickel acetate or nickel oxalate or a combination thereof.
4. according to claim 1 a kind of preparation method of hollow microsphere structure tertiary cathode material it is characterised in that described
Cobalt salt be one of cobalt nitrate, cobalt acetate or cobalt oxalate or a combination thereof.
5. according to claim 1 a kind of preparation method of hollow microsphere structure tertiary cathode material it is characterised in that described
Uniform dielectric be acetone or absolute ethyl alcohol.
6. a kind of hollow microsphere structure tertiary cathode material is it is characterised in that prepare according to the arbitrary methods described of claim 1-5
Obtain.
7. according to claim 6 hollow microsphere structure tertiary cathode material as lithium electricity positive electrode application.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987743A (en) * | 2018-09-04 | 2018-12-11 | 江南大学 | Ternary cathode material of lithium ion battery and preparation method thereof with hollow structure |
| CN109860561A (en) * | 2019-02-13 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | A kind of tiny balloon and its preparation method and application of richness lithium manganese boron |
| CN111498915A (en) * | 2020-04-26 | 2020-08-07 | 株洲升华科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN111841562A (en) * | 2019-04-29 | 2020-10-30 | 北京化工大学 | NH for low-temperature plasma3Catalyst for selective catalytic reduction process and method for preparing the same |
| WO2022237823A1 (en) | 2021-12-23 | 2022-11-17 | 北京当升材料科技股份有限公司 | Positive electrode material having multi-cavity structure and preparation method therefor, and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method for nickel-manganese-cobalt anode material of lithium ion battery |
| CN105914364A (en) * | 2016-05-13 | 2016-08-31 | 安泰科技股份有限公司 | Lithium ion battery ternary positive electrode material with hollow microsphere structure and preparation method thereof |
-
2016
- 2016-11-03 CN CN201610953125.5A patent/CN106450278A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method for nickel-manganese-cobalt anode material of lithium ion battery |
| CN105914364A (en) * | 2016-05-13 | 2016-08-31 | 安泰科技股份有限公司 | Lithium ion battery ternary positive electrode material with hollow microsphere structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 熊文: "球型层状LiNi1/3Mn1/3Co1/3O2的制备及其电化学行为研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987743A (en) * | 2018-09-04 | 2018-12-11 | 江南大学 | Ternary cathode material of lithium ion battery and preparation method thereof with hollow structure |
| CN109860561A (en) * | 2019-02-13 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | A kind of tiny balloon and its preparation method and application of richness lithium manganese boron |
| CN109860561B (en) * | 2019-02-13 | 2022-02-15 | 合肥国轩高科动力能源有限公司 | Lithium-manganese-boron-rich hollow microsphere and preparation method and application thereof |
| CN111841562A (en) * | 2019-04-29 | 2020-10-30 | 北京化工大学 | NH for low-temperature plasma3Catalyst for selective catalytic reduction process and method for preparing the same |
| CN111498915A (en) * | 2020-04-26 | 2020-08-07 | 株洲升华科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| WO2022237823A1 (en) | 2021-12-23 | 2022-11-17 | 北京当升材料科技股份有限公司 | Positive electrode material having multi-cavity structure and preparation method therefor, and lithium ion battery |
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Application publication date: 20170222 |