CN106410184B - A kind of tiny balloon flower-like structure tertiary cathode material and preparation and application - Google Patents
A kind of tiny balloon flower-like structure tertiary cathode material and preparation and application Download PDFInfo
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- CN106410184B CN106410184B CN201610934860.1A CN201610934860A CN106410184B CN 106410184 B CN106410184 B CN 106410184B CN 201610934860 A CN201610934860 A CN 201610934860A CN 106410184 B CN106410184 B CN 106410184B
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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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- 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 present invention provides a kind of tiny balloon flower-like structure tertiary cathode material and preparation and application, 0.2 ~ 0.4 g polyvinylpyrrolidone (PVP) is dissolved in 60 ~ 120 mL organic solvents, and 1 ~ 2 mL deionized water is added thereto, form clear solution, by 2 ~ 4 h of the solution magnetic agitation, until solution is uniformly mixed；Then lithium salts, nickel salt, cobalt salt and manganese salt are added in above-mentioned solution according to stoichiometric ratio, 30 ~ 60 min of the solution magnetic agitation are transferred in reaction kettle, 160 ~ 180 DEG C of 12 ~ 15 h of reaction, natural cooling；By above-mentioned sediment centrifugation, ethanol washing 3 ~ 5 times, in 60 ~ 80 DEG C of 20 ~ 24 h of drying, then by the sediment after drying with the heating rate of 1 ~ 2 DEG C/min in 600 ~ 800 DEG C of 5 ~ 10 h of calcining, obtain target product.Under the conditions of 2 C multiplying powers, first discharge specific capacity is 168 mAh/g, is 153 mAh/g, capacity retention ratio 91.07% by 50 circulation specific discharge capacities.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium electricity positive electrode, more particularly to a kind of tiny balloon flower-like structure three
First positive electrode and preparation and application.
Background technique
With the rapid development of smaller, lighter and higher performance electronics and communication apparatus, people mention to for these equipment
The battery performance of power supply source especially proposes increasingly higher demands to specific energy.But the lithium-ion electric being commercialized at present
The specific capacity of pond and MH/Ni battery has been difficult to continue to improve.Therefore, there is an urgent need to develop the higher batteries of specific energy.Lithium from
Sub- secondary cell has been widely used for mobile communication, laptop, video camera, photograph as high-energy-density electrochmical power source
The fields such as machine, portable instrument, rapidly developing becomes one of currently the most important ones secondary cell.
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 the ratio for adjusting nickel, cobalt, manganese, the ternary electrode material of different performance can be prepared.With new energy vapour
The rise and development of vehicle, ternary material are the hot spots of research.
The present invention prepares the ternary material of tiny balloon flower-like structure using solvent thermal reaction, nanometer sheet assembling.It is hollow micro-
The ternary material of ball flower-like structure has biggish specific surface area, can come into full contact with electrolyte, and then material can be improved
Chemical property.
Summary of the invention
In order to overcome the deficiencies of the prior art, the present invention provides a kind of tiny balloon flower-like structure tertiary cathode material and preparation
And application.
A kind of preparation method of tiny balloon flower-like structure tertiary cathode material, which is characterized in that the specific step of this method
Suddenly are as follows:
(1) 0.2 ~ 0.4 g polyvinylpyrrolidone (PVP) is dissolved in 60 ~ 120 mL organic solvents, and be added thereto
1 ~ 2 mL deionized water forms clear solution, by 2 ~ 4 h of the solution magnetic agitation, until solution is uniformly mixed；
(2) then lithium salts, nickel salt, cobalt salt and manganese salt are added in above-mentioned solution according to stoichiometric ratio, by the solution magnetic
Power stirs 30 ~ 60 min, is transferred in reaction kettle, 160 ~ 180 DEG C of 12 ~ 15 h of reaction, natural cooling；
(3) by the centrifugation of above-mentioned sediment, ethanol washing 3 ~ 5 times, in 60 ~ 80 DEG C of 20 ~ 24 h of drying, after then drying
Sediment with the heating rate of 1 ~ 2 DEG C/min in 600 ~ 800 DEG C of 5 ~ 10 h of calcining, obtain target product.
The organic solvent is one of ethylene glycol or glycerine or combinations thereof.
The lithium salts is one of lithium nitrate, lithium acetate, lithium citrate, lithium formate or lithium lactate or combinations thereof.
The nickel salt is one of nickel nitrate, nickel acetate or nickel oxalate or combinations thereof.
The cobalt salt is one of cobalt nitrate, cobalt acetate or cobalt oxalate or combinations thereof.
A kind of tiny balloon flower-like structure tertiary cathode material, which is characterized in that prepared according to any of the above-described the method
It obtains.
A kind of application of tiny balloon flower-like structure tertiary cathode material as lithium electricity positive electrode.
The present invention provides a kind of tiny balloon flower-like structure tertiary cathode material (LiNi1-x-yCoxMnyO2(0 < x < 1,0 < y <
1) preparation method), the present invention prepare the ternary material of tiny balloon flower-like structure using solvent thermal reaction, nanometer sheet assembling.
The ternary material of tiny balloon flower-like structure has biggish specific surface area, can come into full contact with electrolyte, and then can mention
The chemical property of high material.Under the conditions of 2 C multiplying powers, first discharge specific capacity is 168 mAh/g, by 50 circulations electric discharge ratios
Capacity is 153 mAh/g, capacity retention ratio 91.07%.
Detailed description of the invention
Fig. 1 is 1 tiny balloon flower-like structure LiNi of embodiment1/3Co1/3Mn1/3O2The XRD diagram of material.
Fig. 2 is 2 tiny balloon flower-like structure LiNi of embodiment0.5Co0.3Mn0.2O2The cycle life figure of material.
Specific embodiment
The present invention is described in detail by following specific example, but protection scope of the present invention is not only restricted to these
Examples of implementation.
Embodiment one:
0.2 g polyvinylpyrrolidone (PVP) is dissolved in 60 mL ethylene glycol, and 1 mL deionized water is added thereto,
Clear solution is formed, by 2 h of the solution magnetic agitation, until solution is uniformly mixed；Then by 1 mmol lithium acetate, 0.3333
Mmol nickel acetate, 0.3333 mmol cobalt acetate and 0.3333 mmol manganese acetate are added in above-mentioned solution, which is stirred
60 min are mixed, are transferred in reaction kettle, 160 DEG C of 15 h of reaction, natural cooling；By the centrifugation of above-mentioned sediment, ethanol washing 3
It is secondary, in 60 DEG C of 24 h of drying.Then by the sediment after drying with the heating rate of 1 DEG C/min in 600 DEG C of 10 h of calcining, obtain
To the LiNi of target product tiny balloon flower-like structure1/3Co1/3Mn1/3O2.Fig. 1 is tiny balloon flower-like structure LiNi1/3Co1/ 3Mn1/3O2The XRD diagram of material, through comparing with document, which is pure phase, and R(003)/(104)=1.7, it is greater than 1.2, explanation does not have
Li+With Ni2+Ion mix phenomenon, (006)/(102) and (108)/(110) division peak illustrate that material is layer structure.
Embodiment two:
0.2 g polyvinylpyrrolidone (PVP) is dissolved in 60 mL glycerine, and 1 mL deionized water is added thereto,
Clear solution is formed, by 2 h of the solution magnetic agitation, until solution is uniformly mixed；Then by 1 mmol lithium nitrate, 0.5 mmol nitre
Sour nickel, 0.3 mmol cobalt nitrate and 0.2 mmol manganese nitrate are added in above-mentioned solution, by 30 min of the solution magnetic agitation, by it
It is transferred in reaction kettle, 180 DEG C of 12 h of reaction, natural cooling；By the centrifugation of above-mentioned sediment, ethanol washing 3 times, dried at 80 DEG C
20 h.Then by the sediment after drying with the heating rate of 1 DEG C/min in 800 DEG C of 5 h of calcining, it is hollow to obtain target product
The LiNi of micro-sphere structure0.5Co0.3Mn0.2O2.Fig. 2 is hollow microsphere structure LiNi0.5Co0.3Mn0.2O2The cycle life figure of material, 2
Under the conditions of C multiplying power, first discharge specific capacity 168mAh/g is 153mAh/g by 50 circulation specific discharge capacities, and capacity is protected
Holdup is 91.07%.
Embodiment three:
0.4 g polyvinylpyrrolidone (PVP) is dissolved in 120 mL glycerine, and 1 mL deionization is added thereto
Water forms clear solution, by 4 h of the solution magnetic agitation, until solution is uniformly mixed；Then by 1 mmol lithium nitrate, 0.8
Mmol nickel nitrate, 0.1 mmol cobalt nitrate and 0.1 mmol manganese nitrate are added in above-mentioned solution, by the solution magnetic agitation 60
Min is transferred in reaction kettle, 180 DEG C of 12 h of reaction, natural cooling；Above-mentioned sediment is centrifuged, ethanol washing 3 times,
80 DEG C of 20 h of drying.Then by the sediment after drying with the heating rate of 2 DEG C/min in 750 DEG C of 8 h of calcining, obtain target
The LiNi of product hollow microsphere structure0.8Co0.1Mn0.1O2。
Claims (3)
1. a kind of preparation method of tiny balloon flower-like structure tertiary cathode material, which is characterized in that the specific steps of this method
Are as follows:
(1) 0.2 ~ 0.4 g polyvinylpyrrolidone (PVP) is dissolved in 60 ~ 120 mL organic solvents, and 1 ~ 2 is added thereto
ML deionized water forms clear solution, by 2 ~ 4 h of the solution magnetic agitation, until solution is uniformly mixed；
(2) then lithium salts, nickel salt, cobalt salt and manganese salt are added in above-mentioned solution according to stoichiometric ratio, which is stirred
30 ~ 60 min are mixed, are transferred in reaction kettle, 160 ~ 180 DEG C of 12 ~ 15 h of reaction, natural cooling；
(3) the sediment centrifugation that obtains step (2), ethanol washing 3 ~ 5 times, then will baking in 60 ~ 80 DEG C of 20 ~ 24 h of drying
Sediment after dry, in 600 ~ 800 DEG C of 5 ~ 10 h of calcining, obtains target product with the heating rate of 1 ~ 2 DEG C/min；
The organic solvent is one of ethylene glycol or glycerine or combinations thereof；
The lithium salts is one of lithium nitrate, lithium acetate, lithium citrate, lithium formate or lithium lactate or combinations thereof；
The nickel salt is one of nickel nitrate, nickel acetate or nickel oxalate or combinations thereof；
The cobalt salt is one of cobalt nitrate, cobalt acetate or cobalt oxalate or combinations thereof.
2. a kind of tiny balloon flower-like structure tertiary cathode material, which is characterized in that be prepared into method according to claim 1
It arrives.
3. application of the tiny balloon flower-like structure tertiary cathode material as lithium electricity positive electrode according to claim 2.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107134571B (en) * | 2017-05-11 | 2019-10-22 | 浙江工业职业技术学院 | A kind of preparation method of low partial size tertiary cathode material |
| CN107445214B (en) * | 2017-09-05 | 2019-06-04 | 中南大学 | A kind of lithium ion battery nickel-cobalt-manganternary ternary anode material and preparation method thereof |
| CN107887599A (en) * | 2017-11-01 | 2018-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application |
| 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 |
| CN112357975B (en) * | 2020-09-30 | 2021-09-07 | 宜宾光原锂电材料有限公司 | Preparation method of hollow ternary cathode material precursor and prepared ternary cathode material precursor |
| CN113321246A (en) * | 2021-05-27 | 2021-08-31 | 南京市永信合智能科技有限公司 | Preparation method of in-situ lithium alcoholization ternary nanosheet cathode material |
| CN115947388A (en) * | 2022-12-31 | 2023-04-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ternary nano positive electrode material, product and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868122A (en) * | 2015-05-15 | 2015-08-26 | 北京理工大学 | Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material |
| CN105702936A (en) * | 2016-04-07 | 2016-06-22 | 华南师范大学 | Manganese-base carbon-coated nano lithium-rich oxide and preparation method as well as application thereof |
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- 2016-11-01 CN CN201610934860.1A patent/CN106410184B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868122A (en) * | 2015-05-15 | 2015-08-26 | 北京理工大学 | Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material |
| CN105702936A (en) * | 2016-04-07 | 2016-06-22 | 华南师范大学 | Manganese-base carbon-coated nano lithium-rich oxide and preparation method as well as application thereof |
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