CN109473671A - A kind of preparation method of silicon coating modification tertiary cathode material - Google Patents
A kind of preparation method of silicon coating modification tertiary cathode material Download PDFInfo
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- CN109473671A CN109473671A CN201811306181.5A CN201811306181A CN109473671A CN 109473671 A CN109473671 A CN 109473671A CN 201811306181 A CN201811306181 A CN 201811306181A CN 109473671 A CN109473671 A CN 109473671A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- 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
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Abstract
The invention discloses a kind of preparation methods of silicon coating modification tertiary cathode material, comprising the following steps: a, the preparation of silicon covering liquid: liquid silicon source is added in dehydrated alcohol, and a certain amount of dispersing agent is added, persistently stirs to get silicon covering liquid；B, coating reaction: by ternary compound oxides LiNixCoyMn1‑x‑yO2It is added in silicon covering liquid, it is lasting to stir, carry out coating reaction；C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, is washed, drying, calcining, obtaining silicon coating modification tertiary cathode material after natural cooling.Operation of the present invention is simple, and sintering process is stablized without particular/special requirement, synthesized material structure, and circulation and high-temperature behavior are good, environmental-friendly.
Description
Technical field
The present invention relates to anode material of lithium battery fields, more particularly, to a kind of system of silicon coating modification tertiary cathode material
Preparation Method.
Background technique
Lithium ion battery has many advantages, such as that voltage is high, specific energy is big, has extended cycle life, stable operating voltage, self discharge are small,
It is considered to have one of the battery of development potentiality.Positive electrode is the important component of lithium ion battery, it be both lithium from
The bottleneck that sub- battery capacity improves, and determine the most important factor of lithium ion battery price.Find high discharge capacity, stability
Positive electrode, the honest and clean positive electrode of output object favorable rates becomes the hot spot that industry is persistently attracted attention.The safety of ternary material, energy
Density, output performance, also circulation and cost are in comparison more balanced, and nickelic ternary is increasingly becoming power battery development
Trend.
Current nickelic ternary material is existing, and there is also technical problem underlyings: being the phase transition of particle surface first, is easy
Cause the decaying of battery capacity, cycle performance；Second is that particle fragmentation after circulation, causes chemical property to be decayed, leads to thermostabilization
Property, security performance decline.
In order to improve the stability and chemical property of nickelic ternary material, adulterated in material lattice some metals from
Son and nonmetallic ion coat the suitable compound of some thickness on the surface of the material, are proved to be effective measures.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of silicon coating modification tertiary cathode material is provided
Preparation method, easy to operate, sintering process without particular/special requirement, stablize by synthesized material structure, circulation and high-temperature behavior
It is good, it is environmental-friendly.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: liquid silicon source being added in dehydrated alcohol, and a certain amount of dispersing agent is added, is persistently stirred
It mixes to obtain silicon covering liquid；
B, coating reaction: by ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, it is lasting to stir, into
Row coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, is washed, drying, calcining, obtaining silicon packet after natural cooling
Cover modified tertiary cathode material.
Ni2+、Co2+、Mn2+Molar ratio is 6:2:2 or 8:1:1.
Liquid silicon source in step a is positive one of silester, silicic acid, silane coupling agent, and dispersing agent is triethyl group
One of hexyl phosphoric acid, polyethylene glycol, methyl anyl alcohol.
The mass ratio of liquid silicon source and dehydrated alcohol in step a is 3:400-1:300, the matter of dispersing agent and liquid silicon source
Amount is than being 2:3-4:1.
Mixing time in step a is 1-3h.
The pH of silicon covering liquid in step a is 5-7.
Ternary compound oxides LiNi in step bxCoyMn1-x-yO2Mass ratio with dehydrated alcohol is 1:1.2-1:2.
Mixing time in step b is 2-4h.
Cleaning solution in step c is pure water or dehydrated alcohol, and dosage is ternary compound oxides LiNixCoyMn1-x-yO2
The 25%-35% of quality, washing times are 2-3 times.
Drying temperature in step c is 120-150 DEG C, drying time 3-5h, and calcination temperature is 500-700 DEG C, calcining
Time is 6-10h.
The beneficial effects of the present invention are: low to synthesis device requirement, easy to operate, sintering process is without particular/special requirement.It is closed
At material structure stablize, circulation and high-temperature behavior are good, environmental-friendly, therefore it is suitble to do the positive electrode of power battery.
Specific embodiment
Detailed process of the invention is described further by the following examples.
Embodiment 1:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 0.5g ethyl orthosilicate being added in 120g dehydrated alcohol, and the poly- second of 1.0g is added
Glycol persistently stirs 1h, obtains the silicon covering liquid that pH is 5；
B, coating reaction: by 100g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 6:2:2, persistently stirs 2h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, is then washed 2 times, at 120 DEG C with 30g dehydrated alcohol
Dry 5h, 6h is calcined at 700 DEG C, silicon coating modification tertiary cathode material is obtained after natural cooling.
Embodiment 2:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 0.5g ethyl orthosilicate being added in 120g dehydrated alcohol, and three second of 1.0g are added
Base hexyl phosphoric acid, persistently stirs 1h, obtains the silicon covering liquid that pH is 6；
B, coating reaction: by 100g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 6:2:2, persistently stirs 3h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, is then washed 3 times, at 150 DEG C with 30g dehydrated alcohol
Dry 3h, 10h is calcined at 500 DEG C, silicon coating modification tertiary cathode material is obtained after natural cooling.
Embodiment 3:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 1g ethyl orthosilicate being added in 150g dehydrated alcohol, and the poly- second two of 3.0g is added
Alcohol persistently stirs 1h, obtains the silicon covering liquid that pH is 7；
B, coating reaction: by 120g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 8:1:1, persistently stirs 4h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, and then uses 30g pure water 3 times, is dry at 150 DEG C
3h calcines 10h at 500 DEG C, and silicon coating modification tertiary cathode material is obtained after natural cooling.
Embodiment 4:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 0.5g silicic acid being added in 150g dehydrated alcohol, and the methyl anyl alcohol of 2.0g is added, is held
Continuous stirring 2h, obtains the silicon covering liquid that pH is 5；
B, coating reaction: by 120g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 8:1:1, persistently stirs 2h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, is then washed 2 times, at 120 DEG C with 30g dehydrated alcohol
Dry 5h, 8h is calcined at 600 DEG C, silicon coating modification tertiary cathode material is obtained after natural cooling.
Embodiment 5:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 1.0g silicic acid being added in 200g dehydrated alcohol, and the polyethylene glycol of 3.0g is added, is held
Continuous stirring 2h, obtains the silicon covering liquid that pH is 6；
B, coating reaction: by 100g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 6:2:2, persistently stirs 3h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, is then washed 2 times, at 120 DEG C with 35g dehydrated alcohol
Dry 5h, 8h is calcined at 600 DEG C, silicon coating modification tertiary cathode material is obtained after natural cooling.
Embodiment 6:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 1.0g ethyl orthosilicate being added in 150g dehydrated alcohol, and the methyl of 1.0g is added
Amylalcohol persistently stirs 1h, obtains the silicon covering liquid that pH is 7；
B, coating reaction: by 100g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 6:2:2, persistently stirs 3h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, and then uses 30g pure water 2 times, is dry at 120 DEG C
5h calcines 6h at 700 DEG C, and silicon coating modification tertiary cathode material is obtained after natural cooling.
Embodiment 7:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 1.0g silane coupling agent being added in 150g dehydrated alcohol, and three second of 2.0g are added
Base hexyl phosphoric acid, persistently stirs 3h, obtains the silicon covering liquid that pH is 5；
B, coating reaction: by 100g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 8:1:1, persistently stirs 4h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, is then washed 2 times, at 150 DEG C with 30g dehydrated alcohol
Dry 3h, 6h is calcined at 700 DEG C, silicon coating modification tertiary cathode material is obtained after natural cooling.
Embodiment 8:
A kind of preparation method of silicon coating modification tertiary cathode material, comprising the following steps:
A, prepared by silicon covering liquid: 1.5g silane coupling agent being added in 200g dehydrated alcohol, and the poly- second of 1.0g is added
Glycol persistently stirs 1h, obtains the silicon covering liquid that pH is 7；
B, coating reaction: by 150g ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, Ni2+、Co2 +、Mn2+Molar ratio is 8:1:1, persistently stirs 4h, carries out coating reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, is filtered, and then uses 50g pure water 2 times, is dry at 120 DEG C
5h calcines 6h at 700 DEG C, and silicon coating modification tertiary cathode material is obtained after natural cooling.
Silicon obtained in embodiment 1-8 is coated into LiNixCoyMn1-x-yO2With uncoated LiNixCoyMn1-x-yO2Material exists
Circulation discharge test is carried out under the conditions of 3.0-4.3V, 0.5C multiplying power, test result is as follows table:
In conclusion the present invention is low to synthesis device requirement, easy to operate, sintering process is without particular/special requirement.Synthesized
Material structure is stablized, and circulation and high-temperature behavior are good, environmental-friendly, therefore it is suitble to do the positive electrode of power battery.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon coating modification tertiary cathode material, which comprises the following steps:
A, prepared by silicon covering liquid: liquid silicon source being added in dehydrated alcohol, and a certain amount of dispersing agent is added, is persistently stirred
To silicon covering liquid；
B, coating reaction: by ternary compound oxides LiNixCoyMn1-x-yO2It is added in silicon covering liquid, it is lasting to stir, it is wrapped
Cover reaction；
C, secondary treatment: being separated by solid-liquid separation after reaction, filter, wash, drying, calcining, obtained after natural cooling silicon cladding change
Property tertiary cathode material.
2. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that Ni2+、
Co2+、Mn2+Molar ratio is 6:2:2 or 8:1:1.
3. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step a
In liquid silicon source be positive one of silester, silicic acid, silane coupling agent, dispersing agent is triethyl group hexyl phosphoric acid, poly- second
One of glycol, methyl anyl alcohol.
4. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step a
In liquid silicon source and the mass ratio of dehydrated alcohol be 3:400-1:300, the mass ratio of dispersing agent and liquid silicon source is 2:3-4:
1。
5. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step a
In mixing time be 1-3h.
6. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step a
In silicon covering liquid pH be 5-7.
7. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step b
Middle ternary compound oxides LiNixCoyMn1-x-yO2Mass ratio with dehydrated alcohol is 1:1.2-1:2.
8. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step b
In mixing time be 2-4h.
9. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step c
In cleaning solution be pure water or dehydrated alcohol, dosage be ternary compound oxides LiNixCoyMn1-x-yO2The 25%- of quality
35%, washing times are 2-3 times.
10. a kind of preparation method of silicon coating modification tertiary cathode material according to claim 1, which is characterized in that step c
In drying temperature be 120-150 DEG C, drying time 3-5h, calcination temperature be 500-700 DEG C, calcination time 6-10h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112186187A (en) * | 2020-09-30 | 2021-01-05 | 天津巴莫科技有限责任公司 | Preparation method and application of three-dimensional net-shaped coated ternary material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040091779A1 (en) * | 2002-11-01 | 2004-05-13 | The University Of Chicago | Layered cathode materials for lithium ion rechargeable batteries |
| CN103094520A (en) * | 2012-12-31 | 2013-05-08 | 常州大学 | Anode material for lithium ion battery and preparation method thereof |
| CN105655566A (en) * | 2016-04-12 | 2016-06-08 | 北京工业大学 | Synthesis method of silicon dioxide coated lithium-rich manganese-based cathode material |
-
2018
- 2018-11-05 CN CN201811306181.5A patent/CN109473671A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040091779A1 (en) * | 2002-11-01 | 2004-05-13 | The University Of Chicago | Layered cathode materials for lithium ion rechargeable batteries |
| CN103094520A (en) * | 2012-12-31 | 2013-05-08 | 常州大学 | Anode material for lithium ion battery and preparation method thereof |
| CN105655566A (en) * | 2016-04-12 | 2016-06-08 | 北京工业大学 | Synthesis method of silicon dioxide coated lithium-rich manganese-based cathode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112186187A (en) * | 2020-09-30 | 2021-01-05 | 天津巴莫科技有限责任公司 | Preparation method and application of three-dimensional net-shaped coated ternary material |
| CN112186187B (en) * | 2020-09-30 | 2021-09-14 | 天津巴莫科技有限责任公司 | Preparation method and application of three-dimensional net-shaped coated ternary material |
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