CN108987742A - A kind of nickelic positive electrode of lithium ion battery and preparation method thereof - Google Patents
A kind of nickelic positive electrode of lithium ion battery and preparation method thereof Download PDFInfo
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- CN108987742A CN108987742A CN201810814859.4A CN201810814859A CN108987742A CN 108987742 A CN108987742 A CN 108987742A CN 201810814859 A CN201810814859 A CN 201810814859A CN 108987742 A CN108987742 A CN 108987742A
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- positive electrode
- lithium
- ion battery
- lithium ion
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/50—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 present invention relates to a kind of technical field of lithium-ion battery, and in particular to a kind of nickelic positive electrode of lithium ion battery and preparation method thereof.The chemical formula of the nickelic positive electrode of lithium ion battery of the present invention is LiNixCoyM1‑x‑yO2(0.5≤x≤1,0≤y≤0.5)；Wherein M is one or more of Mn, B, Al, Ga, Si, Mg, Ti, V, Cr, Zr, Mo.The preparation method of the nickelic positive electrode of lithium ion battery of the present invention includes: to mix nickel cobalt hydroxide precursor with lithium compound, and 0.02~20h is sintered at 300~800 DEG C；Resulting material in above-mentioned steps is mixed with sintering aid, adds lithium compound, under oxygen atmosphere, is sintered 0.04~40h at 600~850 DEG C；Resulting materials in above-mentioned steps are washed to alkali content lower than 300umol/g, are dried to obtain the nickelic positive electrode of lithium ion battery.Using nickelic positive electrode prepared by the present invention, specific discharge capacity with higher, excellent cycle performance and storge quality.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, and in particular to a kind of nickelic positive electrode of lithium ion battery and
Preparation method.
Background technique
Positive electrode is material the most key in generally acknowledged lithium ion battery, and it is each that performance quality will directly affect battery
Item performance (energy density, cycle life, safety etc.).Nineteen ninety Sony company is by stratiform cobalt acid lithium (LiCoO2) as anode
Material and realize commercialization promote and apply after, people have found other anode material for lithium-ion batteries in succession, such as stratiform
Lithium nickelate (LiNiO2), lithium manganate having spinel structure (LiMn2O4) and olivine-type LiFePO4 (LiFePO4) etc..
Tertiary cathode material (LiNixCoyMn1-x-yO2) combine LiNiO2、LiCoO2And LiMn2O4Three classes material it is excellent
Point has stable chemical property (higher charge/discharge capacity, good high rate performance, wider electrochemical window) and good
Good security performance, is suitable as the positive electrode of power battery.In ternary material, with the increase of nickel content, mass ratio
Capacity also increases, so the positive electrode for developing nickelic system is the effective hand for improving lithium ion battery energy density and reducing cost
Section.
But there is synthesis difficulty, Capacity fading, high surface activity, thermal stability difference etc. in the positive electrode of nickelic system
Technological challenge.Due to high-nickel material high surface activity, it is easy to and the H in air2O and CO2Reaction generates lithium carbonate and hydroxide
Lithium leads to the alkalinity that material surface is high, these lithium carbonates and lithium hydroxide seriously affect the processing performance for influencing material, gram volume
And cycle performance, while battery can also be made to be easy to produce gas at high temperature.Publication No. CN104091942B,
The patent of invention of CN105244490A, CN107706414A, CN105070908B, CN106654222A, CN107256955A mention
A kind of method for preparing the nickelic positive electrode of lithium ion battery is gone out, has been improved by the means such as addition metal oxide and washing high
The chemical property of nickel material, reduce surface alkali content, but its effect is unsatisfactory.
Present invention is generally directed to the problems of existing nickelic method for preparing anode material to improve.
Summary of the invention
A primary object of the present invention is to overcome at least one defect in the prior art, provides a kind of lithium-ion electric
Nickelic positive electrode in pond and preparation method thereof, by adding sintering aid, preparation method of the present invention can be simply and effectively
It improves the specific discharge capacity of nickelic positive electrode and improves the cycle performance and storge quality of material.
In order to realize above-mentioned technical proposal, the invention adopts the following technical scheme:
According to an aspect of the present invention, a kind of nickelic positive electrode of lithium ion battery, the change of the positive electrode are provided
Formula is LiNixCoyM1-x-yO2(0.5≤x≤1,0≤y≤0.5)；
Wherein, the M is one or more of Mn, B, Al, Ga, Si, Mg, Ti, V, Cr, Zr, Mo.
According to an embodiment of the present invention, the M is Mn element or Al element.
According to another aspect of the present invention, a kind of preparation method of nickelic positive electrode of lithium ion battery is provided, at least
The following steps are included:
S01: nickel cobalt hydroxide precursor is mixed with lithium compound, and 0.02~20h is sintered at 300~800 DEG C,
The molar ratio of Ni, Co, M ion summation is 0.8~1.2 in middle Li ion and presoma；
S02: resulting material in step S01 is mixed with sintering aid, lithium compound is added, under oxygen atmosphere, 600
0.04~40h is sintered at~850 DEG C；
S03: resulting materials in step S02 are washed to alkali content lower than 300umol/g (titration with hydrochloric acid), are dried to obtain lithium
The nickelic positive electrode of ion battery.
According to an embodiment of the present invention, the molecular formula of the nickel cobalt hydroxide precursor is NixCoyM1-x-y
(OH)2(0.5≤x≤1,0≤y≤0.5)；
Wherein, the M is one or more of Mn, B, Al, Ga, Si, Mg, Ti, V, Cr, Zr, Mo.
According to an embodiment of the present invention, the lithium compound be lithia, lithium hydroxide, lithium nitrate, lithium nitride,
One or more of lithium chloride, lithium acetate, lithium borate or lithium oxalate.
According to an embodiment of the present invention, in step S02, the lithium compound being added is relative to nickel cobalt hydroxide
The molar ratio of presoma is 0~0.4.
According to an embodiment of the present invention, in step S02, the sintering aid be Li, Na, K, Rb oxide,
At least one of fluoride, chloride, nitride or hydroxide.
According to an embodiment of the present invention, in step S02, dosage the rubbing relative to presoma of the sintering aid
You are than being 0~0.2.
According to an embodiment of the present invention, in step S03, washing suspension concentration is 100~2000g/ when washing
L, washing temperature are 0~80 DEG C.
As shown from the above technical solution, the present invention has at least one of following advantages and good effect:
(1) reactivity is increased by adding sintering aid, reduces Li/Ni mixing, significantly improves nickelic anode
The chemical property of material.
(2) it since sintering aid is soluble easily in water, is easily washed with water, can reduce since lithium caused in water-washing process is molten
Out, the problems such as performance declines.
Using nickelic positive electrode prepared by preparation method of the present invention, specific discharge capacity with higher, excellent circulation
Performance and storge quality.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, those of ordinary skill in the art are come
It says, without creative efforts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is a kind of nickelic positive electrode LiNi of lithium ion battery of the present invention0.8Co0.15Al0.05O2Scanning electron microscope
Schematic diagram；
Fig. 2 is different embodiments in a kind of nickelic positive electrode of lithium ion battery of the present invention
LiNi0.8Co0.15Al0.05O2Cycle performance contrast schematic diagram.
Specific embodiment
With reference to the accompanying drawing and specific embodiment invention is further described in detail.
Embodiment 1
Referring to Fig. 1, Fig. 1 is a kind of nickelic positive electrode LiNi of lithium ion battery of the present invention0.8Co0.15Al0.05O2's
Scanning electron microscope schematic diagram.
Li:(Ni+Co+Mn in molar ratio)=1.0, by presoma Ni0.85Co0.15Al0.05(OH)2With Li (OH) H2O is mixed
It closes, in 560 DEG C of pre-sintering 6h of low temperature, crushes, sieving, low temperature presintering ramming material is mixed with NaOH, Na:(Ni+Co+Mn after cooling)
=0.06, be sintered 12h at 750 DEG C of oxygen atmosphere medium and high temperature, crushed after cooling, sieving, by resulting materials 25 DEG C,
It is washed in 1000g/L water, is dried to obtain LiNi0.8Co0.15Al0.05O2。
Embodiment 2
Li:(Ni+Co+Mn in molar ratio)=0.9, by presoma Ni0.85Co0.15Al0.05(OH)2With Li (OH) H2O is mixed
It closes, in 560 DEG C of pre-sintering 6h of low temperature, cooling crush, rear sieving are mixed low temperature presintering ramming material with NaOH and LiOH, Na:(Ni+
Co+Mn)=0.06, Li:(Ni+Co+Mn)=0.10,12h is sintered at 750 DEG C of oxygen atmosphere medium and high temperature, crushed after cooling,
Sieving, resulting materials are washed in 25 DEG C, 1000g/L water, are dried to obtain LiNi0.8Co0.15Al0.05O2。
Embodiment 3
Li:(Ni+Co+Mn in molar ratio)=1.0, by presoma Ni0.85Co0.15Al0.05(OH)2With Li (OH) H2O is mixed
Close, in 560 DEG C of pre-sintering 6h of low temperature, cooling crush, rear sieving are mixed low temperature presintering ramming material with KOH, K:(Ni+Co+Mn)=
0.06, it is sintered 12h at 750 DEG C of oxygen atmosphere medium and high temperature, is crushed after cooling, sieving, by resulting materials in 25 DEG C, 1000g/L
It is washed in water, is dried to obtain LiNi0.8Co0.15Al0.05O2。
Comparative example
Li:(Ni+Co+Mn in molar ratio)=1.06, by presoma Ni0.85Co0.15Al0.05(OH)2With Li (OH) H2O is mixed
It closes, in 560 DEG C of pre-sintering 6h of low temperature, cooling crush, rear sieving are sintered 12h, after cooling at 750 DEG C of oxygen atmosphere medium and high temperature
It crushes, sieving, resulting materials is washed in 25 DEG C, 1000g/L water, are dried to obtain LiNi0.8Co0.15Al0.05O2。
The electrochemical property test condition of the nickelic positive electrode of a kind of lithium ion battery of the present invention: in 25 DEG C of temperature
Under, under voltage range 2.75~4.3V, 1C (1C 180mAh/g) current density carry out charge and discharge, and recycle.
The different embodiment chemical properties of table 1 and alkali content
In conclusion in conjunction with attached drawing 1,2, the mass ratio of the high nickel positive active material in the different embodiments of present invention gained
Capacity and cycle performance are shown in table 1, and alkalinity decline after the embodiment washing, gram volume increases, and cycle performance improves.
It should be appreciated that the present invention is not limited in its application to detailed construction and the arrangement side of component proposed in this paper
Formula.The present invention can have other embodiments, and can realize and execute in many ways.Aforesaid deformation form and modification
Form is fallen within the scope of the present invention.It should be appreciated that invention disclosed and defined herein extends in text and/or attached drawing
In mention or all alternative combinations of two or more apparent independent features.Embodiment as described herein illustrates
Know for realizing best mode of the invention, and those skilled in the art will be enable using the present invention.
Claims (9)
1. a kind of nickelic positive electrode of lithium ion battery, which is characterized in that
The chemical formula of the positive electrode is LiNixCoyM1-x-yO2(0.5≤x≤1,0≤y≤0.5)；
Wherein, the M is one or more of Mn, B, Al, Ga, Si, Mg, Ti, V, Cr, Zr, Mo.
2. the nickelic positive electrode of a kind of lithium ion battery according to claim 1, which is characterized in that the M is Mn element
Or Al element.
3. a kind of preparation method of the nickelic positive electrode of lithium ion battery, which is characterized in that at least include the following steps:
S01: nickel cobalt hydroxide precursor is mixed with lithium compound, 0.02~20h is sintered at 300~800 DEG C, wherein Li
The molar ratio of Ni, Co, M ion summation is 0.8~1.2 in ion and presoma；
S02: resulting material in step S01 being mixed with sintering aid, adds lithium compound, under oxygen atmosphere, 600~
0.04~40h is sintered at 850 DEG C；
S03: resulting materials in step S02 are washed to alkali content lower than 300umol/g (titration with hydrochloric acid), are dried to obtain lithium ion
The nickelic positive electrode of battery.
4. a kind of preparation method of the nickelic positive electrode of lithium ion battery according to claim 3, which is characterized in that described
Nickel cobalt hydroxide precursor molecular formula be NixCoyM1-x-y(OH)2(0.5≤x≤1,0≤y≤0.5)；
Wherein, the M is one or more of Mn, B, Al, Ga, Si, Mg, Ti, V, Cr, Zr, Mo.
5. a kind of preparation method of the nickelic positive electrode of lithium ion battery according to claim 3, which is characterized in that described
Lithium compound be lithia, lithium hydroxide, lithium nitrate, lithium nitride, lithium chloride, lithium acetate, lithium borate or lithium oxalate in one
Kind is several.
6. a kind of preparation method of the nickelic positive electrode of lithium ion battery according to claim 3, which is characterized in that in step
In rapid S02, the lithium compound being added is 0~0.4 relative to the molar ratio of nickel cobalt hydroxide precursor.
7. a kind of preparation method of the nickelic positive electrode of lithium ion battery according to claim 3, which is characterized in that in step
In rapid S02, the sintering aid be in oxide, fluoride, chloride, nitride or the hydroxide of Li, Na, K, Rb extremely
Few one kind.
8. a kind of preparation method of the nickelic positive electrode of lithium ion battery according to claim 3, which is characterized in that in step
In rapid S02, the dosage of the sintering aid is 0~0.2 relative to the molar ratio of presoma.
9. a kind of preparation method of the nickelic positive electrode of lithium ion battery according to claim 3, which is characterized in that in step
In rapid S03, washing suspension concentration is 100~2000g/L when washing, and washing temperature is 0~80 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786702A (en) * | 2019-01-04 | 2019-05-21 | 蜂巢能源科技有限公司 | High-nickel material and its preparation method and application |
| CN112831838A (en) * | 2020-12-31 | 2021-05-25 | 南通瑞翔新材料有限公司 | Preparation method of single crystal type nickel cobalt lithium aluminate anode material |
| WO2022208047A1 (en) * | 2021-03-31 | 2022-10-06 | Ev Metals Uk Limited | Process |
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| CN104979552A (en) * | 2014-04-02 | 2015-10-14 | 张联齐 | Preparation method of primary large-particle lithium nickel cobalt aluminate anode material |
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| CN106602015A (en) * | 2016-12-21 | 2017-04-26 | 湖北金泉新材料有限责任公司 | Preparation method for fluorine-doped nickel-cobalt-manganese system ternary positive electrode material and prepared material |
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2018
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| CN104979554A (en) * | 2014-04-02 | 2015-10-14 | 郭建 | Preparation method of lithium nickel cobalt aluminate anode material |
| CN104979552A (en) * | 2014-04-02 | 2015-10-14 | 张联齐 | Preparation method of primary large-particle lithium nickel cobalt aluminate anode material |
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786702A (en) * | 2019-01-04 | 2019-05-21 | 蜂巢能源科技有限公司 | High-nickel material and its preparation method and application |
| CN112831838A (en) * | 2020-12-31 | 2021-05-25 | 南通瑞翔新材料有限公司 | Preparation method of single crystal type nickel cobalt lithium aluminate anode material |
| WO2022208047A1 (en) * | 2021-03-31 | 2022-10-06 | Ev Metals Uk Limited | Process |
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