CN105742596B - A kind of preparation method of anode material for lithium-ion batteries - Google Patents
A kind of preparation method of anode material for lithium-ion batteries Download PDFInfo
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- CN105742596B CN105742596B CN201610126716.5A CN201610126716A CN105742596B CN 105742596 B CN105742596 B CN 105742596B CN 201610126716 A CN201610126716 A CN 201610126716A CN 105742596 B CN105742596 B CN 105742596B
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/485—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
- 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
Abstract
The present invention provides a kind of preparation method of anode material for lithium-ion batteries, and elder generation adds in complexing agent in lithium source solution, adjusts the pH to 57 of lithium source solution, obtains lithium salts colloidal sol；Positive electrode material precursor is added in lithium salts colloidal sol and is mixed into slurry, while stirring heating evaporation solution, obtains dry gel；Dry gel is calcined to get to anode material for lithium-ion batteries.Lithium salts colloidal sol and positive electrode material precursor contact area are big in the present invention, be conducive to the two uniformly mixing, the quick progress of reaction is may advantageously facilitate in high-temperature calcination process, has saved cost, the positive electrode Elemental redistribution of preparation is with there is superior chemical property.
Description
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to a kind of preparation of anode material for lithium-ion batteries
Method.
Background technology
Lithium ion battery has, stable circulation higher than energy, voltage platform is high, self-discharge rate is low and environmental-friendly spy
Point, therefore have a wide range of applications in 3C consumer electronics and power battery field.The beginning of this century is rapidly sent out in new energy field
Under the background of exhibition, searching energy storage density bigger, cycle life are longer, security performance more preferably lithium-ion battery system also becomes
Scientific research institutions and the research emphasis direction of enterprise.High power capacity and high-voltage technology route develop as current field of lithium ion battery
Main flow direction.Positive electrode mainly includes the LiNi of high voltage used by this two technology paths0.5Mn1.5O4Material,
And the layered cathode material of a high power capacity such as ternary electrode Li (NixCoyMn1-x-y)O2(0<x<1,0<y<1), LiNixCo1-xO2
(0≤x≤1), lithium-rich manganese-based electrode xLi2MnO3·(1-x)LiMO2(M=Ni, Co, Mn, 0<x<1)), Li
(NixCoyAl1-x-y)O2(0<x<1,0<y<1).
Common method for preparing anode material is by material precursor and Li2CO3Mechanical mixture, at high-temperature calcination
Reason, obtains finished-product material.But the method for mechanical mixture is larger to the destruction of presoma pattern, such as ternary material forerunner
Body is prepared using coprecipitation, and pattern is generally the secondary spherical particle that crystal grain reunion of sub-micron forms.It is not made
Before finished product, spherical structure is more loose, if using mechanical batch mixing, presoma pattern can be caused to crush, ternary material into
The shortcomings that product tap density is low, poor processability.On the other hand, long the time required to mechanical mix grinding, batch mixing is susceptible to uneven
The phenomenon that, it will also result in Li in sintering process and be segregated, the low result of electrode material performance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of lithium ion battery electrode material, for improving lithium-ion electric
The chemical property of pond positive electrode.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of anode material for lithium-ion batteries, comprises the following steps：
（1）Complexing agent is added in lithium source solution, the pH to 5-7 of lithium source solution is adjusted, obtains lithium salts colloidal sol；
（2）Positive electrode material precursor is added in lithium salts colloidal sol and is mixed into slurry, while stirring heating evaporation solution, is obtained
To dry gel；
（3）Dry gel is calcined to get to anode material for lithium-ion batteries.
Further scheme, lithium source is lithium nitrate, in lithium carbonate, lithium hydroxide in the lithium source solution in the step (1)
It is at least one.
Further scheme, the complexing agent in the step (1) is ammonium hydroxide, and the addition of complexing agent is the 1- of lithium source mole
1.5 again.
Further scheme, the concentration of the lithium salts colloidal sol in the step (1) is 0.1-10mol/L.
Further scheme, the positive electrode material precursor in the step (2) are NixCoyMn1-x-yO2Or NixCoyMn1-x-y
(OH)2Or NixCoyAl1-x-yO2Or NixCoyAl1-x-y(OH)2, wherein 0<x<1,0<y<1；Or it is MnxM1-xO2Or NixCo1-xO2Or
NixCo1-x(OH)2, wherein M=Ni, Co, Mn, 0<x<1.
Further scheme, the molar ratio of lithium salts colloidal sol and positive electrode material precursor in the step (2) is 0.98-1.2：
1, the solid content being mixed into slurry is 40-70wt%.
Further scheme, the calcining in the step (3) be in air or oxygen atmosphere, temperature forges for 800 ~ 950 DEG C
Burn 10-18h.
Positive electrode material precursor mentioned in the present invention is the hydroxide or oxygen of corresponding positive electrode metal salt
Compound.Lithium source solution is that lithium source is dissolved in the solution formed in water or acid.
The beneficial effects of the invention are as follows：
(1) present invention adds in complexing agent ammonium hydroxide lithium ion is complexed, and makes system evenly；Adjust lithium salts sol body simultaneously
The pH of system to 5-7, so as to ensure that the lithium ion being complexed in lithium colloidal sol will not Precipitation, also ensure lithium colloidal sol acidity will not
Corrode positive electrode material precursor；
(2) positive electrode material precursor is added in lithium salts colloidal sol and is mixed into slurry, it is 40- to make solid content in the slurry
70%, ensure that sol system comes into full contact with positive electrode material precursor, and in next step drying process during shortening evaporation of the solvent
Between；
(3) method used in the present invention can allow positive electrode material precursor to be mixed with lithium source evenly, and mixed process has
Beneficial to presoma pattern is kept, improve the chemical property and processing performance of lithium ion anode material；
(4) the characteristics of present invention is using lithium salts colloidal sol and big positive electrode material precursor contact area, is uniformly mixed beneficial to the two
It closes, the quick progress of reaction is may advantageously facilitate in high-temperature calcination process, has saved cost, the positive electrode Elemental redistribution of preparation
With there is superior chemical property.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the button battery first charge-discharge curve made by positive electrode prepared by the embodiment of the present invention 1 and comparative example；
Fig. 2 is positive electrode multiplying power prepared by the embodiment of the present invention 1 and comparative example and Xun Huan figure.
Specific implementation method
The present invention is described in detail with reference to specific embodiment, but embodiments of the present invention are not limited to
This.
Embodiment 1
（1）After lithium carbonate is added in nitric acid dissolving, complexing agent ammonium hydroxide is further added in, the pH to 7 of solution is adjusted, obtains dense
Spend the lithium salts colloidal sol for 2mol/L；
（2）By positive electrode material precursor Ni0.6Co0.2Mn0.2(OH)2It is added in lithium salts colloidal sol and is mixed into slurry, wherein lithium
The molar ratio of salt sol and positive electrode material precursor is 1.02：1, the solid content in slurry is 60wt%, while stirring heating evaporation
Solution obtains dry gel；
（3）In air, by dry gel in 870 DEG C of temperature calcination 15h to get to anode material for lithium-ion batteries
LiNi0.6Co0.2Mn0.2O2。
Comparative example：By Ni0.6Co0.2Mn0.2(OH)2Presoma and Li2CO3Powder is according to molar ratio 1:0.51 ratio carries out machine
Tool mix grinding, then by it in air with 870 DEG C of temperature calcination 15h to get to anode material for lithium-ion batteries.
Using mass ratio as 0.8：0.1：0.1, positive electrode prepared by above-described embodiment 1 and comparative example
LiNi0.6Co0.2Mn0.2O2Lithium battery anode is made after uniformly being mixed with conductive black and Kynoar respectively, cathode is gold
Belong to lithium piece, then test its charge-discharge performance respectively, specifically as shown in Figure 1, 2.
Fig. 1 is first charge-discharge curve.Under 0.1C multiplying powers, the head of lithium battery made of positive electrode prepared by the present invention
Secondary discharge capacity has reached 180.5mAh/g, and the discharge capacity for the first time of lithium battery made of comparative example positive electrode is
173.3mAh/g, i.e., the positive electrode that prepared by the present invention compare the discharge capacity for the first time of positive electrode made of more mechanical mix grinding method
Improve 4%.
Fig. 2 is the multiplying power of positive electrode and Xun Huan figure.Under 2C multiplying powers, the positive electrode of lithium sol method preparation of the present invention
Capacity retention ratio is 89.2%, and 87.0% than mechanical mix grinding method is promoted.After 1C charge-discharge cycles 100 times, prepared by the present invention
The capacity retention ratio of positive electrode reached 98%, 91.0% than mechanical mix grinding method is obviously improved.
Embodiment 2
（1）After lithia lithium is added in nitric acid dissolving, complexing agent ammonium hydroxide is further added in, the pH to 5 of solution is adjusted, obtains
Concentration is the lithium salts colloidal sol of 10mol/L；
（2）By positive electrode material precursor Ni0.8Co0.15Al0.05(OH)2It is added in lithium salts colloidal sol and is mixed into slurry, lithium salts
The molar ratio of colloidal sol and positive electrode material precursor is 1.2：1, the solid content in slurry is 70wt%, and heating evaporation is molten while stirring
Liquid obtains dry gel；
（3）In air, by dry gel in 950 DEG C of temperature calcination 10h to get to anode material for lithium-ion batteries
LiNi0.8Co0.15Al0.05O2。
Further scheme, the positive electrode material precursor in the step (2) are NixCoyMn1-x-yO2Or NixCoyMn1-x-y
(OH)2Or NixCoyAl1-x-yO2Or NixCoyAl1-x-y(OH)2, wherein 0<x<1,0<y<1；Or it is MnxM1-xO2Or NixCo1-xO2,
Wherein M=Ni, Co, Mn, 0<x<1.
Embodiment 3
（1）After lithium nitrate is added to the water dissolving, complexing agent ammonium hydroxide is further added in, the pH to 6 of solution is adjusted, obtains dense
Spend the lithium salts colloidal sol for 0.1mol/L；
（2）By positive electrode material precursor Mn0.7Ni0.2Co0.1(OH)2It is added in lithium salts colloidal sol and is mixed into slurry, lithium salts is molten
The molar ratio of glue and positive electrode material precursor is 0.98：1, the solid content in slurry is 40wt%, and heating evaporation is molten while stirring
Liquid obtains dry gel；
（3）In oxygen atmosphere, by dry gel in 800 DEG C of temperature calcination 18h to get to lithium ion cell positive material
Expect 0.2Li2MnO3·0.8LiMn0.625Ni0.25Co0.125O2。
Above example is only the embodiment of part of the present invention.It should be noted that embodiments of the present invention are from above-mentioned
The limitation of embodiment, it is other it is any without departing from the present invention Spirit Essences with made under principle change, modification, replacement, combine,
Simplify, be regarded as equivalent substitute mode, be included within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of anode material for lithium-ion batteries, it is characterised in that：Comprise the following steps：
（1）Complexing agent is added in lithium source solution, the pH to 5-7 of lithium source solution is adjusted, obtains lithium salts colloidal sol；
（2）Positive electrode material precursor is added in lithium salts colloidal sol and is mixed into slurry, while stirring heating evaporation solution, is done
Dry gel；
（3）Dry gel is calcined to get to anode material for lithium-ion batteries；
Complexing agent in the step (1) is ammonium hydroxide, and the addition of complexing agent is 1-1.5 times of lithium source mole；The step
（2）In to be mixed into solid content in slurry be 40-70wt%.
2. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：The step (1)
In lithium source solution in lithium source be lithium nitrate, lithium carbonate, at least one of lithium hydroxide.
3. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：The step (1)
In lithium salts colloidal sol concentration be 0.1-10mol/L.
4. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：The step (2)
In positive electrode material precursor be NixCoyMn1-x-yO2Or NixCoyMn1-x-y(OH)2Or NixCoyAl1-x-yO2Or NixCoyAl1-x-y
(OH)2, wherein 0<x<1,0<y<1；Or it is MnxM1-xO2Or NixCo1-xO2Or NixCo1-x(OH)2, wherein M=Ni, Co, Mn, 0<x<
1。
5. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：The step (2)
In lithium salts colloidal sol and positive electrode material precursor molar ratio be 0.98-1.2：1.
6. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that：The step (3)
In calcining be in air or oxygen atmosphere, temperature for 800 ~ 950 DEG C calcining 10-18h.
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| CN108736009A (en) * | 2018-05-29 | 2018-11-02 | 中伟新材料有限公司 | Cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN108878821A (en) * | 2018-06-19 | 2018-11-23 | 合肥国轩高科动力能源有限公司 | A kind of nickelic tertiary cathode material and preparation method thereof of surface cladding lanthana |
| CN110790320B (en) * | 2019-10-25 | 2022-03-11 | 合肥国轩高科动力能源有限公司 | Core-shell structure precursor for lithium ion layered positive electrode material and preparation method thereof |
| CN111943281B (en) * | 2020-08-04 | 2022-05-24 | 厦门厦钨新能源材料股份有限公司 | Environment-friendly precursor and composite oxide powder, and preparation method and application thereof |
| CN113683125A (en) * | 2021-07-22 | 2021-11-23 | 宁夏汉尧石墨烯储能材料科技有限公司 | Method for preparing low-cobalt cathode material by sol-gel-solid phase sintering method |
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| CN102709543A (en) * | 2012-06-06 | 2012-10-03 | 株洲泰和高科技有限公司 | Rich-lithium ternary laminar lithium ion battery cathode material |
| CN102709568A (en) * | 2012-06-25 | 2012-10-03 | 天津工业大学 | Preparation method for nickel cobalt lithium manganate LiNixConMn1-x-yO2 of anode material of lithium ion battery |
| CN103413932A (en) * | 2013-08-19 | 2013-11-27 | 北大先行科技产业有限公司 | Modified single crystal type multielement anode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709543A (en) * | 2012-06-06 | 2012-10-03 | 株洲泰和高科技有限公司 | Rich-lithium ternary laminar lithium ion battery cathode material |
| CN102709568A (en) * | 2012-06-25 | 2012-10-03 | 天津工业大学 | Preparation method for nickel cobalt lithium manganate LiNixConMn1-x-yO2 of anode material of lithium ion battery |
| CN103413932A (en) * | 2013-08-19 | 2013-11-27 | 北大先行科技产业有限公司 | Modified single crystal type multielement anode material and preparation method thereof |
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