CN106745337A - A kind of LiNi1/3Co1/3Mn1/3O2Preparation method - Google Patents
A kind of LiNi1/3Co1/3Mn1/3O2Preparation method Download PDFInfo
- Publication number
- CN106745337A CN106745337A CN201710103217.9A CN201710103217A CN106745337A CN 106745337 A CN106745337 A CN 106745337A CN 201710103217 A CN201710103217 A CN 201710103217A CN 106745337 A CN106745337 A CN 106745337A
- Authority
- CN
- China
- Prior art keywords
- lini
- source
- preparation
- ground
- powdery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of LiNi1/3Co1/3Mn1/3O2Preparation method, comprise the following steps：Step 1：Raw material lithium source, nickel source, cobalt source, manganese source and carbon source and appropriate distilled water are ground, rheology phase predecessor is obtained；Wherein, the mol ratio of the lithium source, nickel source, cobalt source, manganese source and carbon source is 1.05:1/3:1/3:1/3:2.05；Step 2：By the rheology phase predecessor in 120 DEG C of air thermostatic drying chambers freeze-day with constant temperature 24h, collect and be ground to powdery；Step 3：Powdery predecessor is heated 6h for 600 DEG C in Muffle furnace, is ground after naturally cooling to room temperature, obtain LiNi1/3Co1/3Mn1/3O2Intermediate product；Step 4：By this LiNi1/3Co1/3Mn1/3O2The intermediate product constant temperature calcining 12h at 800 DEG C, 850 DEG C and 900 DEG C respectively, powdery is ground to after naturally cooling to room temperature, respectively obtains 800 DEG C, 850 DEG C and 900 DEG C of target product LiNi1/3Co1/3Mn1/3O2。
Description
Technical field
The present invention relates to Materials Science and Engineering technical field, more particularly to a kind of LiNi1/3Co1/3Mn1/3O2Preparation side
Method.
Background technology
LiNi1/3Co1/3Mn1/3O2After being synthesized by Ohzuku etc. first in 1999, LiCo1-x-yNiyMnxO2Ternary transition
The research of metal cobalt-nickel-manganese oxide compound is attracted wide attention immediately.At present on LiCo1/3Ni1/3Mn1/3O2Synthesis side
Method mainly has：Low-temperature solid-phase method, hydro-thermal method, coprecipitation, sol-gal process, ullrasonic spraying seasoning and emulsion synthetic method
Deng.
Coprecipitation is to synthesize LiNi at present1/3Co1/3Mn1/3O2A kind of the most commonly used method, its process is by several mistakes
Cross slaine and stoichiometrically match and mixed with solution state, then add appropriate precipitating reagent, while the certain pH of control
Value, makes cation therein while forming infusible precipitate, then to precipitate filtered, wash, the subsequent treatment such as dry after forge
Burning obtains target product.The method has that synthesis reaction temperature is low, product grain pattern is good and product chemistry function admirable etc.
Advantage, but reactant concentration, system temperature and pH value, stir speed (S.S.) in the more such as coprecipitation process of factor of control are needed,
These can all produce considerable influence, therefore system to the crystal formation pattern of target product, grain diameter size and chemical property
Standby process is relative complex；Low-temperature solid-phase method has that process is simple, reaction condition be easily controllable, the low advantage of sintering temperature, can be with
Obtain the good product of uniform component, crystal formation.During its shortcoming is building-up process, each component is difficult to homogeneous blend, inequality of being heated
It is even, need to repeatedly grind and sinter, generated time is extended, cause the waste of energy；Secondly, solid phase products therefrom particle diameter is larger,
It is uneven, the chemical property of material is directly affected, the selection of temperature and raw material is also most important；Hydro-thermal method is with water as molten
Agent, the chemical reaction carried out in the sealing container of HTHP.Hydro-thermal method can obtain the product that purity is high, crystal formation is good, but
Condition is relatively harsh and higher to the material requirement of consersion unit, and industrialized production is more difficult；Sol-gal process is a kind of being adapted in fact
Test room and prepare LiNi1/3Co1/3Mn1/3O2A kind of feasible method, the method mixes transition metal ions and organic complex
Chelate is formed, is solidified by processes such as solution, colloidal sol, gels, and then soild oxide solid solution is obtained after heat treatment.
Sol-gel process raw material is well mixed, and can also reduce sintering temperature, but preparation cost is higher, is not suitable for industrialized production.
The content of the invention
It is an object of the invention to solve the defect that above-mentioned prior art is present, there is provided a kind of LiNi1/3Co1/3Mn1/3O2's
Preparation method.
A kind of LiNi1/3Co1/3Mn1/3O2Preparation method, it is characterised in that comprise the following steps：
Step 1：Raw material lithium source, nickel source, cobalt source, manganese source and carbon source and appropriate distilled water are ground, LiNi is obtained1/ 3Co1/3Mn1/3O2Predecessor；Wherein, the mol ratio of the lithium source, nickel source, cobalt source, manganese source and carbon source is 1.05:1/3:1/3:
1/3:2.05；
Step 2：By the LiNi1/3Co1/3Mn1/3O2Predecessor in 120 DEG C of freeze-day with constant temperature 24h, collect and be ground to powder
Shape；
Step 3：Powdery predecessor is heated 6h at 600 DEG C, is ground after naturally cooling to room temperature, obtain LiNi1/ 3Co1/3Mn1/3O2Intermediate product；
Step 4：By this LiNi1/3Co1/3Mn1/3O2Intermediate product constant temperature calcining 12h, natural cooling at 800 DEG C -900 DEG C
Powdery is ground to after to room temperature, target product LiNi is finally given1/3Co1/3Mn1/3O2。
Further, method as described above, it is characterised in that in the step 4, including by iNi1/3Co1/3Mn1/3O2
The intermediate product constant temperature calcining 12h at 800 DEG C, 850 DEG C and 900 DEG C respectively, powdery is ground to after naturally cooling to room temperature, point
800 DEG C, 850 DEG C and 900 DEG C of target product LiNi is not obtained1/3Co1/3Mn1/3O2。
Further, method as described above, in step 1, the method for the grinding is：Bead is added in ball grinder,
With the rotating speed ball milling 4h of 300r/min, the bead is 20 with the mass ratio of raw material:1.
Zirconia ball in the ball mill that bead herein refers to, the effect of bead is to grind added raw material, makes original
Material eventually becomes the predecessor of rheology phase, and bead is exactly the instrument of ball milling, and the purpose of ball milling, wherein bead are not reached without bead
It is 20 with the mass ratio of raw material:When 1, from ball milling best results.
Further, method as described above, the lithium source is LiOHH2O。
Further, method as described above, the nickel source is Ni (Ac)2·4H2O。
Further, method as described above, the cobalt source is Co (Ac)2·4H2O。
Further, method as described above, the manganese source is Mn (Ac)2·4H2O。
Further, method as described above, the carbon source is citric acid.
Although other sources can also be as the source of corresponding composition, from the synthetic effect, product structure that match each other
Considered with chemical property performance, LiOHH2O、Ni(Ac)2·4H2O、Co(Ac)2·4H2O、Mn(Ac)2·4H2O is most
Good matching.In addition, if the pattern of the target product obtained during using other carbon sources is bad, XRD shows impurity peaks, and
The predecessor agglomeration for obtaining is serious, and pattern is bad, and XRD shows other impurities generation, therefore, the application uses citric acid
As carbon source, while doubling as complexing agent.
Further, method as described above, heating rate is 5 DEG C/min in step 3.
Further, method as described above, heating rate is 5 DEG C/min in step 4.
Heating rate is important influence factor, and reason is that in calcination process, heating rate is produced to synthesized target
The structure and performance impact of thing are very big.The purpose of calcining is that each active ingredient obtains fully oxidized, decomposition in making predecessor
And interaction, particle is reset calmly and ultimately generate structure and all good target product of performance.It is preceding if intensification is too fast
Each active ingredient oxidation in thing is driven, decompose and interacts too fast, particle is reset too fast and reunited, and causes heat transfer inequality
Even, the gaseous matter effusion of generation is accelerated, and is easily destroyed the skeleton profile of crystal so that the internal holes of the target product of generation are straight
Footpath becomes big, short texture is unstable and become to be susceptible to the caving in so as to influence lithium ion in target product of crystal structure
Deintercalation, this certainly will will reduce the chemical property of target product.So heating rate must be controlled in heating process.Cause
This, the application finally determines that the heating rate control in compound experiment is most appropriate in 5 DEG C of rising per minute.
Beneficial effect：
This synthetic method is simple and easily operates, and energy charge is less, influenceed in building-up process and disturbed it is extraneous because
Element less and is easily controlled, and each active principle can be well mixed in building-up process, can sufficiently interact and ultimately generate shape
Looks, structure, granularity (nanoscale) and all preferable target product of chemical property, it is most important that preparation cost is not high, easily
Realize industrialized production.
Brief description of the drawings
Fig. 1 is the LiNi prepared using the inventive method1/3Co1/3Mn1/3O2XRD spectrum；
Fig. 2 is the LiNi prepared using the inventive method1/3Co1/3Mn1/3O2SEM figure；
Fig. 3 (a) is in 800 DEG C of LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Charge/discharge curve
Figure；
Fig. 3 (b) is in 850 DEG C of LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Charge/discharge curve
Figure；
Fig. 3 (c) is in 900 DEG C of LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Charge/discharge curve
Figure；
Fig. 4 is in the LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Cycle performance curve map；
Fig. 5 is in the LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Coulombic efficiency figure；
Fig. 6 is the LiNi prepared at 850 DEG C using the inventive method1/3Co1/3Mn1/3O2In different current densities
The cycle performance figure of discharge capacity；
Fig. 7 is the LiNi prepared using the inventive method1/3Co1/3Mn1/3O2In the frequency range of 0.01-100kHz
Interior electrochemical impedance spectrogram；
Fig. 8 is the LiNi prepared using the inventive method1/3Co1/3Mn1/3O2As electrode material in 0.01-
Diffusion impedance Linear Fit Chart in the frequency range of 100kHz.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below the present invention in technical scheme carry out clearly
Chu, it is fully described by, it is clear that described embodiment is a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
It is that all raw materials for synthesizing target product are put together that rheology is combined to method, is subject to appropriate, appropriate solvent,
All raw materials is namely being synthesized the predecessor of target product in the case of rheology phase between solid phase and liquid phase, then enter one
Step treatment obtains a kind of synthetic method of target product.This method is in LiNi1/3Co1/3Mn1/3O2Synthesis and its doping vario-property
In be rarely reported, the present invention is combined to method using rheology, has prepared particle uniform tiny (reaching nanoscale), crystalline phase more
The complete and good LiNi of chemical property1/3Co1/3Mn1/3O2Material.The cost of this synthetic method is relatively low, and process is easy
Operation and control, especially with the synthesis quantity that lifting target product is easier after appropriate ball mill, are relatively adapted to laboratory
And the research and development centre of enterprise prepares to amplify sample or even be extended to enterprise and produces.
Embodiment
Rheology is combined to method and prepares LiNi1/3Co1/3Mn1/3O2
Respectively with lithium hydroxide, nickel acetate, cobalt acetate, manganese acetate and citric acid are used as lithium source, nickel source, cobalt source, manganese source
It is 1.05 according to mol ratio with carbon source (citric acid makees carbon source simultaneously as complexing agent):1/3:1/3:1/3:2.05 ratio claims
Take the LiOHH of 0.0441mol2The Ni (Ac) of O, 0.014mol2·4H2O, 0.014mol Co (Ac)2·4H2O, 0.014mol
Mn(Ac)2·4H2The citric acid of O and 0.0861mol and appropriate distilled water add the zirconia ball grinding jar of planetary ball mill
Middle mixing, bead and the powderous primary material weight ratio for adding are 20 in ball grinder:With the rotating speed ball of 300r/min in the case of 1
Mill 4h, then by the early stage reaction rheology phase predecessor that the obtains freeze-day with constant temperature 24h in 120 DEG C of air thermostatic drying chambers,
Collect simultaneously be ground to powdery with agate mortar, powdery predecessor in Muffle furnace 600 DEG C heating 6h (heating rate for 5 DEG C/
Min), it is ground with agate mortar after naturally cooling to room temperature, obtains LiNi1/3Co1/3Mn1/3O2Intermediate product, by this
LiNi1/3Co1/3Mn1/3O2Intermediate product respectively at 800 DEG C, 850 DEG C and 900 DEG C constant temperature calcining 12h (heating rate is 5
DEG C/min), naturally cool to and collect after room temperature and be ground to powdery with agate mortar, respectively obtain 800 DEG C, 850 DEG C and 900
DEG C target product LiNi1/3Co1/3Mn1/3O2。
Fig. 1 is LiNi1/3Co1/3Mn1/3O2XRD spectrum；Wherein, the LiNi synthesized when curve a is 800 DEG C1/3Co1/ 3Mn1/3O2, the LiNi that curve b synthesizes when being 850 DEG C1/3Co1/3Mn1/3O2, the LiNi that curve c synthesizes when being 900 DEG C1/3Co1/ 3Mn1/3O2, from figure 1 it appears that all diffraction maximums are all based on the diffraction maximum of target product, there is no impurity peaks to occur, these
Diffraction maximum clearly shows that the product obtained under three synthesis temperatures all has the a-NaFeO for typically belonging to hexagonal crystal system2Knot
Structure, its space group is R3m, be can be seen that from 800 DEG C from the intensity of diffraction maximum, and 850 DEG C to 900 DEG C, intensity is with temperature
Rising is gradually strengthened.
Fig. 2 is the LiNi prepared using the inventive method1/3Co1/3Mn1/3O2SEM figure, wherein, figure a, b be 800
DEG C when the LiNi that synthesizes1/3Co1/3Mn1/3O2, the LiNi that figure c, d synthesize when being 850 DEG C1/3Co1/3Mn1/3O2, when figure c, d are 900 DEG C
The LiNi of synthesis1/3Co1/3Mn1/3O2, from figure 2 it can be seen that sintering temperature is have aobvious for the granule size of material and distribution
Write influence.When sintering temperature selection is 800 DEG C, the size distribution of target product is 100nm-200nm；Sintering temperature is selected
At 850 DEG C, the size distribution of target product is 200nm-300nm；When sintering temperature selection is 900 DEG C, the granularity of target product
200nm-300nm is distributed as, with the rising of sintering temperature, the size distribution of target product is gradually increasing, and this should attribution
When sintering temperature increase especially high temperature sintering, original short grained target product is bonded together, then in SEM figures
Under obtained granularity increase phenomenon.Certainly, observed from whole SEM figures, in the size distribution of target product, sintering temperature
Spend for 800 DEG C when product particle size it is minimum, but the uniformity of granularity is not fine；Product grain when sintering temperature is 900 DEG C
Degree it is bigger than normal, and particle uniformity also substantially be not so good as 800 DEG C when product；Product when only sintering temperature is 850 DEG C
Thing, its whether size distribution or product grain uniformity be significantly better than other two temperature when product.This is at certain
Material as chemical property during lithium ion battery electrode material will be influenced whether in the degree of kind.
Fig. 3 (a) is in 800 DEG C of LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Charge/discharge curve
Figure；Fig. 3 (b) is in 850 DEG C of LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Charge/discharge curve figure；Fig. 3
C () is in 900 DEG C of LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Charge/discharge curve figure, from Fig. 3 (a)-
As can be seen that 800 DEG C of target products as positive electrode when being assembled into battery testing in Fig. 3 (b), in given test condition
Under, its initial discharge capacity is 160mAh/g, and after charge and discharge cycles 20 are enclosed, capacity attenuation is 145mAh/g, charge and discharge cycles 50
After circle, capacity attenuation is 136mAh/g；When 850 DEG C of target products are assembled into battery testing as positive electrode, in given survey
Under the conditions of examination, its initial discharge capacity is 181mAh/g, and after charge and discharge cycles 20 are enclosed, capacity attenuation is 173mAh/g, discharge and recharge
After the circle of circulation 50, capacity attenuation is 170mAh/g；When 900 DEG C of target products are assembled into battery testing as positive electrode, giving
Under fixed test condition, its initial discharge capacity is 163mAh/g, and after charge and discharge cycles 20 are enclosed, capacity attenuation is 147mAh/g,
After charge and discharge cycles 50 are enclosed, capacity attenuation is 140mAh/g.When the target product synthesized at three temperature is as positive electrode, with
The increase capacity of charge and discharge cycles number of times all in decay, this sends out mainly due to the crystal structure of material in charge and discharge cycles
Change is given birth to, the turnover to lithium ion causes certain obstruction caused.Among these with 850 DEG C of target product situations as best.
Fig. 4 is in the LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Cycle performance curve map；Wherein, it is bent
The LiNi that line a synthesizes when being 800 DEG C1/3Co1/3Mn1/3O2, the LiNi that curve b synthesizes when being 850 DEG C1/3Co1/3Mn1/3O2, curve c
For 900 DEG C when the LiNi that synthesizes1/3Co1/3Mn1/3O2, figure 4, it is seen that the target product under three different temperatures has
Preferable cyclical stability, wherein under identical current density and the circulation number of turns, the specific capacity of target product at 850 DEG C
Significantly it is better than the target product at other two temperature with cycle performance.
Fig. 5 is in the LiNi for preparing using the inventive method1/3Co1/3Mn1/3O2Coulombic efficiency figure；Wherein, curve a
For 800 DEG C when the LiNi that synthesizes1/3Co1/3Mn1/3O2, the LiNi that curve b synthesizes when being 850 DEG C1/3Co1/3Mn1/3O2, curve c is
The LiNi synthesized at 900 DEG C1/3Co1/3Mn1/3O2, from figure 5 it can be seen that the target product under three different temperatures is suffered from
Preferable cyclical stability, wherein under identical current density and the circulation number of turns, the coulombic efficiency of target product at 850 DEG C
Significantly it is better than the target product at other two temperature.
Fig. 6 is the LiNi prepared at 850 DEG C using the inventive method1/3Co1/3Mn1/3O2In different current densities
The cycle performance figure of discharge capacity；From fig. 6 it can be seen that the figure that the data obtained from experiment are drawn can be seen that
Specific capacity situation of target product at 850 DEG C when making positive electrode under different current densities, in different current density feelings
When carrying out charge and discharge cycles under condition, target product at 850 DEG C has good charge and discharge stability.Wherein：Current density is distinguished
During for 20,50,100,200 and 400mA/g, its corresponding specific discharge capacity is respectively 181,157,132m, 111 and 70mAh/g,
And when material by current density for the charge and discharge cycles of 400mA/g return the charge and discharge cycles that current density is 20mA/g
When, its specific capacity remains to be maintained at 174mA/g or so, closely its initial specific capacities, and this can be seen that and is harmonious using rheology
Target product at obtain into method 850 DEG C has extraordinary cycle performance.
Fig. 7 is the LiNi prepared using the inventive method1/3Co1/3Mn1/3O2In the frequency range of 0.01-100kHz
Interior electrochemical impedance spectrogram；Wherein, the LiNi synthesized when curve a is 800 DEG C1/3Co1/3Mn1/3O2, synthesize when curve b is 850 DEG C
LiNi1/3Co1/3Mn1/3O2, the LiNi that curve c synthesizes when being 900 DEG C1/3Co1/3Mn1/3O2, it can be seen from figure 7 that Fig. 7 exhibitions
The electrochemistry resistance of the target product being combined to using rheology at 800 DEG C, 850 DEG C and 900 DEG C three temperature that method is obtained is shown
Anti- experimental conditions, two depressed semicircles represent surface membrane impedance in the case of high-frequency and medium as experimental result respectively in figure
Charge-transfer resistance in the case of intensity frequency.Electrochemical analysis are carried out when testing using the button cell of new assembling.
The theory of Kinetic differences analysis foundation is the equivalent circuit AC AC impedance models of Randles.Rs in figure represents electrolyte
The Ohmic resistance of solution, Rct represents the resistance of charge transfer process, CdlIt is the double-layer electric capacity of electrode material and electrolyte,
ZwIt is Warburg impedances.The analysis of experimental data is carried out by appropriate equivalent circuit.It can be seen that 850 DEG C of targets
The Rct values of product are significantly lower than the Rct values of the target product under other two temperature conditionss, 850 DEG C of depressed semicircles of target product
Also other two depressed semicircles are significantly less than, this is further showed that, 850 DEG C of target products have good chemical property ratio
Relatively it is suitable as anode material for lithium-ion batteries.Certainly, on the other hand, method synthesis LiNi is combined to using rheology1/3Co1/ 3Mn1/3O2When, as synthesis temperature is increased to 900 DEG C, cell parameter reduces the cation mixing that the result brought is Li and Ni,
This causes that crystal structure local chaotic and insertion that be unfavorable for lithium ion and deintercalation occurs so as to reduce the capacity of material, so
The appropriate synthesis temperature of selection is to LiNi1/3Co1/3Mn1/3O2Synthesis it is critical that.
Fig. 8 is the LiNi prepared using the inventive method1/3Co1/3Mn1/3O2As electrode material in 0.01-
Diffusion impedance Linear Fit Chart in the frequency range of 100kHz, wherein, the LiNi that curve a synthesizes when being 800 DEG C1/3Co1/3Mn1/ 3O2, the LiNi that curve b synthesizes when being 850 DEG C1/3Co1/3Mn1/3O2, the LiNi that curve c synthesizes when being 900 DEG C1/3Co1/3Mn1/3O2,
As can be seen from Figure 8, shown in Fig. 8, Warburg coefficients (Aw) are equal to Z '-ω under low frequency-1/2The slope of line, ω is that angular frequency is handed over
Stream electricity.The Warburg coefficients (Aw) of LNCMO-800, LNCMO-850 and LNCMO-900 are respectively 9.3,16.5 and 8.5, according to
Equation explains that the ionic conductivity that LNCMO-850 is determined is bigger than LNCMO-800 and LNCMO-900, also just illustrates
LNCMO-850 shows more excellent chemical property.
In sum, the LiNi that prepared by the inventive method1/3Co1/3Mn1/3O2The LiNi prepared with existing other technologies1/ 3Co1/3Mn1/3O2Compare, all have in terms of the chemical property such as cycle performance, specific capacity and stable charge/discharge in product
There is certain advantage, these advantages are mostly derived from the building-up process of rheological phase method selection and the preparation of predecessor to raw material
With treatment, the LiNi for especially being prepared at 850 DEG C1/3Co1/3Mn1/3O2。
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
Modified with to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (10)
1. a kind of LiNi1/3Co1/3Mn1/3O2Preparation method, it is characterised in that comprise the following steps：
Step 1：Raw material lithium source, nickel source, cobalt source, manganese source and carbon source and appropriate distilled water are ground, LiNi is obtained1/3Co1/ 3Mn1/3O2Predecessor；Wherein, the mol ratio of the lithium source, nickel source, cobalt source, manganese source and carbon source is 1.05:1/3:1/3:1/3:
2.05；
Step 2：By the LiNi1/3Co1/3Mn1/3O2Predecessor in 120 DEG C of freeze-day with constant temperature 24h, collect and be ground to powdery；
Step 3：Powdery predecessor is heated 6h at 600 DEG C, is ground after naturally cooling to room temperature, obtain LiNi1/3Co1/ 3Mn1/3O2Intermediate product；
Step 4：By this LiNi1/3Co1/3Mn1/3O2Intermediate product constant temperature calcining 12h at 800 DEG C -900 DEG C, naturally cools to room
Powdery is ground to after temperature, target product LiNi is finally given1/3Co1/3Mn1/3O2。
2. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that in the step 4, bag
Include LiNi1/3Co1/3Mn1/3O2Intermediate product constant temperature calcining 12h, natural cooling at 800 DEG C, 850 DEG C and 900 DEG C respectively
Powdery is ground to after to room temperature, 800 DEG C, 850 DEG C and 900 DEG C of target product LiNi is respectively obtained1/3Co1/3Mn1/3O2。
3. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that it is described to grind in step 1
The method of mill is：Bead is added in ball grinder, with the rotating speed ball milling 4h of 300r/min, the bead is with the mass ratio of raw material
20:1。
4. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that the lithium source is
LiOH·H2O。
5. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that the nickel source be Ni
(Ac)2·4H2O。
6. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that the cobalt source be Co
(Ac)2·4H2O。
7. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that the manganese source be Mn
(Ac)2·4H2O。
8. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that the carbon source be lemon
Acid.
9. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that heating rate in step 3
It is 5 DEG C/min.
10. LiNi according to claim 11/3Co1/3Mn1/3O2Preparation method, it is characterised in that in step 4 heat up speed
Rate is 5 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710103217.9A CN106745337A (en) | 2017-02-24 | 2017-02-24 | A kind of LiNi1/3Co1/3Mn1/3O2Preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710103217.9A CN106745337A (en) | 2017-02-24 | 2017-02-24 | A kind of LiNi1/3Co1/3Mn1/3O2Preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106745337A true CN106745337A (en) | 2017-05-31 |
Family
ID=58960409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710103217.9A Pending CN106745337A (en) | 2017-02-24 | 2017-02-24 | A kind of LiNi1/3Co1/3Mn1/3O2Preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106745337A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109286015A (en) * | 2018-09-30 | 2019-01-29 | 西北有色金属研究院 | A kind of hollow porous TiO2The preparation method and applications of nanocube material |
| CN109860563A (en) * | 2018-12-17 | 2019-06-07 | 中科廊坊过程工程研究院 | A kind of oxygen place doped nickel cobalt aluminium positive electrode and its preparation method and application |
| CN112786875A (en) * | 2020-12-30 | 2021-05-11 | 华南理工大学 | Potassium ion doped carbon-coated lithium-rich ternary positive electrode material and preparation method and application thereof |
| CN114864949A (en) * | 2022-07-08 | 2022-08-05 | 四川新能源汽车创新中心有限公司 | Positive electrode material and preparation method and application thereof |
| CN115849462A (en) * | 2022-12-07 | 2023-03-28 | 合肥国轩高科动力能源有限公司 | Nickel-cobalt-manganese ternary cathode material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326232A (en) * | 2000-05-25 | 2001-12-12 | 中国科学院成都有机化学研究所 | Process for preparing lithium manganese oxide as positive electrode of lithium ion battery |
| CN101967055A (en) * | 2010-10-20 | 2011-02-09 | 河南联合新能源有限公司 | Method for preparing Co-Ni-Mn ternary anode materials by microwave sintering |
| CN102780002A (en) * | 2012-07-28 | 2012-11-14 | 湘西自治州金鸿矿业有限责任公司 | Preparation method of ternary positive electrode material of lithium-manganese dioxide battery |
| CN102810668A (en) * | 2012-08-14 | 2012-12-05 | 安徽亚兰德新能源材料股份有限公司 | Lithium ion battery nickel-cobalt-manganese ternary composite anode material and method for preparing precursor thereof |
| CN102930383A (en) * | 2012-10-18 | 2013-02-13 | 沈阳创达技术交易市场有限公司 | Intellectual property service platform structure |
| CN102956882A (en) * | 2012-11-01 | 2013-03-06 | 彩虹集团公司 | Metal-doped ternary material and preparation method thereof |
| CN103066269A (en) * | 2012-12-25 | 2013-04-24 | 贵州省开阳安达磷化工有限公司 | Preparation method for ternary positive electrode active material and battery |
| CN104466295A (en) * | 2015-01-08 | 2015-03-25 | 兰州理工大学 | Method for regenerating positive electrode active material in LiNi1/3Co1/3Mn1/3O2 waste lithium ion battery |
| CN104934593A (en) * | 2015-05-22 | 2015-09-23 | 郑州德朗能微波技术有限公司 | Method and device for preparing LiNi<1/3>Co<1/3>Mn<1/3>O2 material by microwave sintering |
| CN105680015A (en) * | 2016-01-28 | 2016-06-15 | 深圳大学 | Cathode material formed by coating lanthanum oxide on surface of ternary material and preparation method of cathode material |
-
2017
- 2017-02-24 CN CN201710103217.9A patent/CN106745337A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326232A (en) * | 2000-05-25 | 2001-12-12 | 中国科学院成都有机化学研究所 | Process for preparing lithium manganese oxide as positive electrode of lithium ion battery |
| CN101967055A (en) * | 2010-10-20 | 2011-02-09 | 河南联合新能源有限公司 | Method for preparing Co-Ni-Mn ternary anode materials by microwave sintering |
| CN102780002A (en) * | 2012-07-28 | 2012-11-14 | 湘西自治州金鸿矿业有限责任公司 | Preparation method of ternary positive electrode material of lithium-manganese dioxide battery |
| CN102810668A (en) * | 2012-08-14 | 2012-12-05 | 安徽亚兰德新能源材料股份有限公司 | Lithium ion battery nickel-cobalt-manganese ternary composite anode material and method for preparing precursor thereof |
| CN102930383A (en) * | 2012-10-18 | 2013-02-13 | 沈阳创达技术交易市场有限公司 | Intellectual property service platform structure |
| CN102956882A (en) * | 2012-11-01 | 2013-03-06 | 彩虹集团公司 | Metal-doped ternary material and preparation method thereof |
| CN103066269A (en) * | 2012-12-25 | 2013-04-24 | 贵州省开阳安达磷化工有限公司 | Preparation method for ternary positive electrode active material and battery |
| CN104466295A (en) * | 2015-01-08 | 2015-03-25 | 兰州理工大学 | Method for regenerating positive electrode active material in LiNi1/3Co1/3Mn1/3O2 waste lithium ion battery |
| CN104934593A (en) * | 2015-05-22 | 2015-09-23 | 郑州德朗能微波技术有限公司 | Method and device for preparing LiNi<1/3>Co<1/3>Mn<1/3>O2 material by microwave sintering |
| CN105680015A (en) * | 2016-01-28 | 2016-06-15 | 深圳大学 | Cathode material formed by coating lanthanum oxide on surface of ternary material and preparation method of cathode material |
Non-Patent Citations (1)
| Title |
|---|
| LIN LI ET AL.: "AlPO4 coated LiNi1/3Co1/3Mn1/3O2 for high performance cathode material in lithium batteries", 《J MATER SCI: MATER ELECTRON》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109286015A (en) * | 2018-09-30 | 2019-01-29 | 西北有色金属研究院 | A kind of hollow porous TiO2The preparation method and applications of nanocube material |
| CN109860563A (en) * | 2018-12-17 | 2019-06-07 | 中科廊坊过程工程研究院 | A kind of oxygen place doped nickel cobalt aluminium positive electrode and its preparation method and application |
| CN109860563B (en) * | 2018-12-17 | 2021-12-03 | 廊坊绿色工业技术服务中心 | Oxygen-site-doped nickel-cobalt-aluminum cathode material and preparation method and application thereof |
| CN112786875A (en) * | 2020-12-30 | 2021-05-11 | 华南理工大学 | Potassium ion doped carbon-coated lithium-rich ternary positive electrode material and preparation method and application thereof |
| CN114864949A (en) * | 2022-07-08 | 2022-08-05 | 四川新能源汽车创新中心有限公司 | Positive electrode material and preparation method and application thereof |
| CN115849462A (en) * | 2022-12-07 | 2023-03-28 | 合肥国轩高科动力能源有限公司 | Nickel-cobalt-manganese ternary cathode material and preparation method and application thereof |
| CN115849462B (en) * | 2022-12-07 | 2024-04-09 | 合肥国轩高科动力能源有限公司 | Nickel-cobalt-manganese ternary positive electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103094550B (en) | Preparation method of lithium-rich anode material | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN106745337A (en) | A kind of LiNi1/3Co1/3Mn1/3O2Preparation method | |
| CN108767239A (en) | A kind of nickelic low cobalt tertiary cathode material and preparation method thereof | |
| CN103794782B (en) | A kind of lithium-rich manganese base material, its preparation method and lithium ion battery | |
| CN105789581A (en) | Production method for high-capacity long-cycle lithium-rich type-622 ternary positive electrode material | |
| CN107204429A (en) | The preparation method and anode material for lithium-ion batteries and lithium ion battery of nickel-cobalt-manganese ternary material | |
| CN108604672A (en) | The method for preparing cathode material for lithium ion battery | |
| CN103708434B (en) | LiFePO 4 material and preparation method thereof | |
| CN102583583B (en) | A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN102790210A (en) | Method for preparing cathode material lithium manganate of lithium ion battery by supercritical hydrothermal reaction | |
| CN105826550A (en) | Preparation method of lithium manganate cathode material with ferri-containing compound coating | |
| CN105489842B (en) | A kind of lithium-rich manganese-based anode material and preparation method thereof | |
| CN111933899B (en) | Composite oxide electrode material and preparation method thereof | |
| CN105720242A (en) | Method for modifying lithium ion battery cathode material | |
| CN103606669A (en) | Preparation method of trivalent scandium or chromium-doped spinel-type lithium-rich lithium manganate cathode material | |
| Malik et al. | Effect of Synthesis Method on the Electrochemical Performance of LiNi x MnCo 1-xy O 2 (NMC) Cathode for Li-Ion Batteries: A Review | |
| CN105932274A (en) | Preparation method of titanium-dioxide-coated spinel lithium-rich lithium manganite positive electrode material | |
| CN103594704B (en) | The preparation method of the spinel lithium-rich lithium manganate cathode material of doping titanic ion | |
| CN106946296B (en) | A kind of micron order monocrystalline lithium nickelate and its preparation method and application | |
| CN103811745B (en) | Method for preparing high-specific-capacity lithium-enriched lithium battery material | |
| CN104466167A (en) | Method for preparing positive material LiNi1/3Co1/3Mn1/3O2 of lithium ion battery | |
| CN103594706A (en) | Preparation method for yttrium-doped spinel lithium-rich lithium manganate positive electrode material | |
| CN103594701B (en) | Mix the preparation method of nickel spinel type lithium-rich lithium manganate cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |