CN109052490A - A kind of ternary cathode material of lithium ion battery and preparation method thereof - Google Patents
A kind of ternary cathode material of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN109052490A CN109052490A CN201810744438.9A CN201810744438A CN109052490A CN 109052490 A CN109052490 A CN 109052490A CN 201810744438 A CN201810744438 A CN 201810744438A CN 109052490 A CN109052490 A CN 109052490A
- Authority
- CN
- China
- Prior art keywords
- cathode material
- preparation
- carbon ball
- lithium
- lithium ion
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
Abstract
The invention belongs to lithium ion cell electrode fields, more particularly, to a kind of ternary cathode material of lithium ion battery and preparation method thereof.Submicron order richness nickel tertiary cathode material has been prepared using coprecipitation by the way that carbon ball that oxygen-containing functional group and granularity are 300nm-700nm is contained as template in surface in the present invention.After the present invention is obtained material assembled battery, in the case where current density is the voltage window of 0.1C and 2.7-4.5V, first discharge specific capacity reaches 255mAh g‑1, still have 154mAh g after the circle of circulation 70‑1Specific capacity.The preparation method of tertiary cathode material of the present invention is easy to operate, at low cost, and operating voltage is high, can be applied to industrialized production.
Description
Technical field
The invention belongs to lithium ion cell electrode fields, more particularly, to a kind of ternary cathode material of lithium ion battery
And preparation method thereof.
Background technique
Lithium ion battery is used in mobile phone, laptop, digital phase because of the advantages that its is light, energy density is high extensively
In the portable electronic devices such as machine, and in the fast development of the fields such as extensive energy storage and high power system (electric vehicle).Lithium ion
Cell positive material is to restrict one of further key of lithium ion battery, therefore need to develop a kind of with height ratio capacity, safety
Stablize, prepare simple positive electrode.The wherein ternary metal layered oxide Li (Ni of rich nickel1-x-yCoxMny) with very high
Theoretical specific capacity (> 220mAh g-1), discharge platform high (> 3.6V), it is cheap and easy to get the advantages that cause the concern of people, become one
Kind is suitable as the volume high-energy positive electrode of power battery, and present many commercialized electric cars have all used ternary material
Material is used as battery component.But due to Ni in nickel-cobalt-manganese ternary material+2Ionic radiusAnd Li+Radius it is closeThe phenomenon that cationic mixing can seriously occur；On the other hand, material will appear volume during removal lithium embedded
The problem of expansion.These reasons cause the change and dusting of the material structure in cyclic process.Therefore preparing one kind has
This problem can be effectively relieved in the hollow material of height layer structure.
If Chinese patent CN 105914364A is using citric acid as precipitating reagent, using sol-gel method be prepared for a kind of lithium from
Sub- battery tertiary cathode material, obtained diameter is in the hollow microsphere of 20 μm of sizes, but the capacity of material is not high, in circulation 20
Only 140mAg h after circle-1Left and right.Chinese patent CN106981652A uses active carbon or resin for template, and use is coprecipitated
Shallow lake method prepares ternary material, and material has preferable chemical property, but active carbon and resin price are more expensive, and synthesizes
Material be sintered together, obtain the tertiary cathode material of micron and micron dimensions above, particle size is larger, connects with electrolyte
It touches bad, causes cycle performance of battery poor.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of lithium ion battery tertiary cathode materials
Material and preparation method thereof, sufficiently combines the preparation characteristic and demand of ternary cathode material of lithium ion battery, to nickel-cobalt-manganese ternary
The preparation method of positive electrode is redesigned, and is accordingly obtained a kind of with layered crystal structure and hollow structure and granularity
Thus range solves the tertiary cathode material of the prior art in the lithium ion tertiary cathode material Ni-Co-Mn of 300-600nm
Particle size is big, bad with electrolyte contacts, the technical problem that circulation volume is low, chemical property is poor.
To achieve the above object, according to one aspect of the present invention, a kind of ternary cathode material of lithium ion battery is provided,
The tertiary cathode material is the spheric granules for having hollow structure, which is 300nm-600nm, and the spheric granules
Crystal structure be layer structure, chemical composition LiNi(1-x-y)CoxMnyO2, wherein x value range is 0.1-0.3, and y takes
Value range is 0.1-0.3.
Preferably, include in the tertiary cathode material mass fraction be the nickel of 30%-80%, 10%-30% cobalt and
The manganese of 10%-30%.
Other side according to the invention provides the preparation side of ternary cathode material of lithium ion battery described in one kind
Method includes the following steps:
(1) after mixing carbon ball, nickel salt, cobalt salt and manganese salt, dehydrated alcohol is added, stirs to get mixing suspension；Wherein,
Contain oxygen-containing functional group, and a diameter of 300nm-700nm in the carbon ball surface；
(2) precipitating reagent is added into the mixing suspension, after stirring, is separated by solid-liquid separation, collects precipitating；
(3) it will be ground after the washing of precipitate, drying, carry out pre-oxidation under an oxygen-containing atmosphere, obtain metal oxidation
Object spheric granules；
(4) the metal oxide spherical shape particle is mixed with lithium salts, is calcined in oxygen-containing atmosphere, after being cooled to room temperature
To the ternary cathode material of lithium ion battery of hollow structure.
Preferably, the carbon ball is prepared as follows to obtain: in deionized water by carbon source dispersion, obtaining transparent equal
One solution carries out hydro-thermal reaction, obtains carbon ball template.
Preferably, the carbon ball is prepared as follows to obtain: glucose or sucrose being dispersed in deionized water, obtained
To transparent uniform solution, the mass concentration of the glucose in solutions or sucrose is 5%-10%, in 150 DEG C of -220 DEG C of progress water
Thermal response -15 hours 6 hours, it will be freeze-dried after obtained solid water and ethanol washing, obtain the carbon ball template.
Preferably, the molar ratio of nickel element, cobalt element and manganese element is (1 in step (1) nickel salt, cobalt salt and manganese salt
~8): (1~1.5): 1.
Preferably, the mass ratio of step (1) carbon ball and step (3) described metal oxide is 1:0.5-3.
Preferably, step (2) described precipitating reagent is the ammonium hydroxide that concentration is 0.05~0.1mol/L, the volume of the precipitating reagent
Volume ratio with step (1) described mixing suspension is 0.5~2:1.
Preferably, step (3) Pre oxidation is 350~650 DEG C, and preoxidation time is 1~4h.
Preferably, step (4) lithium source is lithium hydroxide, lithium carbonate or lithium acetate, elemental lithium and step in the lithium source
Suddenly the molar ratio of (3) described metal oxide is 0.8~2:1.
Preferably, step (4) calcination temperature is 720~880 DEG C, and calcination time is 8~20h.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) present invention is adopted by the way that carbon ball that oxygen-containing functional group and granularity are 300nm-700nm is contained as template in surface
Rich nickel tertiary cathode material is prepared with coprecipitation, material has good layer structure, can provide good lithium
The problem of ion transfer channels, the hollow structure of another aspect material can alleviate the volume expansion in charge and discharge process.
(2) ternary cathode material of lithium ion battery that the present invention is prepared is particle size range in the hollow of 300-600nm
Microballoon, granularity are submicron order, facilitate it and come into full contact with electrolyte, preferably the effect of performance positive electrode, improve battery
Chemical property.
(3) the ternary cathode material of lithium ion battery Ni-Co-Mn that the present invention is prepared is assembled into battery, close in electric current
When degree is 2.7~4.5V of 0.1C and voltage window, the specific discharge capacity of first circle reaches 255mAh g-1, circulation 70 is enclosed still to be had later
154mAh g-1Capacity, wherein coulombic efficiency be 99.9%.
(4) ternary cathode material of lithium ion battery preparation method of the present invention is easy to operate, at low cost, and operating voltage is high, can
Applied to industrialized production.
Detailed description of the invention
Fig. 1 is the particle size distribution figure for the carbon ball that the embodiment of the present invention 1 is prepared；
Fig. 2 is the infared spectrum on the carbon ball surface that the embodiment of the present invention 1 is prepared；
Fig. 3 is the particle size distribution figure for the ternary material that the embodiment of the present invention 1 is prepared；
1 gained ternary material SEM of Fig. 4 embodiment of the present invention figure；
1 gained ternary material TEM of Fig. 5 embodiment of the present invention figure；
1 gained ternary material XRD diagram of Fig. 6 embodiment of the present invention；
1 gained ternary material of Fig. 7 embodiment of the present invention first five circle CV figure；
Fig. 8 comparative example 1 of the present invention resulting ternary material SEM figure.
First five circle charging and discharging curve of 2 gained ternary material of Fig. 9 embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
A kind of ternary cathode material of lithium ion battery, the tertiary cathode material are the spheric granules for having hollow structure, the ball
Shape particle diameter is 300nm-600nm, and the crystal structure of the spheric granules is layer structure.Include in the tertiary cathode material
Mass fraction is nickel, the cobalt of 10%-30% and the manganese of 10%-30% of 30%-80%.Its chemical composition is LiNi(1-x-y)
CoxMnyO2, wherein x value range is 0.1-0.3, and y value range is 0.1-0.3.
The preparation method of ternary cathode material of lithium ion battery provided by the invention, includes the following steps:
(1) after mixing carbon ball, nickel salt, cobalt salt and manganese salt, dehydrated alcohol is added, stirs to get mixing suspension；Wherein,
Contain oxygen-containing functional group, and a diameter of 300nm-700nm in the carbon ball surface；Carbon ball is prepared as follows to obtain: will
Carbon source disperses in deionized water, to obtain transparent uniform solution, carries out hydro-thermal reaction, obtains carbon ball template.Preferred carbon ball
Preparation process are as follows: using glucose or sucrose as carbon source, stirring is preferably stirred by ultrasonic, 20-60 minutes ultrasonic, disperses carbon source
In deionized water, transparent uniform solution is obtained, the mass concentration of the glucose in solutions or sucrose is 5%-10%,
150 DEG C -220 DEG C, preferably 180-200 DEG C carry out hydro-thermal reaction -15 hours 6 hours, 10-12 hours more preferable, consolidate what is obtained
It is freeze-dried after body water and ethanol washing, obtains carbon ball template.The mass ratio of carbon source and deionized water is 1:10~20, more
It is preferred that 1:12~15, which directly affects the size of carbon ball, and then influences the partial size of material.Contain oxygen-containing function in carbon ball surface
Group can make adsorption of metal ions in the carbon ball template surface, and must control hydrothermal condition, make carbon ball partial size need be in 300nm-
Within the scope of 700nm, it can guarantee the lesser particle size range of the tertiary cathode material being finally prepared.Nickel salt, cobalt salt and manganese salt
The molar ratio of middle nickel element, cobalt element and manganese element be (1~8): (1~1.5): 1, preferred molar ratio be 1:1:1,6:2:2,
5:3:2 or 8:1:1, the tertiary cathode material performance being prepared is more preferably.
(2) precipitating reagent is added into the mixing suspension, after stirring, is separated by solid-liquid separation, collects precipitating；Precipitating reagent is preferably
Concentration is the ammonium hydroxide of 0.05~0.1mol/L, and the volume ratio of the volume and step (1) described mixing suspension of the precipitating reagent is
0.5~2:1.The concentration of precipitating reagent is most important for the hollow of tertiary cathode material, the layer structure of the invention of preparing, and this
With excellent chemical property when special structure ensure that the material for battery.
(3) it will be ground after the washing of precipitate, drying, carry out pre-oxidation under an oxygen-containing atmosphere, obtain hollow structure
Metal oxide spherical shape particle；The mass ratio of step (1) carbon ball and step (3) described metal oxide is 1:0.5-3,
Preferably 1:1-1.5；Preferred Pre oxidation is 350~650 DEG C, and more preferable 450-550 DEG C, preoxidation time is 1~4h.
(4) the metal oxide spherical shape particle of the hollow structure is mixed with lithium salts, is calcined in oxygen-containing atmosphere, it is natural
The NCM tertiary cathode material of hollow structure is obtained after being cooled to room temperature.Preferably, lithium source is lithium hydroxide, lithium carbonate or acetic acid
Lithium, the molar ratio of elemental lithium and step (3) described metal oxide is 0.8~2:1, more preferably 1-1.5:1 in the lithium source；
Preferred calcination temperature is 720~880 DEG C, and calcination time is 8~20h, more preferably 10-15 hours.
Surface is prepared rich in oxygen-containing group by selecting specific carbon source in the present invention under certain synthesis technology
(such as hydroxyl, carboxyl), diameter are the carbon ball of 300-700nm as template, and nickel-cobalt-manganese ternary is prepared using coprecipitation
Positive electrode, carbon ball surface are conducive to metal cation rich in oxygen-containing group and are adsorbed on carbon ball table by physically or chemically effect
Face.Carbon ball diameter control can aid in the formation of the tertiary cathode material of suitable particle size range in suitable range.Co-precipitation
The concentration control of the precipitating reagent of Shi Caiyong is also particularly critical, and the present invention selects the ammonium hydroxide of 0.05~0.1mol/L as co-precipitation
Agent.
The selection of carbon source of the present invention is most important, once attempts to replace glucose as carbon source using starch in experimentation
Or sucrose, however, it was found that it can not form carbon ball template.The carbon ball template of suitable dimension is the hollow tertiary cathode material of the present invention
Material is able to the necessary condition synthesized, is precipitated in carbon ball template surface, and pre-oxidation carbon ball is ablated, obtains with hollow structure
Nickel, cobalt and manganese metal oxide；Then it further mixes, calcines with lithium salts on the hollow metallic oxide surface
To the NCM tertiary cathode material with layer structure.
The present invention controls preparation condition, crystal is finally prepared in Optimizing Process Parameters by selecting raw material type meticulously
Structure is layer structure and the nickel-cobalt-manganese ternary positive electrode particle material with hollow structure, and grain graininess is thinner, with electrolyte
Contact is good, and layer structure has high theoretical capacity and a two-dimensional diffusion channel, hollow structure can alleviate in charge and discharge because
Particle caused by volume expansion crushes, and the cycle performance of battery and capacity to obtain excellent lay the foundation.
The present invention has obtained rich nickel tertiary cathode material using co-precipitation by template, which has good stratiform
Structure, can provide good lithium ion transmission channels, and the hollow structure of another aspect material can be alleviated in charge and discharge process
In volume expansion the problem of.The material is assembled into battery, it is first at 2.7~4.5V of voltage window, the current density of 0.1C
The specific discharge capacity of circle reaches 255mAh g-1, circulation 70 is enclosed still 154mAh g later-1Capacity, wherein coulombic efficiency be
99.9%.
The following are embodiments:
Embodiment 1
It takes 2.4g glucose to be dissolved in 30ml deionized water, is placed on 180 DEG C of hydro-thermals in 50ml water heating kettle after stirring 1h
10h is centrifuged obtains carbon ball template using freeze-drying after water and ethanol washing later.
It is 200mg according to tenor, a certain amount of NiCl is added in 80ml dehydrated alcohol2·6H2O、CoCl2·
6H2O、MnCl2·4H2Wherein the ratio of three kinds of metallic elements is 8:1:1, while the carbon ball template of 200mg is added in O, rear to stir
Suspension made from ultrasound.It is then slowly added into the ammonia spirit that 80ml concentration is 0.07mol/L, continues to stir 4h, centrifugation is washed
After washing, dried in 60 DEG C of blast drier.
The presoma of drying is obtained into metal oxide after 500 DEG C of calcining 3h under air atmosphere, is added later a certain amount of
Anhydrous Li2CO3, it is ensured that the atomic ratio of Li and metal is 1.1:1 in material, and 10h is calcined after 800 DEG C are warming up to after grinding, cooling
Tertiary cathode material is obtained to room temperature.
Fig. 1 is the particle size distribution figure for the carbon ball that the embodiment of the present invention 1 is prepared；It can be seen that obtained carbon ball distribution is equal
Even, particle size is between 350-450nm.
Fig. 2 is the infared spectrum on the carbon ball surface that the embodiment of the present invention 1 is prepared；Contain it can be seen that material surface is rich
Oxygen functional group (hydroxyl, carboxyl etc.), these functional groups can good adsorbing metal cations.
The particle size distribution figure for the ternary material that Fig. 3 embodiment of the present invention 1 is prepared.It can be seen that made from the present embodiment
The particle size range of ternary material is between 350-400nm.
1 gained ternary material SEM of Fig. 4 embodiment of the present invention figure；It can be seen that material maintains the basic apperance of carbon ball,
Grain size is between 350-500nm.
1 gained ternary material TEM of Fig. 5 embodiment of the present invention figure；It can be seen that material has hollow structure.
1 gained ternary material XRD diagram of Fig. 6 embodiment of the present invention；It can be seen that 18 ° or so diffraction maximum (003) intensity and 45 °
Diffraction maximum (104) intensity ratio 1.4 or so, illustrate that material keeps good layer structure.I (003)/I (104) diffraction
P-ratio is bigger, and the layer structure for representing material is better.From the figure, it can be concluded that, which is Li
(Ni0.8Co0.1Mn0.1)O2。
1 gained ternary material of Fig. 7 embodiment of the present invention first five circle CV figure, it can be seen that material oxidation electricity with higher
Position, so that material has high specific energy density.
Comparative example 1
It takes 2.4g starch dissolution in 30ml deionized water, is placed on 180 DEG C of hydro-thermal 10h in 50ml water heating kettle after stirring 1h,
It is centrifuged later and obtains carbon ball template using freeze-drying after water and ethanol washing.
It is 200mg according to tenor, a certain amount of NiCl is added in 80ml dehydrated alcohol2·6H2O、CoCl2·
6H2O、MnCl2·4H2Wherein the ratio of three kinds of metallic elements is 8:1:1, while the carbon ball template of 200mg is added in O, rear to stir
Suspension made from ultrasound.It is then slowly added into the ammonia spirit that 80ml concentration is 0.07mol/L, continues to stir 4h, centrifugation is washed
After washing, dried in 60 DEG C of blast drier.
The presoma of drying is obtained into metal oxide after 500 DEG C of calcining 3h under air atmosphere, is added later a certain amount of
Anhydrous Li2CO3, it is ensured that the atomic ratio of Li and metal is 1.1:1 in material, and 10h is calcined after 800 DEG C are warming up to after grinding, cooling
Tertiary cathode material is obtained to room temperature.
Fig. 8 is 1 gained ternary material SEM of comparative example figure of the present invention, it can be seen that obtained globs of material is got together, not
It is tangible at sphere structure.
Embodiment 2
It takes 2.4g glucose to be dissolved in 30ml deionized water, is placed on 180 DEG C of hydro-thermals in 50ml water heating kettle after stirring 1h
10h is centrifuged obtains carbon ball template using freeze-drying after water and ethanol washing later.
It is 200mg according to tenor, a certain amount of NiCl is added in 80ml dehydrated alcohol2·6H2O、CoCl2·
6H2O、MnCl2·4H2Wherein the ratio of three kinds of metallic elements is 1:1:1, while the carbon ball template of 200mg is added in O, rear to stir
Suspension made from ultrasound.It is then slowly added into the ammonia spirit that 80ml concentration is 0.07mol/L, continues to stir 4h, centrifugation is washed
After washing, dried in 60 DEG C of blast drier.
The presoma of drying is obtained into metal oxide after 500 DEG C of calcining 3h under air atmosphere, is added later a certain amount of
Anhydrous Li2CO3, it is ensured that the atomic ratio of Li and metal is 1.2:1 in material, and 15h is calcined after 750 DEG C are warming up to after grinding, cooling
Tertiary cathode material is obtained to room temperature, which is Li (Ni0.33Co0.33Mn0.33)O2。
Fig. 9 is first five circle charging and discharging curve of 2 gained ternary material of the embodiment of the present invention, it can be seen that material has high ratio
Capacity and good cyclical stability.
Embodiment 3
It takes 2.4g glucose to be dissolved in 30ml deionized water, is placed on 160 DEG C of hydro-thermals in 50ml water heating kettle after stirring 1h
20h is centrifuged obtains carbon ball template using freeze-drying after water and ethanol washing later.
It is 200mg according to metal oxide content, a certain amount of NiCl is added in 80ml dehydrated alcohol2·6H2O、
CoCl2·6H2O、MnCl2Wherein the ratio of three kinds of metallic elements is 5:3:2, while the carbon ball template of 200mg is added in 4H2O,
Suspension made from stirring ultrasound afterwards.It is then slowly added into the ammonia spirit that 80ml concentration is 0.10mol/L, continues to stir 4h,
After centrifuge washing, dried in 60 DEG C of blast drier.
The presoma of drying is obtained into metal oxide after 500 DEG C of calcining 3h under air atmosphere, is added later a certain amount of
LiOHH2O, it is ensured that Li and metallic atom ratio are 1.2:1 in material, calcine 10h after 800 DEG C are warming up to after grinding, are cooled to
Room temperature obtains tertiary cathode material, which is Li (Ni0.5Co0.3Mn0.2)O2。
Embodiment 4
It takes 2.4g sucrose to be dissolved in 30ml deionized water, is placed on 200 DEG C of hydro-thermal 10h in 50ml water heating kettle after stirring 1h,
It is centrifuged later and obtains carbon ball template using freeze-drying after water and ethanol washing.
It is 200mg according to metal oxide content, a certain amount of NiCl is added in 80ml dehydrated alcohol2·6H2O、
CoCl2·6H2O、MnCl2·4H2Wherein the ratio of three kinds of metallic elements is 6:2:2, while the carbon ball template of 200mg is added in O,
Suspension made from stirring ultrasound afterwards.It is then slowly added into the ammonia spirit that 80ml concentration is 0.10mol/L, continues to stir 4h,
After centrifuge washing, dried in 60 DEG C of blast drier.
The presoma of drying is obtained into metal oxide after 550 DEG C of calcining 4h under air atmosphere, is added later a certain amount of
LiOHH2O, it is ensured that Li and metallic atom ratio are 1.5:1 in material, calcine 15h after 850 DEG C are warming up to after grinding, are cooled to
Room temperature obtains tertiary cathode material, which is Li (Ni0.6Co0.2Mn0.2)O2。
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of ternary cathode material of lithium ion battery, which is characterized in that the tertiary cathode material is the spherical shape for having hollow structure
Particle, which is 300nm-600nm, and the crystal structure of the spheric granules is layer structure, chemical composition
For LiNi(1-x-y)CoxMnyO2, wherein x value range is 0.1-0.3, and y value range is 0.1-0.3.
2. tertiary cathode material as described in claim 1, which is characterized in that be including mass fraction in the tertiary cathode material
The manganese of the nickel of 30%-80%, the cobalt of 10%-30% and 10%-30%.
3. the preparation method of ternary cathode material of lithium ion battery as claimed in claim 1 or 2, which is characterized in that including such as
Lower step:
(1) after mixing carbon ball, nickel salt, cobalt salt and manganese salt, dehydrated alcohol is added, stirs to get mixing suspension；Wherein, described
Contain oxygen-containing functional group, and a diameter of 300nm-700nm in carbon ball surface；
(2) precipitating reagent is added into the mixing suspension, after stirring, is separated by solid-liquid separation, collects precipitating；
(3) it will be ground after the washing of precipitate, drying, carry out pre-oxidation under an oxygen-containing atmosphere, obtain metal oxide spheres
Shape particle；
(4) the metal oxide spherical shape particle is mixed with lithium salts, is calcined in oxygen-containing atmosphere, obtained after being cooled to room temperature
The ternary cathode material of lithium ion battery of hollow structure.
4. preparation method as claimed in claim 3, which is characterized in that the carbon ball is prepared as follows to obtain: by carbon
Source disperses in deionized water, to obtain transparent uniform solution, carries out hydro-thermal reaction, obtains carbon ball template.
5. preparation method as claimed in claim 4, the carbon ball is prepared as follows to obtain: by glucose or Sucrose
It dissipating in deionized water, obtains transparent uniform solution, the mass concentration of the glucose in solutions or sucrose is 5%-10%,
150 DEG C -220 DEG C of progress hydro-thermal reaction -15 hours 6 hours, will be freeze-dried, obtain after obtained solid water and ethanol washing
The carbon ball template.
6. preparation method as claimed in claim 3, which is characterized in that nickel member in step (1) nickel salt, cobalt salt and manganese salt
The molar ratio of element, cobalt element and manganese element is (1~8): (1~1.5): 1.
7. preparation method as claimed in claim 3, which is characterized in that step (1) carbon ball and step (3) described metal oxygen
The mass ratio of compound is 1:0.5-3.
8. preparation method as claimed in claim 3, which is characterized in that step (2) described precipitating reagent be concentration be 0.05~
The ammonium hydroxide of 0.1mol/L, the volume of the precipitating reagent and the volume ratio of step (1) described mixing suspension are 0.5~2:1.
9. preparation method as claimed in claim 3, which is characterized in that step (3) Pre oxidation is 350~650 DEG C,
Preoxidation time is 1~4h.
10. preparation method as claimed in claim 3, which is characterized in that step (4) lithium source is lithium hydroxide, lithium carbonate
Or lithium acetate, the molar ratio of elemental lithium and step (3) described metal oxide is 0.8~2:1 in the lithium source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810744438.9A CN109052490B (en) | 2018-07-09 | 2018-07-09 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810744438.9A CN109052490B (en) | 2018-07-09 | 2018-07-09 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109052490A true CN109052490A (en) | 2018-12-21 |
| CN109052490B CN109052490B (en) | 2019-11-22 |
Family
ID=64819642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810744438.9A Active CN109052490B (en) | 2018-07-09 | 2018-07-09 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109052490B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888197A (en) * | 2018-12-26 | 2019-06-14 | 河南科隆新能源股份有限公司 | A kind of high magnification long circulating performance multi-element composite positive pole material and preparation method thereof |
| CN112768685A (en) * | 2021-04-09 | 2021-05-07 | 湖南长远锂科股份有限公司 | Long-cycle and high-power lithium ion battery cathode material and preparation method thereof |
| CN113830844A (en) * | 2021-09-28 | 2021-12-24 | 蜂巢能源科技有限公司 | Hollow porous ternary cathode material, preparation method thereof and lithium ion battery |
| CN114464789A (en) * | 2022-01-19 | 2022-05-10 | 华中科技大学 | Energy storage secondary battery layered positive electrode material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938459A (en) * | 2012-11-14 | 2013-02-20 | 浙江南都电源动力股份有限公司 | Method for preparing positive material of high-power lithium ion battery |
| CN104241630A (en) * | 2014-07-10 | 2014-12-24 | 奇瑞汽车股份有限公司 | Lithium nickel cobalt manganate hollow sphere as well as preparation method and application thereof |
| CN104393284A (en) * | 2014-11-17 | 2015-03-04 | 天津大学 | Nickel oxide nano-particle loaded porous hard carbon sphere negative electrode material and preparation method thereof |
| CN105977462A (en) * | 2016-06-01 | 2016-09-28 | 中物院成都科学技术发展中心 | Preparation method of lithium-rich manganese-based positive electrode material with hollow structure |
| CN106025260A (en) * | 2016-07-06 | 2016-10-12 | 上海交通大学 | Ternary cathode material of hollow spherical nano-structure and preparing method thereof |
| CN107069032A (en) * | 2016-11-17 | 2017-08-18 | 北京师范大学 | A kind of preparation method of lithium ion battery hollow ball shape lithium-rich manganese-based anode material |
| CN108091871A (en) * | 2017-12-28 | 2018-05-29 | 清远佳致新材料研究院有限公司 | A kind of porous spherical ternary cathode material of lithium ion battery and preparation method thereof |
-
2018
- 2018-07-09 CN CN201810744438.9A patent/CN109052490B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938459A (en) * | 2012-11-14 | 2013-02-20 | 浙江南都电源动力股份有限公司 | Method for preparing positive material of high-power lithium ion battery |
| CN104241630A (en) * | 2014-07-10 | 2014-12-24 | 奇瑞汽车股份有限公司 | Lithium nickel cobalt manganate hollow sphere as well as preparation method and application thereof |
| CN104393284A (en) * | 2014-11-17 | 2015-03-04 | 天津大学 | Nickel oxide nano-particle loaded porous hard carbon sphere negative electrode material and preparation method thereof |
| CN105977462A (en) * | 2016-06-01 | 2016-09-28 | 中物院成都科学技术发展中心 | Preparation method of lithium-rich manganese-based positive electrode material with hollow structure |
| CN106025260A (en) * | 2016-07-06 | 2016-10-12 | 上海交通大学 | Ternary cathode material of hollow spherical nano-structure and preparing method thereof |
| CN107069032A (en) * | 2016-11-17 | 2017-08-18 | 北京师范大学 | A kind of preparation method of lithium ion battery hollow ball shape lithium-rich manganese-based anode material |
| CN108091871A (en) * | 2017-12-28 | 2018-05-29 | 清远佳致新材料研究院有限公司 | A kind of porous spherical ternary cathode material of lithium ion battery and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888197A (en) * | 2018-12-26 | 2019-06-14 | 河南科隆新能源股份有限公司 | A kind of high magnification long circulating performance multi-element composite positive pole material and preparation method thereof |
| CN109888197B (en) * | 2018-12-26 | 2021-12-10 | 河南科隆新能源股份有限公司 | High-rate long-cycle-performance multi-element composite cathode material and preparation method thereof |
| CN112768685A (en) * | 2021-04-09 | 2021-05-07 | 湖南长远锂科股份有限公司 | Long-cycle and high-power lithium ion battery cathode material and preparation method thereof |
| CN113830844A (en) * | 2021-09-28 | 2021-12-24 | 蜂巢能源科技有限公司 | Hollow porous ternary cathode material, preparation method thereof and lithium ion battery |
| CN114464789A (en) * | 2022-01-19 | 2022-05-10 | 华中科技大学 | Energy storage secondary battery layered positive electrode material and preparation method thereof |
| CN114464789B (en) * | 2022-01-19 | 2023-03-10 | 华中科技大学 | Energy storage secondary battery layered positive electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109052490B (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109052490B (en) | A kind of ternary cathode material of lithium ion battery and preparation method thereof | |
| CN109167056B (en) | Tungsten ion doped high-nickel layered oxide lithium battery positive electrode material and preparation method thereof | |
| CN113023794B (en) | Cobalt-free high-nickel positive electrode material, preparation method thereof, lithium ion battery positive electrode and lithium ion battery | |
| CN112928252A (en) | Sodium-ion battery positive electrode material and preparation method and application thereof | |
| CN112018341A (en) | High-capacity high-nickel cathode material and preparation method thereof | |
| CN108987708A (en) | A kind of sodium-ion battery positive material, preparation method and sodium-ion battery | |
| CN105449169A (en) | Lithium ion battery cathode material, preparation method and lithium ion battery | |
| CN106207138A (en) | A kind of method for preparing anode material of lithium-ion battery and application thereof | |
| CN107845781B (en) | Negative electrode active material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery | |
| CN102163713A (en) | Method for preparing high-voltage spinel anode material of lithium-ion secondary battery | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN102013481A (en) | Method for synthesizing spherical gradient lithium-rich anode material | |
| CN107275634B (en) | Method for synthesizing high-tap-density and high-capacity spherical lithium-rich manganese-based positive electrode material without complexing agent | |
| CN108899480A (en) | A kind of long circulation life height ratio capacity nickel cobalt aluminium positive electrode and preparation method thereof | |
| CN102891299A (en) | High-rate lithium ion battery cathode material and preparation method and application thereof | |
| CN103094550A (en) | Preparation method of lithium-rich anode material | |
| CN107785551A (en) | The lithium-rich oxide material and preparation method of a kind of phase structure ratio gradient | |
| CN104934591A (en) | High-volume-energy-density spherical Li-rich cathode material and preparing method of high-volume-energy-density spherical Li-rich cathode material | |
| CN110683590A (en) | Preparation method of nickel-cobalt-aluminum hydroxide precursor based on aluminum element concentration gradient distribution | |
| CN102751470A (en) | Preparation method of lithium ion battery high-voltage composite cathode material | |
| CN106129360A (en) | A kind of high-tap density lithium-rich manganese-based anode material and preparation method thereof | |
| CN110416530B (en) | Flower-like manganese dioxide/carbon composite material and preparation method and application thereof | |
| WO2014169717A1 (en) | Electrochemical energy storage device of aqueous alkali metal ions | |
| CN105140472A (en) | Tungsten-modified lithium-rich manganese-based layered cathode material for lithium ion battery and preparation method thereof | |
| CN103855372B (en) | High-manganese composite cathode material and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |