CN109449382A - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
- Publication number
- CN109449382A CN109449382A CN201811106607.2A CN201811106607A CN109449382A CN 109449382 A CN109449382 A CN 109449382A CN 201811106607 A CN201811106607 A CN 201811106607A CN 109449382 A CN109449382 A CN 109449382A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- presoma
- anode material
- ratio
- 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
-
- 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
-
- 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
-
- 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 discloses a kind of height ratio capacity lithium abundant cathode material for lithium ion batteries and preparation method thereof, are related to technical field of lithium ion.Lithium-rich anode material chemical formula is Li1.2‑xMx[Ni0.13Co0.13Mn0.54]O2, wherein 0≤x≤0.3, M are metal Na or K.Positive electrode includes above-mentioned rich lithium material, and positive plate of lithium battery coats above-mentioned positive electrode.The positive electrode not only has good spherical morphology, and using this material as the lithium ion battery of positive plate, the cycle performance of rich anode material of lithium battery is improved under the premise of keeping high specific discharge capacity, it solves that existing rich anode material of lithium battery specific capacity is low, defect of poor circulation, shows good chemical property.
Description
Technical field
The present invention relates to lithium-enriched cathodic material of lithium ion battery technical field, especially a kind of height ratio capacity lithium ion battery
With lithium-rich anode material and preparation method thereof.
Background technique
Lithium ion battery is due to its height ratio capacity, high working voltage, excellent cycle life, memory-less effect, pollution-free
The advantages that receive the whole world and widely pay close attention to, become the hot spot of countries nowadays energy storage technologies research.Generally it is applicable in
In numerous areas such as Aeronautics and Astronautics, extensive energy storage, portable electronic device, pure electric automobile and hybrid vehicles.
With the development of mobile communication equipment and electric car, the demand to high-energy-density density lithium ion battery is increasingly
Greatly.Also to performances such as the specific capacity of lithium ion battery, specific power, cycle lives, more stringent requirements are proposed for this.Quotient at this stage
The anode material for lithium-ion batteries of product includes stratiform LiCoO2, stratiform ternary material (NCM and NCA), olivine-type LiFeO4With
Spinelle shape LiMn2O4, actual specific capacity is difficult to meet electric car to high energy density lithium ion in 100~180mAh/g
The market demand of battery, therefore, the specific capacity of positive electrode have become the bottleneck of limiting lithium ion cell energy density raising.This
Outside, the Department of Science and Technology " 13 " planning, which proposes single battery energy density, need to reach the index of 300Wh/kg, therefore develop high
Voltage, height ratio capacity, long circulating, powerful anode material for lithium-ion batteries become one of hot spot studied at present.
Lithium-rich anode material has big specific capacity (>=250mAh/g) and high discharge voltage (3.8V), and theoretical energy is close
Degree is up to 900Wh/kg, has high-energy-density, high power, high circulation service life, advantages of environment protection, especially its high-energy
Density (150Wh/kg, 650Wh/L) makes it have powerful competitiveness in power vehicle field, is the reason of the following power battery
Think positive electrode, be widely used in the equipment such as small-sized electronic product and electric car, thus studies height ratio capacity richness lithium
Positive electrode has very important realistic meaning.Although lithium-rich anode material specific capacity with higher, electric discharge is imitated for the first time
Rate is lower, and structure changes in cyclic process, and cyclical stability is caused to decline；And oxygen is analysed in cyclic process and brings safety
Hidden danger；The problems such as capacity attenuation is larger under high magnification influences its practical application.It is ground in view of the above problems, needing to be modified it
Study carefully, to overcome shortcoming, common method of modifying includes surface cladding and bulk phase-doped.
Surface cladding can between guard electrode material and electrolyte interface stability, reduce between electrode and electrolyte
Side reaction, reduce cyclic process middle impedance increase, improve the rate capability and cycle-index of material.Coating substance can also
Retain oxygen loss and is formed by Lacking oxygen, improve the charge/discharge capacity of material, maintains the material of stabilizing and increasing of crystal structure
Security performance.The material of cladding is usually to be able to suppress electrolyte to the electrochemistry of the corrosion of active material and reduction oxygen release
Inert substance.Mainly carbon material (such as C, graphene oxide), oxide (such as Al2O3), fluoride (such as AlF3), phosphate (such as
LiFePO4) and organic matter (such as PPY) cladding.Surface cladding preparation process is cumbersome, and required covering material compares complexity,
Environmental pollution is big, requires capsulation condition high.Such as 105244490 A of CN discloses a kind of nickelic positive material of cobalt manganese cladding
Material and preparation method thereof.The preparation method of such nickelic positive electrode be by nickelic positive electrode kernel with containing certain density
Ammonia spirit mixing, then saline solution (Co and Mn) and the dropwise addition of lye cocurrent are reacted, at least one of positive electrode surface
Divide upper formation at least containing the oxide cladding layers of Li, Co and Mn, finally heat treatment obtains the nickelic positive electrode.But
The defect of the program is, can not reduce the residual alkali amount on positive electrode surface, poor processability, and preparation method is cumbersome, cladding
Layer preparation process is difficult to control.
It is coated compared to surface, bulk phase-doped is a kind of simple and effective means for improving electrode material chemical property, energy
Enough significantly improve the structural stability and high rate performance of material.It generally selects and element similar in the ionic radius of replaced element
Modification is doped to rich lithium material, to improve the electric conductivity of material, increases cell parameter, forms stronger metal-oxygen key, from
And the structural stability of material is improved, promote Li+Migration promotes the chemical property of rich lithium material.Doping mainly include sun from
Son doping and anion doped and cation-anion co-doping are miscellaneous.Cation doping is studied relatively broad, have Co, Mo, Cr, Fe,
The doping such as Ti, Ru, Se, Si, Sn, Ba.But these doped chemical prices phases are costly, cause serious pollution to the environment, and after doping
Capacity of lithium ion battery expanded reach it is little, and at present which kind of element, which is most suitable for mixing, is not shown for the research of doping
It is miscellaneous.In this case, finding a kind of suitable doped chemical has very big research significance.
Summary of the invention
The object of the present invention is to provide a kind of height ratio capacity lithium abundant cathode material for lithium ion battery and its preparation sides
Method is doped using common element, and solving rich lithium battery while keeping high specific capacity, discharging efficiency is low for the first time
The problem of.
The present invention provides a kind of height ratio capacity lithium abundant cathode material for lithium ion battery, molecular formula Li1.2-xMx
[Ni0.13Co0.13Mn0.54]O2, wherein 0≤x≤0.3, it is preferred that x=0.15；M is doped metallic elements Na and K.
In a first aspect, the present invention provides a kind of height ratio capacity lithium abundant cathode material for lithium ion battery, chemical formula is
Li1.05Na0.15[Ni0.13Co0.13Mn0.54]O2, the preparation method of the positive electrode follows the steps below:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide is as complexing agent, carbon
Sour hydrogen ammonium as reaction bottom liquid, by adjust precipitating reagent and ammonium hydroxide sample introduction speed control reaction solution pH value 9 ± 0.2, into
Row coprecipitation reaction, (MnNiCo) CO that will be obtained after reaction3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma and sodium carbonate according to molar ratio 1.05:1:0.15 carry out ground and mixed, carry out after mixing
High-temperature calcination；Calcination process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 1~5 DEG C of speed per minute
500 DEG C, 5h is kept the temperature, then 900 DEG C of calcining 15h is warming up to according still further to identical heating rate, is cooled down at room temperature after the completion of sintering,
It obtains rich lithium and mixes sodium positive electrode Li1.05Na0.15[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, presoma positive electrode are added sequentially to N- first according to the ratio of mass ratio 1:1:8
It in base-pyrrolidones, after being stirred, is coated, dries, obtain lithium ion battery richness lithium and mix sodium positive electrode.
Second aspect, the present invention provide a kind of height ratio capacity lithium abundant cathode material for lithium ion battery, and chemical formula is
Li1.05K0.15[Ni0.13Co0.13Mn0.54]O2, the preparation method of the positive electrode follows the steps below:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide is as complexing agent, carbon
Sour hydrogen ammonium as reaction bottom liquid, by adjust precipitating reagent and ammonium hydroxide sample introduction speed control reaction solution pH value 9 ± 0.2, into
Row coprecipitation reaction, (MnNiCo) CO that will be obtained after reaction3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma and potassium chloride according to molar ratio 1.05:1:0.15 carry out ground and mixed, carry out after mixing
High-temperature calcination；Calcination process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 1~5 DEG C of speed per minute
500 DEG C, 5h is kept the temperature, then 900 DEG C of calcining 15h is warming up to according still further to identical heating rate, is cooled down at room temperature after the completion of sintering,
It obtains rich lithium and mixes potassium positive electrode Li1.05K0.15[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, presoma positive electrode are added sequentially to N- first according to the ratio of mass ratio 1:1:8
It in base-pyrrolidones, after being stirred, is coated, dries, obtain lithium ion battery richness lithium and mix potassium positive electrode.
The third aspect, the present invention provide a kind of height ratio capacity lithium abundant cathode material for lithium ion battery, chemical formula Li1.2
[Ni0.13Co0.13Mn0.54]O2, it is used for blank control group.The preparation method of the richness anode material of lithium battery according to the following steps into
Row:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide leads to as complexing agent
The pH value of the sample introduction speed control reaction solution of precipitating reagent and ammonium hydroxide is overregulated 9 ± 0.2, carries out coprecipitation reaction, reaction terminates
(MnNiCo) CO that will be obtained afterwards3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma according to molar ratio 1.2:1 carry out ground and mixed, carry out high-temperature calcination after mixing；Calcining
Process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 500 DEG C with 1~5 DEG C of speed per minute, keeps the temperature 5h,
Then 900 DEG C of calcining 15h are warming up to according still further to identical heating rate, are cooled down at room temperature after the completion of sintering, obtains lithium-rich anode
Material Li1.2[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, positive persursor material are added sequentially to N- first according to the ratio of mass ratio 1:1:8
In base-pyrrolidones, after being stirred, it is coated, dries, obtain lithium-enriched cathodic material of lithium ion battery.
The present invention has the advantage that compared to the prior art
1) ammonium hydrogen carbonate is added in preparation method in the liquid of bottom, forms Na2CO3-NH4OH-NH4HCO3System can be adjusted well
PH value in reaction obtains the good spherical precursor of pattern；
2) positive electrode is doped using common sodium and potassium element, is replaced compared to other Co, Mo, Cr, Fe, Ti, Ru
For the position Ni/Co/Mn difference, what Na and K replaced is the position Li, since Na/K atomic radius ratio Li is big, can be expanded after doping
The interplanar distance of material, to be conducive to Li+Diffusion.And sodium source and potassium resource are cheap, and environmental pollution is small, preparation
Technological operation is simple, easily controllable；
3) the rich lithium ion battery specific discharge capacity of the lithium-rich anode material after sodium contaminated/potassium, preparation is higher, puts to battery
Electric specific capacity promotion becomes apparent from.
Detailed description of the invention
Fig. 1 is gained (MnNiCo) CO in the embodiment of the present invention 13The SEM of presoma schemes.
Fig. 2 is gained (MnNiCo) CO in comparative example 3 of the present invention3The SEM of presoma schemes.
Fig. 3 is gained Li in the embodiment of the present invention 11.05Na0.15[Ni0.13Co0.13Mn0.54]O2SEM figure.
Fig. 4 is the first charge-discharge curve comparison of embodiment 1, embodiment 2 and 3 gained positive electrode of comparative example assembling button electricity
Figure.
Specific embodiment
The present invention will be further explained with reference to the examples below, needs to show following the description merely to solution
The present invention is released, its content is not defined.
Embodiment 1: a kind of height ratio capacity lithium abundant cathode material for lithium ion battery, chemical formula Li are provided1.05Na0.15
[Ni0.13Co0.13Mn0.54]O2.The positive electrode follows the steps below preparation:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide is as complexing agent, carbon
Sour hydrogen ammonium as reaction bottom liquid, by adjust precipitating reagent and ammonium hydroxide sample introduction speed control reaction solution pH value 9 ± 0.2, into
Row coprecipitation reaction, (MnNiCo) CO that will be obtained after reaction3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma and sodium carbonate according to molar ratio 1.05:1:0.15 carry out ground and mixed, carry out after mixing
High-temperature calcination；Calcination process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 1~5 DEG C of speed per minute
500 DEG C, 5h is kept the temperature, then 900 DEG C of calcining 15h is warming up to according still further to identical heating rate, is cooled down at room temperature after the completion of sintering,
It obtains rich lithium and mixes sodium positive electrode Li1.05Na0.15[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, presoma positive electrode are added sequentially to N- first according to the ratio of mass ratio 1:1:8
It in base-pyrrolidones, after being stirred, is coated, dries, obtain lithium ion battery richness lithium and mix sodium positive electrode.
Embodiment 2: a kind of height ratio capacity lithium abundant cathode material for lithium ion battery, chemical formula Li are provided1.05K0.15
[Ni0.13Co0.13Mn0.54]O2.The positive electrode follows the steps below preparation:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide is as complexing agent, carbon
Sour hydrogen ammonium as reaction bottom liquid, by adjust precipitating reagent and ammonium hydroxide sample introduction speed control reaction solution pH value 9 ± 0.2, into
Row coprecipitation reaction, (MnNiCo) CO that will be obtained after reaction3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma and potassium chloride according to molar ratio 1.05:1:0.15 carry out ground and mixed, carry out after mixing
High-temperature calcination；Calcination process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 1~5 DEG C of speed per minute
500 DEG C, 5h is kept the temperature, then 900 DEG C of calcining 15h is warming up to according still further to identical heating rate, is cooled down at room temperature after the completion of sintering,
It obtains rich lithium and mixes potassium positive electrode Li1.05K0.15[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, presoma positive electrode are added sequentially to N- first according to the ratio of mass ratio 1:1:8
It in base-pyrrolidones, after being stirred, is coated, dries, obtain lithium ion battery richness lithium and mix potassium positive electrode.
Embodiment 3: a kind of height ratio capacity lithium abundant cathode material for lithium ion battery, chemical formula Li are provided1.2
[Ni0.13Co0.13Mn0.54]O2.The positive electrode follows the steps below preparation:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide leads to as complexing agent
The pH value of the sample introduction speed control reaction solution of precipitating reagent and ammonium hydroxide is overregulated 9 ± 0.2, carries out coprecipitation reaction, reaction terminates
(MnNiCo) CO that will be obtained afterwards3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma according to molar ratio 1.2:1 carry out ground and mixed, carry out high-temperature calcination after mixing；Calcining
Process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 500 DEG C with 1~5 DEG C of speed per minute, keeps the temperature 5h,
Then 900 DEG C of calcining 15h are warming up to according still further to identical heating rate, are cooled down at room temperature after the completion of sintering, obtains lithium-rich anode
Material Li1.2[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, positive persursor material are added sequentially to N- first according to the ratio of mass ratio 1:1:8
In base-pyrrolidones, after being stirred, it is coated, dries, obtain lithium-enriched cathodic material of lithium ion battery.
Embodiment 1, embodiment 2 and comparative example 3, which are obtained positive electrode, takes piece to be assembled into button electricity (cathode metal lithium sheet)
Test charge-discharge performance, cycle performance.
As can be seen that the preparation method provided using this patent, obtained presoma pattern phase from the SEM figure of Fig. 1-2
The presoma obtained compared with commonsense method (comparative example 3) has better spherical morphology, and uniform in size.From the SEM figure of Fig. 3
Find out, the positive electrode fired after doping vario-property still remains presoma spherical looks well, this Fabrication of High Specific Capacitance to material
Amount and for the first time discharging efficiency play a positive role.
Fig. 4 is the first charge-discharge curve comparison figure of embodiment 1, embodiment 2 and 3 resulting materials of comparative example at 0.1C.
From the figure, it can be seen that doping Na/K modified material has higher first discharge specific capacity compared to the material to undope, protect
Hold height ratio capacity advantage.
Furthermore the present invention proposes that element involved in the method for modifying to lithium-rich anode material is common and cheap Na, K
Salt is of great significance for the cost and environmental contamination that reduce material modification, while preparation process is simple, it is easy to accomplish work
Industry large-scale production provides high operability value to prepare positive electrode.
It should be noted that embodiment described above is only the skill to the illustrative and not limiting of technical solution of the present invention
The equivalent replacement of art field those of ordinary skill or other modifications made according to the prior art, as long as no beyond the present invention
The thinking and range of technical solution, should be included within interest field of the presently claimed invention.
Claims (8)
1. a kind of lithium-rich anode material, which is characterized in that the molecular formula of the lithium-rich anode material is Li1.2-xMx
[Ni0.13Co0.13Mn0.54]O2, wherein 0≤x≤0.3.
2. according to claim 1, it is preferable that x=0.15；The molecular formula of the lithium-rich anode material is
Li1.05M0.15[Ni0.13Co0.13Mn0.54]O2。
3. according to claim 1, wherein M is metal Na；The molecular formula of the lithium-rich anode material is
Li1.05Na0.15[Ni0.13Co0.13Mn0.54]O2。
4. according to claim 1, wherein M is metal K；The molecular formula of the lithium-rich anode material is
Li1.05K0.15[Ni0.13Co0.13Mn0.54]O2。
5. lithium-enriched cathodic material of lithium ion battery described in -4 according to claim 1, which is characterized in that positive electrode includes rich lithium
Material, conductive agent and binder, three's mass ratio are 8:1:1；Conductive agent uses conductive black, and binder uses polyvinylidene fluoride
Alkene.
6. the preparation method of height ratio capacity lithium-enriched cathodic material of lithium ion battery described in -5, feature exist according to claim 1
In being made by the steps:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide is as complexing agent, carbon
Sour hydrogen ammonium as reaction bottom liquid, by adjust precipitating reagent and ammonium hydroxide sample introduction speed control reaction solution pH value 9 ± 0.2, into
Row coprecipitation reaction, (MnNiCo) CO that will be obtained after reaction3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma and sodium carbonate according to molar ratio 1.05:1:0.15 carry out ground and mixed, carry out after mixing
High-temperature calcination；Calcination process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 1~5 DEG C of speed per minute
500 DEG C, 5h is kept the temperature, then 900 DEG C of calcining 15h is warming up to according still further to identical heating rate, is cooled down at room temperature after the completion of sintering,
Obtain presoma lithium-rich anode material Li1.05Na0.15[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, presoma positive electrode are added sequentially to N- first according to the ratio of mass ratio 1:1:8
It in base-pyrrolidones, after being stirred, is coated, dries, obtain lithium ion battery richness lithium and mix sodium positive electrode.
7. the preparation method of height ratio capacity lithium-enriched cathodic material of lithium ion battery described in -5, feature exist according to claim 1
In being made by the steps:
1) it is calculated with molar ratio, the metal salt of manganese sulfate, cobaltous sulfate, nickel sulfate is dissolved in deionization according to the ratio of 4:1:1
In water, continuously metal salt solution is pumped into reaction kettle with peristaltic pump, uses Na2CO3As precipitating reagent, ammonium hydroxide is as complexing agent, carbon
Sour hydrogen ammonium as reaction bottom liquid, by adjust precipitating reagent and ammonium hydroxide sample introduction speed control reaction solution pH value 9 ± 0.2, into
Row coprecipitation reaction, (MnNiCo) CO that will be obtained after reaction3After suction filtration, washing, drying, presoma is made；
2) by Li2CO3, presoma and potassium chloride according to molar ratio 1.05:1:0.15 carry out ground and mixed, carry out after mixing
High-temperature calcination；Calcination process carries out under Muffle furnace air atmosphere, using stage temperature control, is warming up to 1~5 DEG C of speed per minute
500 DEG C, 5h is kept the temperature, then 900 DEG C of calcining 15h is warming up to according still further to identical heating rate, is cooled down at room temperature after the completion of sintering,
Obtain presoma lithium-rich anode material Li1.05K0.15[Ni0.13Co0.13Mn0.54]O2；
3) Kynoar, conductive black, presoma positive electrode are added sequentially to N- first according to the ratio of mass ratio 1:1:8
It in base-pyrrolidones, after being stirred, is coated, dries, obtain lithium ion battery richness lithium and mix potassium positive electrode.
8. during preparing precursor preparation, ammonium hydrogen carbonate is added in the liquid of bottom according to claim 6-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811106607.2A CN109449382A (en) | 2018-09-21 | 2018-09-21 | A kind of anode material for lithium-ion batteries and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811106607.2A CN109449382A (en) | 2018-09-21 | 2018-09-21 | A kind of anode material for lithium-ion batteries and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109449382A true CN109449382A (en) | 2019-03-08 |
Family
ID=65530830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811106607.2A Pending CN109449382A (en) | 2018-09-21 | 2018-09-21 | A kind of anode material for lithium-ion batteries and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109449382A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111554920A (en) * | 2020-05-19 | 2020-08-18 | 江西远东电池有限公司 | Lithium-rich manganese-based positive electrode material containing sodium ions, precursor thereof and preparation method |
| CN111661880A (en) * | 2020-06-16 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Positive electrode material and preparation method thereof |
| CN111916728A (en) * | 2020-07-15 | 2020-11-10 | 中国科学院宁波材料技术与工程研究所 | Electrochemical doping method of lithium-rich manganese-based positive electrode material and lithium-rich manganese-based positive electrode material doped with same |
| CN112062167A (en) * | 2020-08-28 | 2020-12-11 | 常熟理工学院 | Micron-sized binary doped lithium-rich material and preparation method and application thereof |
| CN112599765A (en) * | 2020-12-18 | 2021-04-02 | 西北工业大学 | Sodium/potassium-doped high-performance lithium-manganese-nickel-based positive electrode material and preparation method thereof |
| WO2021175233A1 (en) * | 2020-03-03 | 2021-09-10 | 北京当升材料科技股份有限公司 | Lithium-manganese-rich material, preparation method for same, and applications thereof |
| CN115986105A (en) * | 2023-01-04 | 2023-04-18 | 宁德时代新能源科技股份有限公司 | Positive electrode material, preparation method thereof, secondary battery and power utilization device |
-
2018
- 2018-09-21 CN CN201811106607.2A patent/CN109449382A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4047688A4 (en) * | 2020-03-03 | 2023-11-29 | Beijing Easpring Material Technology Co., Ltd. | Lithium-manganese-rich material, preparation method for same, and applications thereof |
| US11958757B2 (en) | 2020-03-03 | 2024-04-16 | Beijing Easpring Material Technology Co., Ltd. | Lithium-manganese-rich material, preparation method for same, and applications thereof |
| WO2021175233A1 (en) * | 2020-03-03 | 2021-09-10 | 北京当升材料科技股份有限公司 | Lithium-manganese-rich material, preparation method for same, and applications thereof |
| JP2022545571A (en) * | 2020-03-03 | 2022-10-27 | 北京当升材料科技股▲フン▼有限公司 | Lithium manganese rich material, method of making and use thereof |
| JP7204049B2 (en) | 2020-03-03 | 2023-01-13 | 北京当升材料科技股▲フン▼有限公司 | Lithium manganese rich material, method of making and use thereof |
| CN111554920A (en) * | 2020-05-19 | 2020-08-18 | 江西远东电池有限公司 | Lithium-rich manganese-based positive electrode material containing sodium ions, precursor thereof and preparation method |
| CN111661880A (en) * | 2020-06-16 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Positive electrode material and preparation method thereof |
| CN111661880B (en) * | 2020-06-16 | 2022-08-09 | 中国科学院宁波材料技术与工程研究所 | Positive electrode material and preparation method thereof |
| CN111916728A (en) * | 2020-07-15 | 2020-11-10 | 中国科学院宁波材料技术与工程研究所 | Electrochemical doping method of lithium-rich manganese-based positive electrode material and lithium-rich manganese-based positive electrode material doped with same |
| CN112062167A (en) * | 2020-08-28 | 2020-12-11 | 常熟理工学院 | Micron-sized binary doped lithium-rich material and preparation method and application thereof |
| CN112062167B (en) * | 2020-08-28 | 2023-09-22 | 常熟理工学院 | Micron-sized binary doped lithium-rich material and preparation method and application thereof |
| CN112599765A (en) * | 2020-12-18 | 2021-04-02 | 西北工业大学 | Sodium/potassium-doped high-performance lithium-manganese-nickel-based positive electrode material and preparation method thereof |
| CN115986105B (en) * | 2023-01-04 | 2023-11-21 | 宁德时代新能源科技股份有限公司 | Positive electrode material, preparation method thereof, secondary battery and power utilization device |
| CN115986105A (en) * | 2023-01-04 | 2023-04-18 | 宁德时代新能源科技股份有限公司 | Positive electrode material, preparation method thereof, secondary battery and power utilization device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109449382A (en) | A kind of anode material for lithium-ion batteries and preparation method thereof | |
| CN104966823B (en) | Material surface has nickel cobalt lithium aluminate cathode material of component concentration gradient and preparation method thereof | |
| CN106450282A (en) | Large monocrystal lithium nickel manganate anode material and preparation method thereof | |
| CN102214819B (en) | Method for manufacturing cobalt nickel lithium manganate oxide as gradient anode active material of lithium ion battery | |
| CN104953172A (en) | Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries | |
| CN108390039A (en) | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| CN108987711A (en) | A kind of spherical shape sodium-ion battery anode quaternary material and preparation method thereof | |
| CN106340638A (en) | High multiplying power lithium-enriched manganese-based anode material with double-layer hollow structure and preparation method thereof | |
| CN106622116A (en) | Preparation method of spinel type lithium ion sieve | |
| CN106960955A (en) | Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof | |
| CN108483516A (en) | A kind of anode material for lithium-ion batteries and its synthetic method with superlattices ordered structure | |
| CN108550791A (en) | A kind of layered cathode material and its preparation method and application of spinelle cladding | |
| CN113903884B (en) | Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery | |
| CN106410183A (en) | Low-temperature lithium ion battery anode material and method for preparing same | |
| CN108172808A (en) | A kind of method of modifying of cerium tin composite oxides cladding lithium-rich manganese-based anode material | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN106299342A (en) | Lithium-rich anode material of K ion doping and high-voltage spinel/carbon double-coating and preparation method thereof | |
| CN108963242B (en) | Amorphous sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery | |
| CN109713260A (en) | A kind of method of modifying of Phosphate coating lithium-rich manganese-based anode material | |
| CN105470468A (en) | Fluorine-doped lithium ferric manganese phosphate cathode material and preparation method thereof | |
| CN115241450A (en) | Preparation and application of doped sodium ion nickel-iron-manganese-based single crystal battery positive electrode material | |
| CN102832381A (en) | Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life | |
| CN106328923A (en) | Preparation method of positive electrode material of lithium battery | |
| CN106129400A (en) | A kind of lanthanum part replaces spherical lithium-rich manganese-based anode material of manganese and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190308 |