CN108172809A - A kind of preparation method of lithium ion conductor cladding lithium cobaltate cathode material - Google Patents
A kind of preparation method of lithium ion conductor cladding lithium cobaltate cathode material Download PDFInfo
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- CN108172809A CN108172809A CN201810052625.0A CN201810052625A CN108172809A CN 108172809 A CN108172809 A CN 108172809A CN 201810052625 A CN201810052625 A CN 201810052625A CN 108172809 A CN108172809 A CN 108172809A
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- lithium
- lithium ion
- ion conductor
- niobium
- cobalt acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation methods of lithium ion conductor cladding lithium cobaltate cathode material, the method is simple to operation, it is at low cost, it takes short, the method adulterates Nb ions in positive electrode, same order elements are carried out to the Co ionic sites in positive electrode lattice, change lattice parameter, excellent electrochemical performance；The present invention will inorganic fast lithium ion conductor precursor solution and anode material for lithium-ion batteries at a certain temperature after mixing, obtain the anode material for lithium-ion batteries that surface coats fast lithium ion conductor colloid, the surface is coated into the anode material for lithium-ion batteries of fast lithium ion conductor colloid after heat treatment, one layer of uniform clad is formed on positive electrode particle surface, the transmission activity of lithium ion inside electrode material can be promoted, improve the interface of electrolyte and positive interpolar, promote the performance of battery.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of system of lithium ion conductor cladding lithium cobaltate cathode material
Preparation Method.
Background technology
LiCoO2The main positive electrode of current commercial Li-ion battery, but it there are it is expensive, be unfavorable for
Environmental protection, the shortcomings such as specific capacity is low.LiNbO2The positive electrode of doping Co elements is provided with LiNbO simultaneously2The higher electric discharge ratio of material
Capacity, and the layer structure of material is stabilized, the cyclical stability of material is enhanced, but there is also overcharging resisting energy for this material
The defects of force difference, thermal stability are poor, electric discharge irreversible capacity is higher for the first time.
It is using a kind of excellent material of physical and chemical performance, in positive electrode particle surface that solwution method, which carries out coating modification,
Form one layer of guard method uniformly coated.For the liquid lithium ionic cell for using liquid electrolyte, due in battery
Charge and discharge cycles during, electrolyte to positive electrode have corrosiveness, lead to the Crystal Structure Distortion of positive electrode, follow
The ring service life is lower.In solid lithium battery, the interface problem of electrolyte and positive interpolar is more notable, does not have between electrode material
The infiltration of liquid electrolyte, leads to the lithium ion transport poor-performing in anode portion, and battery entirety chemical property reduces.Cause
This, coating modification is often applied to improve the chemical property of positive electrode.It is different that existing research is directed to above problem application
Method coating modification has been carried out to anode material for lithium-ion batteries, some personnel using atomic layer deposition method, magnetron sputtering method
Deng being coated to positive electrode, but its operating difficulties, cost are higher, it is impossible to carry out large-scale industrialization production.
Invention content
The present invention provides a kind of preparation method of lithium ion conductor cladding lithium cobaltate cathode material, and the method is simply easily grasped
Make, at low cost, time-consuming short, the method adulterates Nb ions in positive electrode, to the Co ionic sites in positive electrode lattice
Same order elements are carried out, change lattice parameter, excellent electrochemical performance；The present invention will inorganic fast lithium ion conductor precursor solution and
Anode material for lithium-ion batteries after mixing, obtains the lithium ion that surface coats fast lithium ion conductor colloid at a certain temperature
Cell positive material, by the anode material for lithium-ion batteries of the fast lithium ion conductor colloid of surface cladding after heat treatment,
Positive electrode particle surface forms one layer of uniform clad, can promote the transmission activity of lithium ion inside electrode material, improve electricity
The interface of the positive interpolars of Xie Zhiyu promotes the performance of battery.
To achieve these goals, the present invention provides a kind of preparation side of lithium ion conductor cladding lithium cobaltate cathode material
Method, this method comprises the following steps：
（1）It prepares niobium and is modified cobalt acid lithium
The chemical formula that the niobium is modified cobalt acid lithium is LiCo1-x-yFexNbyO2, wherein：X=0.12-0.15, y=0.02-0.03, according to
The mole of Li, Fe, Nb, Co in above-mentioned chemical formula weigh lithium carbonate, ferric acetate, niobium oxide and cobalt oxide, with suitable water
It is decentralized medium with ethyl alcohol, wet ball grinding batch mixing, the slurry mixed is carried out to the raw material weighed；The slurry that will be mixed
It is spray-dried, obtains cobalt acid lithium precursor；
Plasma-arc is imposed under reducing atmosphere to precursor, melts reaction powder, plasma electric arc voltage 20-
40kV, plasma electric arc current 500-1000A；
Frit reaction powder is spurted into reducibility gas in cooling device, particle is crushed and screened after cooling, screening obtains
Granular size be 5-10 microns of niobium modified cobalt acid lithium material；The wherein described nozzle diameter 2-5mm for injection；
（2）Prepare the precursor mixed solution of lithium ion conductor
According to chemical formula Li5La3.5Zr1.5O10Proportioning, lithium nitrate, lanthanum nitrate, zirconium nitrate are added in mixing vessel, added in suitable
Amount ethylene glycol, oxalic acid are stirred at room temperature 4-6 hours, obtain the precursor mixed solution of lithium ion conductor；
（3）According to Li5La3.5Zr1.5O10The mass ratio that cobalt acid lithium is modified with niobium is 1:Above-mentioned niobium is modified cobalt acid lithium by 150-180
Material is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution in, the two is mixed at room temperature
Uniformly, ultrasonic step and whipping step are alternately repeated progress by the ultrasound 2-3h and in ultrasonic disperse machine, ultrasonic 12-15min,
15-20min is stirred, to ensure the two mixture homogeneity of material and the dispersibility of storeroom, obtains mixed solution；
（4）Mixed solution is placed at 65-70 DEG C and stirs 6-8h, with the volatilization of solvent in mixed solution, is gradually become sticky
Thick class colloidal materials, by such colloidal materials turn be dried, after solvent volatilization completely after, transfer them in crucible
Heat treatment 6-8h is carried out at 680-720 DEG C, obtains lithium ion conductor cladding lithium cobaltate cathode material.
The invention has the advantages that and remarkable result：
（1）The method is simple to operation, at low cost, and time-consuming short, the method adulterates Nb ions in positive electrode, to anode
Co ionic sites in material lattice carry out same order elements, change lattice parameter, excellent electrochemical performance.
（2）The present invention will inorganic fast lithium ion conductor precursor solution and anode material for lithium-ion batteries at a certain temperature
After mixing, the anode material for lithium-ion batteries that surface coats fast lithium ion conductor colloid is obtained, the surface is coated fast
The anode material for lithium-ion batteries of lithium ion conductor colloid after heat treatment, forms one layer of uniform cladding on positive electrode particle surface
Layer can promote the transmission activity of lithium ion inside electrode material, improve the interface of electrolyte and positive interpolar, promote the property of battery
Energy.
Specific embodiment
Embodiment one
The chemical formula that the present embodiment niobium is modified cobalt acid lithium is LiCo0.86Fe0.12Nb0.02O2, according in above-mentioned chemical formula Li, Fe,
The mole of Nb, Co weigh lithium carbonate, ferric acetate, niobium oxide and cobalt oxide, using suitable water and ethyl alcohol as decentralized medium, symmetrically
The raw material taken carries out wet ball grinding batch mixing, the slurry mixed；The slurry mixed is spray-dried, obtains cobalt acid
Lithium precursor.
Plasma-arc is imposed under reducing atmosphere to precursor, melts reaction powder, plasma electric arc voltage
20kV, plasma electric arc current 500A；Frit reaction powder is spurted into reducibility gas in cooling device, after cooling to
Grain crushes and screens, and the granular size sieved is 5 microns of niobium modified cobalt acid lithium material；The wherein described nozzle for injection
Diameter 2mm.
According to chemical formula Li5La3.5Zr1.5O10Proportioning, by lithium nitrate, lanthanum nitrate, zirconium nitrate add in mixing vessel in, add
Enter proper amount of glycol, oxalic acid is stirred at room temperature 4 hours, obtain the precursor mixed solution of lithium ion conductor.
According to Li5La3.5Zr1.5O10The mass ratio that cobalt acid lithium is modified with niobium is 1:150, by above-mentioned niobium modified cobalt acid lithium material
It is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution in, the two is uniformly mixed at room temperature,
And the ultrasound 2h in ultrasonic disperse machine, ultrasonic step and whipping step are alternately repeated progress, ultrasonic 12min stirs 15min,
To ensure the two mixture homogeneity of material and the dispersibility of storeroom, mixed solution is obtained.
Mixed solution is placed at 65 DEG C and stirs 6h, with the volatilization of solvent in mixed solution, is gradually become viscous
Such colloidal materials are turned to be dried, after solvent volatilization completely, be transferred them in crucible at 680 DEG C by class colloidal materials
Under carry out heat treatment 6h, obtain lithium ion conductor cladding lithium cobaltate cathode material.
Embodiment two
The chemical formula that the present embodiment niobium is modified cobalt acid lithium is LiCo0.82Fe0.15Nb0.03O2.According in above-mentioned chemical formula Li, Fe,
The mole of Nb, Co weigh lithium carbonate, ferric acetate, niobium oxide and cobalt oxide, using suitable water and ethyl alcohol as decentralized medium, symmetrically
The raw material taken carries out wet ball grinding batch mixing, the slurry mixed；The slurry mixed is spray-dried, obtains cobalt acid
Lithium precursor.
Plasma-arc is imposed under reducing atmosphere to precursor, melts reaction powder, plasma electric arc voltage
40kV, plasma electric arc current 1000A；Frit reaction powder is spurted into reducibility gas in cooling device, it is right after cooling
Particle crushes and screens, and the granular size sieved is 10 microns of niobium modified cobalt acid lithium material；It is wherein described to be used for what is sprayed
Nozzle diameter 5mm.
According to chemical formula Li5La3.5Zr1.5O10Proportioning, by lithium nitrate, lanthanum nitrate, zirconium nitrate add in mixing vessel in, add
Enter proper amount of glycol, oxalic acid is stirred at room temperature 6 hours, obtain the precursor mixed solution of lithium ion conductor.
According to Li5La3.5Zr1.5O10The mass ratio that cobalt acid lithium is modified with niobium is 1:180, by above-mentioned niobium modified cobalt acid lithium material
It is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution in, the two is uniformly mixed at room temperature,
And the ultrasound 3h in ultrasonic disperse machine, ultrasonic step and whipping step are alternately repeated progress, ultrasonic 15min stirs 20min,
To ensure the two mixture homogeneity of material and the dispersibility of storeroom, mixed solution is obtained.
Mixed solution is placed at 70 DEG C and stirs 8h, with the volatilization of solvent in mixed solution, is gradually become viscous
Such colloidal materials are turned to be dried, after solvent volatilization completely, be transferred them in crucible at 720 DEG C by class colloidal materials
Under carry out heat treatment 8h, obtain lithium ion conductor cladding lithium cobaltate cathode material.
Claims (1)
1. a kind of preparation method of lithium ion conductor cladding lithium cobaltate cathode material, this method comprises the following steps：
（1）It prepares niobium and is modified cobalt acid lithium
The chemical formula that the niobium is modified cobalt acid lithium is LiCo1-x-yFexNbyO2, wherein：X=0.12-0.15, y=0.02-0.03, according to
The mole of Li, Fe, Nb, Co in above-mentioned chemical formula weigh lithium carbonate, ferric acetate, niobium oxide and cobalt oxide, with suitable water
It is decentralized medium with ethyl alcohol, wet ball grinding batch mixing, the slurry mixed is carried out to the raw material weighed；The slurry that will be mixed
It is spray-dried, obtains cobalt acid lithium precursor；
Plasma-arc is imposed under reducing atmosphere to precursor, melts reaction powder, plasma electric arc voltage 20-
40kV, plasma electric arc current 500-1000A；
Frit reaction powder is spurted into reducibility gas in cooling device, particle is crushed and screened after cooling, screening obtains
Granular size be 5-10 microns of niobium modified cobalt acid lithium material；The wherein described nozzle diameter 2-5mm for injection；
（2）Prepare the precursor mixed solution of lithium ion conductor
According to chemical formula Li5La3.5Zr1.5O10Proportioning, lithium nitrate, lanthanum nitrate, zirconium nitrate are added in mixing vessel, added in suitable
Amount ethylene glycol, oxalic acid are stirred at room temperature 4-6 hours, obtain the precursor mixed solution of lithium ion conductor；
（3）According to Li5La3.5Zr1.5O10The mass ratio that cobalt acid lithium is modified with niobium is 1:Above-mentioned niobium is modified cobalt acid lithium by 150-180
Material is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution in, the two is mixed at room temperature
Uniformly, ultrasonic step and whipping step are alternately repeated progress by the ultrasound 2-3h and in ultrasonic disperse machine, ultrasonic 12-15min,
15-20min is stirred, to ensure the two mixture homogeneity of material and the dispersibility of storeroom, obtains mixed solution；
（4）Mixed solution is placed at 65-70 DEG C and stirs 6-8h, with the volatilization of solvent in mixed solution, is gradually become sticky
Thick class colloidal materials, by such colloidal materials turn be dried, after solvent volatilization completely after, transfer them in crucible
Heat treatment 6-8h is carried out at 680-720 DEG C, obtains lithium ion conductor cladding lithium cobaltate cathode material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113353988A (en) * | 2021-02-18 | 2021-09-07 | 厦门厦钨新能源材料股份有限公司 | Lithium ion battery positive electrode material and preparation method thereof, lithium ion battery positive electrode and all-solid-state lithium battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN107226455A (en) * | 2017-08-05 | 2017-10-03 | 苏州思创源博电子科技有限公司 | A kind of niobium is modified the preparation method of lithium cobaltate cathode material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN107226455A (en) * | 2017-08-05 | 2017-10-03 | 苏州思创源博电子科技有限公司 | A kind of niobium is modified the preparation method of lithium cobaltate cathode material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113353988A (en) * | 2021-02-18 | 2021-09-07 | 厦门厦钨新能源材料股份有限公司 | Lithium ion battery positive electrode material and preparation method thereof, lithium ion battery positive electrode and all-solid-state lithium battery |
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