CN105932251A - Preparation method and application of metal oxide coated cathode material for lithium ion battery - Google Patents
Preparation method and application of metal oxide coated cathode material for lithium ion battery Download PDFInfo
- Publication number
- CN105932251A CN105932251A CN201610389932.9A CN201610389932A CN105932251A CN 105932251 A CN105932251 A CN 105932251A CN 201610389932 A CN201610389932 A CN 201610389932A CN 105932251 A CN105932251 A CN 105932251A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- metal
- ion battery
- lithium ion
- oxide coated
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method and application of a metal oxide coated cathode material for a lithium ion battery. After ball milling and mixing are carried out on nanoscale metal powder and a cathode material, water is added to the obtained mixture for reaction, thereby obtaining the cathode material of which surface is coated by metal hydroxide colloid; the cathode material of which surface is coated by the metal hydroxide colloid is calcined at a high temperature, thereby obtaining the cathode material of which surface forms a metal oxide coating layer. The metal oxide coating layer is compact and even and is good in stability. The prepared metal oxide coated cathode material for the lithium ion battery can be used for preparing the lithium ion battery which is high in cycling stability and long in cycling life. The preparation method of the metal oxide coated cathode material for the lithium ion battery is characterized in low cost, simple operation and environmental friendliness and can be applied to industrial production on a large scale.
Description
Technical field
The present invention relates to the preparation method of a kind of cell positive material, be specifically related to the preparation method of a kind of metal-oxide coated lithium ion battery positive electrode and the application in lithium ion battery thereof, belong to technical field of lithium ion.
Background technology
Nowadays, mobile electronic device, such as smart mobile phone, digital camera, notebook computer, and electric automobile and developing rapidly of hybrid vehicle promote advancing by leaps and bounds of lithium rechargeable battery technology.But, current anode material for lithium-ion batteries, such as cobalt acid lithium, spinel lithium manganate, LiFePO4, all there is the shortcoming that cycle life is low, it is impossible to enough meet the requirement of following pure electrical equipment.Therefore, study and develop a kind of positive electrode with high cycle life and become the common objective of whole world research worker.
Coating modification is the material using a kind of physical and chemical performance excellent, forms the guard method of one layer of uniform clad at target material particle surface.Owing to, during the charge and discharge cycles of lithium ion battery, electrolyte has corrosiveness to positive electrode, causing the Crystal Structure Distortion of positive electrode, cycle life reduces.Therefore, coating modification is often applied to improving the chemical property of positive electrode.Each quasi-metal oxides was widely used in the surface coating modification of anode material for lithium-ion batteries in recent years.The methods such as some research worker utilize atom deposition method, magnetron sputtering method carry out the coating modification of metal-oxide, but owing to operating process is complicated, preparation technology is loaded down with trivial details and the shortcoming such as high cost, it is impossible to be applied to industrialized production on a large scale.
Summary of the invention
The defect existed for prior art, it is an object of the invention to there are provided the preparation method of the modification lithium-ion battery anode material of a kind of metal-oxide clad with dense uniform, good stability, this preparation method is simple to operate, low cost, environmental friendliness, beneficially industrialized production.
Another object of the present invention is to be to provide the application of described metal-oxide coated lithium ion battery positive electrode, can prepare the lithium ion battery having extended cycle life as lithium ion anode material.
In order to realize above-mentioned technical purpose, the invention provides the preparation method of a kind of metal-oxide coated lithium ion battery positive electrode, the method be nano level metal powder is mixed with positive electrode ball milling after, react at a temperature of 40 DEG C～80 DEG C with water, obtain the positive electrode of surface clad hydroxide colloid；The positive electrode of described surface clad hydroxide colloid is calcined at a temperature of being placed in 200 DEG C～900 DEG C, to obtain final product.
Preferably scheme, nano level metal powder quality is the 0.5%～10.0% of positive electrode quality.
More preferably scheme, nano level metal powder particle diameter is distributed as 50nm～500nm.
More preferably scheme, nano level metal powder is at least one in nanoscale rubidium powder, nano-grade lanthanum powder, nano-scale cerium powder, nanoscale yttrium powder, nanoscale magnesium powder, nanoscale aluminium powder.
Further preferred scheme, nano level metal powder carries out pre-activate process by acid corrosion method.
Most preferably scheme, acid corrosion method is to be that the hydrochloric acid of 0.1mol/L～1.0mol/L, sulphuric acid, nitric acid carry out immersion treatment by concentration.
More preferably scheme, positive electrode is the LiM with spinel structure2O4, M=Ni and/or Mn；And/or there is the LiMO of layer structure2, in M=Ni, Co, Mn, Al at least one；And/or richness lithium manganese anode material xLi2MnO3·(1-x)LiMO2, in M=Ni, Co, Mn at least one.
Preferably scheme, ball milling is realized by planetary ball mill or roller shaft type ball mill, and drum's speed of rotation is 400～800p/min, and Ball-milling Time is 1h～8h.Ball grinder is with Achates, corundum, nylon or steel matter, and abrading-ball is zirconia ball, steel ball or agate ball.
Preferably scheme, the response time is 0.5h～5.0h.
Preferably scheme, calcination time is 5h～20h.
Present invention also offers the application of described metal-oxide coated lithium ion battery positive electrode, lithium ion battery is prepared in described metal-oxide coated lithium ion battery positive electrode application.
The method preparing metal-oxide coated lithium ion battery positive electrode of the present invention includes step in detail below:
1) by least one metal dust in particle diameter rubidium (Rb) between 50nm～500nm, lanthanum (La), cerium (Ce), yttrium (Y), magnesium (Mg), aluminum (Al) and the LiM with spinel structure2O4(M=Ni and/or Mn), and/or there is the LiMO of layer structure2(at least one in M=Ni, Co, Mn, Al), and/or rich lithium manganese anode material xLi2MnO3·(1-x)LiMO2(at least one in M=Ni, Co, Mn), mixed by planetary ball mill or roller shaft type ball mill ball milling, drum's speed of rotation is 400～800p/min, incorporation time is 1h～8h, nanometre metal powder is 0.005:1.0～0.1:1.0 with the mass ratio of positive electrode, and ball-milling medium can be zirconia ball, steel ball or agate ball；
2) add water to step 1) in the mixture that obtains, in the water-bath of 40 DEG C～80 DEG C, be incubated 0.5h～5.0h, prepare the positive electrode after metal hydroxides cladding；
3) positive electrode after being coated with by metal hydroxides, after sucking filtration, washing, is put into and is dried 8～14h in vacuum drying oven at 70～120 DEG C, obtain the positive electrode material precursor after metal hydroxides cladding；
4) described presoma is proceeded in Muffle furnace, between 200 DEG C～900 DEG C, be incubated 5h～20h, naturally cool to room temperature, finally give the positive electrode after metal-oxide cladding.
Metal-oxide coated lithium ion battery positive electrode prepared by the present invention is for preparing lithium ion battery: by metal-oxide coated lithium ion battery positive electrode and conductive agent (conductive black) and binding agent (PVDF) and NMP is ground on a small quantity is thoroughly mixed to form uniform pastel, it is coated in foil substrate as test electrode, making button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1).
Technical scheme utilizes ball-milling method or acid corrosion method that nano metal powder is carried out surface activation process, nano metal powder after activation processing reacts generation metal hydroxides under suitable condition with water, the metal hydroxides surface generated is electrically charged, energy uniform adsorption is on positive electrode surface, metal hydroxides is further utilized at high temperature to be dehydrated generation metal oxide nano particles, the metal oxide nano particles in-situ deposition generated, on positive electrode surface, obtains the metal-oxide clad of dense uniform, good stability.
Hinge structure, the Advantageous Effects that technical scheme is brought:
Metal-oxide clad dense uniform in metal-oxide coated lithium ion battery positive electrode prepared by technical scheme, good stability, can effectively prevent during the charge and discharge cycles of lithium ion battery, the electrolyte corrosiveness to positive electrode, substantially prolongs the cycle life of lithium ion battery.
The method preparing metal-oxide coated lithium ion battery positive electrode of the present invention, take full advantage of nano level metal powder and water and react generation metal hydroxides colloidal sol and metal hydroxides has preferable adsorptivity, and metal hydroxides colloidal sol pyrolytic generates the principle of metal-oxide.Form dense uniform, the metal oxide layer of good stability on positive electrode surface, can effectively prevent positive active material and electrolyte solution contacts and loss by dissolution, substantially prolongs the cycle life of battery；Substantially increase ion and the electronic conductivity of electrode simultaneously, improve the chemical property of lithium ion battery.
The combining the method for high temperature sintering by low temperature synthesis persursor material and prepare of the metal-oxide coated lithium ion battery positive electrode of the present invention, there is cost of material low, the feature being simple to operate and friendly to environment, overcome in traditional metal-oxide coating modification method, owing to cost of material is high, the shortcomings such as operating process complexity is loaded down with trivial details with technique.
The method preparing metal-oxide coated lithium ion battery positive electrode of the present invention passes through ball-milling method or acid corrosion method, makes metal surface activation, substantially increases the efficiency that metal reacts with water, makes process simplification, mild condition.
The metal-oxide coated lithium ion battery positive electrode of the present invention prepares positive pole, is applied to lithium ion battery, shows the cycle performance of excellence, substantially prolongs cycle life.
Accompanying drawing explanation
[Fig. 1] is the LiNi in embodiment 1 before coating modification0.8Co0.15Al0.05O2Positive electrode scanning electron microscope (SEM) photograph (SEM).
[Fig. 2] is Al in embodiment 12O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode scanning electron microscope (SEM) photograph (SEM).
[Fig. 3] is the LiNi without coating modification0.8Co0.15Al0.05O2The Al that positive electrode and embodiment 1 prepare2O3LiNi after coating modification0.8Co0.15Al0.05O2100 cycle performance curve charts of positive electrode.
Detailed description of the invention
Following example are intended to be described in further details present invention, and the protection domain of the claims in the present invention is not limited by the example.
Embodiment 1
(1) superfine aluminium power that particle diameter is 50nm is weighed aluminium powder and LiNi respectively according to the mass percent that relative positive electrode is 1%0.8Co0.15Al0.05O2Positive electrode, join capacity be 250mL and fill zirconia ball agate jar in, then adjust rotating speed grind 2h to 400p/min.
(2) mixture after grinding joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 1h at 50 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the LiNi that aluminium hydroxide is coated with0.8Co0.15Al0.05O2The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 5 hours at 450 DEG C, obtains Al2O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode.
(5) the above-mentioned prepared Al of 0.48g is weighed2O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
Use Al prepared by the present embodiment2O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode, its material characterization and chemical property as shown in Figures 1 to 3:
Fig. 1 can be seen that the LiNi without coating modification0.8Co0.15Al0.05O2The class spherical structure that positive electrode is made up of the primary particle of a size of 300～800nm, smooth surface.
Fig. 2 can be seen that through Al2O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode particle surface has the lamellar clad being evenly distributed.
Fig. 3 shows use Al2O3LiNi after coating modification0.8Co0.15Al0.05O2The electrode that positive electrode is made, at room temperature under 1C multiplying power during constant-current discharge, after circulating 100 times, specific capacity may remain in 190mAh/g；Show good cycle performance.
Embodiment 2
(1) superfine magnesium powder that particle diameter is 100nm is weighed magnesium powder and 0.3Li respectively according to the mass percent that relative positive electrode is 0.5%2MnO3·0.7LiNi0.333Co0.333Mn0.333O2Positive electrode, joins capacity and is 250mL and fills in the corundum ball grinder of steel ball, then adjusts rotating speed and grinds 4h to 500p/min.
(2) mixture after grinding joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 2h at 40 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the 0.3Li that magnesium hydroxide is coated with2MnO3·0.7LiNi0.333Co0.333Mn0.333O2The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 3 hours at 400 DEG C, obtains the 0.3Li after MgO coating modification2MnO3·0.7LiNi0.333Co0.333Mn0.333O2Positive electrode.
(5) 0.3Li after the above-mentioned prepared MgO coating modification of 0.48g is weighed2MnO3·0.7LiNi0.333Co0.333Mn0.333O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
0.3Li after MgO coating modification prepared by employing the present embodiment2MnO3·0.7LiNi0.333Co0.333Mn0.333O2Positive electrode is assembled into button cell for electrode and with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 267mAh/g, shows good cycle performance.
Embodiment 3
(1) the ultra-fine cerium powder that particle diameter is 200nm is weighed cerium powder and 0.5Li respectively according to the mass percent that relative positive electrode is 2.0%2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Positive electrode, join capacity be 250mL and fill agate ball nylon ball grinder in, then adjust rotating speed grind 6h to 600p/min.
(2) mixture after grinding joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 3h at 60 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the 0.5Li that cerium hydroxide is coated with2MnO3·0.5LiNi0.5Co0.2Mn0.3O2The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 8 hours at 600 DEG C, obtains CeO20.5Li after coating modification2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Positive electrode.
(5) the above-mentioned prepared CeO of 0.48g is weighed20.5Li after coating modification2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
Use CeO prepared by the present embodiment20.5Li after coating modification2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Positive electrode is assembled into button cell for electrode and with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 274mAh/g, shows good cycle performance.
Embodiment 4
(1) the ultra-fine rubidium powder that particle diameter is 300nm is weighed rubidium powder and 0.7Li respectively according to the mass percent that relative positive electrode is 4.0%2MnO3·0.3LiNi0.6Co0.2Mn0.2O2Positive electrode, join capacity be 250mL and fill steel ball agate jar in, then adjust rotating speed grind 8h to 800p/min.
(2) mixture after grinding joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 5h at 80 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the 0.7Li that rubidium hydroxide is coated with2MnO3·0.3LiNi0.6Co0.2Mn0.2O2The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 12 hours at 600 DEG C, obtains RbO20.7Li after coating modification2MnO3·0.3LiNi0.6Co0.2Mn0.2O2Positive electrode.
(5) the above-mentioned prepared RbO of 0.48g is weighed20.7Li after coating modification2MnO3·0.3LiNi0.6Co0.2Mn0.2O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
Use RbO prepared by the present embodiment20.7Li after coating modification2MnO3·0.3LiNi0.6Co0.2Mn0.2O2Positive electrode is assembled into button cell for electrode and with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 282mAh/g, shows good cycle performance.
Embodiment 5
(1) the ultra fine yttrium powder that particle diameter is 500nm is weighed yttrium powder and LiNi respectively according to the mass percent that relative positive electrode is 6.0%0.5Mn1.5O4Positive electrode, joining capacity is 250mL's and fill in the nylon ball grinder of agate ball, then adjusts rotating speed and grinds 5h to 600p/min.
(2) mixture after grinding joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 5h at 70 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the LiNi that Yttrium trihydroxide is coated with0.5Mn1.5O4The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 16 hours at 800 DEG C, obtains Y2O3LiNi after coating modification0.5Mn1.5O4Positive electrode.
(5) the above-mentioned prepared Y of 0.48g is weighed2O3LiNi after coating modification0.5Mn1.5O4Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
Use Y prepared by the present embodiment2O3LiNi after coating modification0.5Mn1.5O4Positive electrode is assembled into button cell for electrode and with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 142mAh/g, and discharge voltage is maintained at 4.5V, shows good cycle performance.
Embodiment 6
(1) the ultra-fine lanthanum powder that particle diameter is 300nm is weighed lanthanum powder and LiNi respectively according to the mass percent that relative positive electrode is 10.0%0.6Co0.2Mn0.2O2Positive electrode, joins capacity and is 250mL and fills in the steel ball grinder of agate ball, then adjusts rotating speed and grinds 4h to 500p/min.
(2) mixture after grinding joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 5h at 50 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the LiNi that lanthanum hydroxide is coated with0.6Co0.2Mn0.2O2The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 8 hours at 550 DEG C, obtains La2O3LiNi after coating modification0.6Co0.2Mn0.2O2Positive electrode.
(5) the above-mentioned prepared La of 0.48g is weighed2O3LiNi after coating modification0.6Co0.2Mn0.2O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
Use La prepared by the present embodiment2O3LiNi after coating modification0.6Co0.2Mn0.2O2Positive electrode is assembled into button cell for electrode and with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 185mAh/g, shows good cycle performance
Embodiment 7
(1) superfine aluminium power that particle diameter is 300nm is joined capacity be 250mL and fill the there-necked flask that concentration is 0.1mol/L hydrochloric acid is carried out soak activation processing.
(2) aluminium powder after overactivation and LiNi are weighed in step (1) respectively according to the mass percent that relative positive electrode is 2.0%0.333Co0.333Mn0.333O2Positive electrode joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 5h at 60 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the LiNi that aluminium hydroxide is coated with0.333Co0.333Mn0.333O2The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 8 hours at 500 DEG C, obtains Al2O3LiNi after coating modification0.333Co0.333Mn0.333O2Positive electrode.
(5) the above-mentioned prepared Al of 0.48g is weighed2O3LiNi after coating modification0.333Co0.333Mn0.333O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
Use Al prepared by the present embodiment2O3LiNi after coating modification0.333Co0.333Mn0.333O2Positive electrode is assembled into button cell for electrode and with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 172mAh/g, shows good cycle performance.
Embodiment 8
(1) superfine magnesium powder that particle diameter is 400nm is joined capacity be 250mL and fill the there-necked flask that concentration is 0.5mol/L sulphuric acid is carried out soak activation processing.
(2) magnesium powder after overactivation and LiNi are weighed in step (1) respectively according to the mass percent that relative positive electrode is 3.0%0.85Co0.05Mn0.1O2Positive electrode joins in the there-necked flask that capacity is 250mL and adds 100mL deionized water, stirring reaction 5h at 60 DEG C.
(3) it is washed with deionized the precipitation 3 times that step (2) obtains, then with absolute ethanol washing 3 times, then filters, filter cake be incubated 12 hours in the convection oven of 80 DEG C, obtain the LiNi that magnesium hydroxide is coated with0.85Co0.05Mn0.1O2The presoma of positive electrode.
(4) presoma step (3) obtained loads in crucible, is incubated 8 hours at 500 DEG C, obtains the LiNi after MgO coating modification0.85Co0.05Mn0.1O2Positive electrode.
(5) LiNi after the above-mentioned prepared MgO coating modification of 0.48g is weighed0.85Co0.05Mn0.1O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
LiNi after MgO coating modification prepared by employing the present embodiment0.85Co0.05Mn0.1O2Positive electrode is assembled into button cell for electrode and with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 186mAh/g, shows good cycle performance.
Claims (10)
1. the preparation method of a metal-oxide coated lithium ion battery positive electrode, it is characterised in that: by nanometer
After level metal dust mixes with positive electrode ball milling, react at a temperature of 40 DEG C～80 DEG C with water, obtain table
Bread covers the positive electrode of metal hydroxides colloid；The positive pole material of described surface clad hydroxide colloid
Material is calcined at a temperature of being placed in 200 DEG C～900 DEG C, to obtain final product.
The preparation method of metal-oxide coated lithium ion battery positive electrode the most according to claim 1, its
It is characterised by: nano level metal powder quality is the 0.5%～10.0% of positive electrode quality.
The preparation method of metal-oxide coated lithium ion battery positive electrode the most according to claim 2, its
It is characterised by: described nano level metal powder particle diameter is distributed as 50nm～500nm.
4. according to the preparation of the metal-oxide coated lithium ion battery positive electrode described in any one of claims 1 to 3
Method, it is characterised in that: described nano level metal powder is nanoscale rubidium powder, nano-grade lanthanum powder, nanoscale
At least one in cerium powder, nanoscale yttrium powder, nanoscale magnesium powder, nanoscale aluminium powder.
The preparation method of metal-oxide coated lithium ion battery positive electrode the most according to claim 4, its
It is characterised by: described nanometre metal powder carries out pre-activate process by acid corrosion method.
The preparation method of metal-oxide coated lithium ion battery positive electrode the most according to claim 5, its
It is characterised by: described acid corrosion method is to be the hydrochloric acid of 0.1mol/L～1.0mol/L, sulphuric acid, nitre by concentration
Acid carries out immersion treatment.
The preparation method of metal-oxide coated lithium ion battery positive electrode the most according to claim 1 and 2,
It is characterized in that: described positive electrode is: have the LiM of spinel structure2O4, M=Ni and/or Mn；
And/or there is the LiMO of layer structure2, in M=Ni, Co, Mn, Al at least one；
And/or richness lithium manganese anode material xLi2MnO3·(1-x)LiMO2, 0.1 < x < 0.9, M=Ni, in Co, Mn extremely
Few one.
The preparation method of metal-oxide coated lithium ion battery positive electrode the most according to claim 1, its
It is characterised by: described ball milling is realized by planetary ball mill or roller shaft type ball mill, and drum's speed of rotation is
400～800p/min, Ball-milling Time is 1h～8h.
9. according to the metal-oxide coated lithium ion battery positive pole material described in claims 1 to 3,5,6,8 any one
The preparation method of material, it is characterised in that: the response time is 0.5h～5.0h；Calcination time is 5h～20h.
10. the metal-oxide coated lithium ion battery positive electrode described in claims 1 to 3,5,6,8 any one
Application, it is characterised in that: lithium ion battery is prepared in application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610389932.9A CN105932251B (en) | 2016-06-03 | 2016-06-03 | A kind of preparation method and applications of metal oxide coated lithium ion battery positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610389932.9A CN105932251B (en) | 2016-06-03 | 2016-06-03 | A kind of preparation method and applications of metal oxide coated lithium ion battery positive electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105932251A true CN105932251A (en) | 2016-09-07 |
| CN105932251B CN105932251B (en) | 2018-05-04 |
Family
ID=56832521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610389932.9A Active CN105932251B (en) | 2016-06-03 | 2016-06-03 | A kind of preparation method and applications of metal oxide coated lithium ion battery positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105932251B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232150A (en) * | 2017-12-29 | 2018-06-29 | 贵州振华义龙新材料有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
| CN108390065A (en) * | 2018-01-25 | 2018-08-10 | 湖北师范大学 | A method of in li-ion electrode materials surface coating cerium oxide |
| CN108550803A (en) * | 2018-03-21 | 2018-09-18 | 北京旭碳新材料科技有限公司 | Ternary anode material for lithium-ion batteries and preparation method thereof |
| CN111916697A (en) * | 2020-07-14 | 2020-11-10 | 蜂巢能源科技有限公司 | Cobalt-free cathode material, preparation method thereof, lithium ion battery cathode and lithium battery |
| CN112151797A (en) * | 2020-08-21 | 2020-12-29 | 湖南长远锂科股份有限公司 | Lithium-rich manganese-based positive electrode material coated by multi-metal composite oxide and preparation method thereof |
| CN113937262A (en) * | 2021-09-22 | 2022-01-14 | 浙江钠创新能源有限公司 | Metal oxide modified positive electrode material for sodium ion battery and preparation method and application thereof |
| WO2024087363A1 (en) * | 2022-10-26 | 2024-05-02 | 荆门市格林美新材料有限公司 | Modified quaternary precursor, and preparation method therefor and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107899A (en) * | 2011-01-11 | 2011-06-29 | 上海理工大学 | Preparation method of lamellar gamma-phase nano aluminum oxide |
| CN104393277A (en) * | 2014-10-20 | 2015-03-04 | 上海空间电源研究所 | Ternary material coated with metal oxide on surface and used for lithium ion battery, and preparation method of ternary material |
-
2016
- 2016-06-03 CN CN201610389932.9A patent/CN105932251B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107899A (en) * | 2011-01-11 | 2011-06-29 | 上海理工大学 | Preparation method of lamellar gamma-phase nano aluminum oxide |
| CN104393277A (en) * | 2014-10-20 | 2015-03-04 | 上海空间电源研究所 | Ternary material coated with metal oxide on surface and used for lithium ion battery, and preparation method of ternary material |
Non-Patent Citations (1)
| Title |
|---|
| 张正国等: "Al2O3包覆对三元正极材料结构和性能的影响", 《中国陶瓷》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232150A (en) * | 2017-12-29 | 2018-06-29 | 贵州振华义龙新材料有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
| CN108390065A (en) * | 2018-01-25 | 2018-08-10 | 湖北师范大学 | A method of in li-ion electrode materials surface coating cerium oxide |
| CN108550803A (en) * | 2018-03-21 | 2018-09-18 | 北京旭碳新材料科技有限公司 | Ternary anode material for lithium-ion batteries and preparation method thereof |
| CN111916697A (en) * | 2020-07-14 | 2020-11-10 | 蜂巢能源科技有限公司 | Cobalt-free cathode material, preparation method thereof, lithium ion battery cathode and lithium battery |
| CN112151797A (en) * | 2020-08-21 | 2020-12-29 | 湖南长远锂科股份有限公司 | Lithium-rich manganese-based positive electrode material coated by multi-metal composite oxide and preparation method thereof |
| CN113937262A (en) * | 2021-09-22 | 2022-01-14 | 浙江钠创新能源有限公司 | Metal oxide modified positive electrode material for sodium ion battery and preparation method and application thereof |
| WO2024087363A1 (en) * | 2022-10-26 | 2024-05-02 | 荆门市格林美新材料有限公司 | Modified quaternary precursor, and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105932251B (en) | 2018-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Miao et al. | Li2ZrO3-coated 0.4 Li2MnO3· 0.6 LiNi1/3Co1/3Mn1/3O2 for high performance cathode material in lithium-ion battery | |
| CN102832389B (en) | High-nickel positive active material of surface-modified lithium ion battery and preparation method of positive active material | |
| JP6472520B2 (en) | Method for producing positive electrode active material | |
| Dai et al. | Ultrathin-Y2O3-coated LiNi0. 8Co0. 1Mn0. 1O2 as cathode materials for Li-ion batteries: synthesis, performance and reversibility | |
| CN105938899B (en) | A kind of preparation method and application of fast-ionic conductor coating modification anode material for lithium-ion batteries | |
| CN103456936B (en) | Sodium ion secondary battery and the preparation method of layered titanate active substance, electrode material, both positive and negative polarity and active substance | |
| CN102169990B (en) | Ternary cathode material and production method thereof | |
| CN105932251B (en) | A kind of preparation method and applications of metal oxide coated lithium ion battery positive electrode | |
| Yi et al. | Effective enhancement of electrochemical performance for spherical spinel LiMn2O4 via Li ion conductive Li2ZrO3 coating | |
| JP2019503052A (en) | Method for making a battery electrode | |
| CN107681147B (en) | Preparation method and application of solid electrolyte coated modified lithium ion battery positive electrode material | |
| Zhang et al. | Improved cycling performance of Li2MoO4-inlaid LiNi0. 5Co0. 2Mn0. 3O2 cathode materials for lithium-ion battery under high cutoff voltage | |
| JP2016103477A (en) | Positive electrode material for sodium secondary battery | |
| Du et al. | A high-powered concentration-gradient Li (Ni0. 85Co0. 12Mn0. 03) O2 cathode material for lithium ion batteries | |
| Iqbal et al. | Systematic study of the effect of calcination temperature and Li/M molar ratio on high performance Ni-rich layered LiNi0. 9Co0. 1O2 cathode materials | |
| Huang et al. | Synthesis of Ni0. 8Co0. 1Mn0. 1 (OH) 2 precursor and electrochemical performance of LiNi0. 8Co0. 1Mn0. 1O2 cathode material for lithium batteries | |
| JP2014502245A (en) | Lithium manganese composite oxide and method for producing the same | |
| Xu et al. | Understanding the enhanced electrochemical performance of samarium substituted Li [Li0. 2Mn0. 54− xSmxCo0. 13Ni0. 13] O2 cathode material for lithium ion batteries | |
| CN102315440A (en) | Spinel composite material, preparation method and application thereof | |
| CN103794782A (en) | Lithium-rich manganese-based material, preparation method thereof and lithium-ion battery | |
| CN104466102A (en) | Porous V2O5/C composite microspheres of lithium secondary battery positive electrode material and preparation method of porous V2O5/C composite microspheres | |
| WO2024046046A1 (en) | Positive electrode active material and use thereof | |
| CN105826550A (en) | Preparation method of lithium manganate cathode material with ferri-containing compound coating | |
| CN113845152A (en) | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery | |
| Li et al. | W-doped LiNi1/3Co1/3Mn1/3O2 with excellent high-rate performance synthesized via hydrothermal lithiation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |