CN105977476A - Electrode material surface coating method and application thereof - Google Patents
Electrode material surface coating method and application thereof Download PDFInfo
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- CN105977476A CN105977476A CN201610614711.7A CN201610614711A CN105977476A CN 105977476 A CN105977476 A CN 105977476A CN 201610614711 A CN201610614711 A CN 201610614711A CN 105977476 A CN105977476 A CN 105977476A
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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- 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 relates to an electrode material surface coating method and application thereof. The method includes the steps that an electrode material and lithium hydrate are mixed; then TiO2 and/or Al2O3 are added into the obtained mixture and continue to be mixed; the obtained mixture is sintered at the first temperature and heated to the second higher temperature to be sintered to obtain the electrode material coated with an oxide layer, wherein the second temperature is higher than or equal to the first temperature, and the first temperature is higher than or equal to 400 DEG C. The method is easy to operate and suitable for large-scale production, and a coating layer of a prepared product is complete and even. A battery made of the electrode material coated with the oxide layer is excellent in circulating performance and high temperature performance and good in safety performance, the 500-cycle capacity retention ratio at the normal temperature is 93.5% or more, and the 500-cycle capacity retention ratio at the high temperature is 89.2% or more.
Description
Technical field
The invention belongs to electrode material preparation and technical field of lithium ion, relate to the table of a kind of electrode material
The electrode material of bread coating method, the oxide skin(coating) prepared in this way cladding, and comprise this oxidation
The lithium ion battery of the electrode material of nitride layer cladding.
Background technology
Lithium ion battery has that energy density is big, discharge platform is high, have extended cycle life and memory-less effect etc.
Advantage, is widely used to the fields such as mobile phone, camera and notebook computer, also begins to be applied to electronic simultaneously
The electrokinetic cell such as bicycle, electric automobile field.
Lithium cobaltate cathode material is to realize business-like positive electrode the earliest, but cobalt resource is limited and price is held high
Expensive, pollute big, limit it and further develop.Polynary positive pole material is because of low cost, hypotoxicity and height
Reversible capacity just becoming the succedaneum of cobalt acid lithium, but polynary positive pole material, especially when nickel content is higher,
Being susceptible to H2-H3 phase in version in charge and discharge process causes volume contraction to cause capacity attenuation, cycle performance
Difference, and Ni4+There is the strongest reduction inclination, be susceptible to Ni4+→Ni3+Reaction, in order to keep electric charge put down
Weighing apparatus, can discharge oxygen in material, so that material heat stability is deteriorated.Change multicomponent material electrochemistry
One effective ways of energy are that material carries out Surface coating, and cladding material defines between material and electrolyte
Overcoat, effectively prevent the dissolving of metal ion, reduces the interface resistance in cyclic process, postpones
Phase in version, improves the cycle performance of material, thermal stability and security performance.
Traditional multicomponent material method for coating has liquid-phase precipitation method, sol-gal process and solid phase method etc., and liquid phase is sunk
Shallow lake method, the advantage of sol-gal process are that being evenly coated property is good, and shortcoming is complex process, and cost is high, coating
Easily there is material surface with graininess in matter, is formed without complete clad.The advantage of solid phase method is operation
Simply, low cost, beneficially large-scale production, shortcoming is that being evenly coated property is bad.
Chinese invention patent CN103872331A discloses the aluminum method for coating of a kind of lithium ion anode material,
Positive electrode without cladding is joined in the aluminum salt solution of inorganic aluminate and solvent preparation by the method, and stirring rises
Temperature is to backflow, and after 30min, sucking filtration removes solvent, carries out roasting after vacuum drying in Muffle furnace, the coldest
But arrive room temperature and obtain the positive electrode of aluminum cladding.Although the method is easy to operate, step is simple, but during
Using a large amount of organic solvent, cost is high, is unfavorable for industrialized production, and reflux course is easily at material surface
Remaining a large amount of functional group, these functional groups form lithium carbonate at roasting process, cause the residual alkali number of material high, no
It is beneficial to the security performance of material.
Chinese invention patent CN103956472A discloses the system of the polynary positive pole material of a kind of titanium-oxide-coated
Preparation Method, the method is by LiNi1-x-y-zCoxAlyTbzO2Join the titanium chloride that concentration is 0.05～0.1mol/L
In solution, it is sufficiently stirred for 1～2h, during stirring, adds the ammonia spirit that concentration is 1～2mol/L,
Form the LiNi of cladding titanium hydroxide1-x-y-zCoxAlyTbzO2Precipitation, precipitated product is carried out sucking filtration, dry
After sieve, the product after sieving carries out high-temperature process 4～6h at 600～700 DEG C, obtains final products.
Although the method is conducive to titanium oxide ground uniformly cladding, but titanium oxide is easily present in material list with graininess
Face, it is impossible to forming complete clad, the method uses a large amount of aqueous solution simultaneously, can cause the molten of manganese element
Solving, cause the multicomponent material gram volume containing manganese to reduce, the scope of application is the widest.
Summary of the invention
For overcoming the defect of prior art, it is an object of the invention to provide a kind of simple to operate, it is adaptable to big
Large-scale production, and make electrode material surface form the surface coating method of complete and uniform oxide skin(coating),
And use the method to prepare jacketed electrode material the purposes for lithium ion battery.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
First aspect, the present invention provides the surface coating method of a kind of electrode material, described method to include as follows
Step:
(1) electrode material is mixed with Lithium hydrate；
(2) add by TiO in the mixture of step (1)2Or Al2O3Any a kind or 2 kinds composition
Oxide, continue mixing；
(3) mixture of step (2) is sintered in the first temperature, carries out in the second temperature the most again
Sintering, obtains the electrode material of oxide skin(coating) cladding；
Wherein, the second temperature >=the first temperature >=400 DEG C.
The surface coating method of the present invention, by first sintering at a temperature of relatively low first, makes Lithium hydrate melt
Melting, under driving force, Lithium hydrate trends towards being evenly distributed in electrode material surface, is then raised to
Sinter at a temperature of higher second, make titanium dioxide and/or aluminium oxide react with Lithium hydrate, generate LiTi's
Oxide (Li-Ti-O oxide), the oxide (Li-Al-O compound) of LiAl or the oxidation of LiAlTi
Thing (Li-Al-Ti-O compound), these oxides obtained, by means of reaction power, are uniformly coated on electricity
The surface of pole material forms oxide skin(coating).
Heretofore described " titanium dioxide and/or aluminium oxide " refers to: can be titanium dioxide, it is also possible to be oxygen
Change aluminum, it is also possible to be the mixture of titanium dioxide and aluminium oxide.
Electrode material of the present invention can be anode material for lithium ion battery, negative electrode for lithium ion battery material
Material or other electrode materials, preferably polynary positive pole material, more preferably LiNixM1‐xO2, wherein
0.1≤x≤1, M is any 1 in Co, Mn, Al, Mg, Ti, V, Cr, Zr, Nb, Ga or Sr
Plant or the combination of at least 2 kinds.
Preferably, the mass ratio of step (1) described Lithium hydrate and described electrode material is 0.1～2:100, example
As for 0.1:100,0.2:100,0.5:100,0.8:100,1.0:100,1.3:100,1.5:100 or 2:100
Deng, preferably 0.5:100.
Preferably, the mode of step (1) described mixing is for being placed in batch mixer mixing, and described batch mixer is ball
In mill mixer, VC mixer, fusion machine or three-dimensional mixer any a kind, preferably VC mixer.
Preferably, during the described mixing of step (1), the rotating speed of mixer is 800～2000r/min, such as may be used
For 800r/min, 900r/min, 1000r/min, 1200r/min, 1500r/min, 1800r/min or
2000r/min etc., preferably 1000r/min.
Preferably, the time of step (1) described mixing is 0.1～10h, for example, 0.1h, 0.4h, 0.6h,
1h, 2h, 3h, 4.5h, 5.5h, 6h, 7h, 8h or 10h etc., preferably 1h.
Step (2) described oxide is 0.1～5:100 with the mass ratio of described electrode material, for example,
0.1:100、0.3:100、0.5:100、0.7:100、1:100、1.5:100、1.7:100、2:100、
2.2:100,2.5:100,3:100,3.5:100,4:100 or 5:100 etc., preferably 0.4:100.
Step (2) described oxide is by TiO2Or Al2O3Any a kind or 2 kinds composition, it may be assumed that can
To be TiO2, it is also possible to it is Al2O3, it is also possible to it is TiO2And Al2O3Mixture.
Preferably, during step (2) described continuation mixing, the rotating speed of mixer is 800～2000r/min, example
As can be 800r/min, 1000r/min, 1200r/min, 1250r/min, 1500r/min, 1650r/min,
1800r/min or 2000r/min etc., preferably 1000r/min.
Preferably, step (2) described continue mixing time be 0.1～5h, for example, 0.1h, 0.3h,
0.5h, 0.8h, 1h, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h etc., be preferably
1h。
In the present invention, it is sintered in sintering furnace carrying out described in step (3).
Preferably, it is sintered in air atmosphere and/or oxygen atmosphere described in step (3) carrying out.
Preferably, in described air atmosphere or oxygen atmosphere, the flow of air or oxygen independently be 1～20
L/h, for example, 1L/h, 3L/h, 5L/h, 10L/h, 12L/h, 15L/h or 20L/h etc..
Preferably, described first temperature of step (3) is 400～600 DEG C, can be such as 400 DEG C, 450 DEG C,
500 DEG C, 550 DEG C, 575 DEG C or 600 DEG C etc., preferably 500 DEG C.
Preferably, step (3) is described is 2～20h in the time that the first temperature is sintered, for example, 2h,
4h, 6h, 8.5h, 10h, 12.5h, 15h, 17h or 20h etc., preferably 5h.
In the present invention, by sintering a period of time in the first relatively low temperature, Lithium hydrate occurs melted, molten
The Lithium hydrate melted can occur anti-with titanium dioxide and/or aluminium oxide at a temperature of follow-up higher second
Should, and melted Lithium hydrate may also operate as the effect of binding agent.
Preferably, described second temperature of step (3) is 600～1000 DEG C, for example, 600 DEG C, 650 DEG C,
700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 875 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C etc., be preferably
700℃。
Preferably, step (3) is described is 6～30h in the time that the second temperature is sintered, for example, 6h,
8h, 10h, 13.5h, 15h, 18h, 20h, 22h, 25h, 27.5h or 30h etc., preferably 8h.
In the present invention, when the first temperature=the second temperature, then without heating up, directly after the first temperature sintering
It is connected under heat-retaining condition and continues sintering in this temperature.
Preferably, when second temperature ＞ the first temperature, it is warmed up to the intensification speed of the second temperature from the first temperature
Degree is 1～10 DEG C/min, for example, 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C
/ min, 8 DEG C/min or 10 DEG C/min etc..
In the present invention, sinter a period of time by the first the most relatively low temperature, then in the second higher temperature
Sintering a period of time, titanium dioxide and/or aluminium oxide react with melted Lithium hydrate, are changed into oxidation
Thing, described oxide is the oxide (Li-Ti-O oxide) of LiTi, the oxide (Li-Al-O of LiAl
Compound) or the oxide (Li-Al-Ti-O compound) of LiAlTi, the above-mentioned oxide that reaction generates is equal
Cover the surface at electrode material evenly, form complete clad rather than particulate material；Meanwhile, hydrogen
Lithium oxide also assists in reaction and is changed into anaerogenic stable form, the oxide of the most above-mentioned LiTi, LiAl
Oxide or the oxide of LiAlTi.
As the optimal technical scheme of surface coating method of the present invention, described method is additionally included in step
(1) step (1) ' is carried out so that electrode material is carried out remove impurity before: mixed with water by electrode material, stir
Mix, be then peeled off and be dried, obtain the electrode material after remove impurity.
Preferably, described in step (1) ', the mass ratio of water and electrode material is 0.5～10:1, for example,
0.5:1、1:1、1.5:1、2:1、2.3:1、2.5:1、3:1、3.5:1、4:1、4.5:1、5.5:1、6:1、
7:1,8:1,9:1 or 10:1 etc..
Preferably, described in step (1) ' stirring time be 1～10h, for example, 1h, 2h, 3h, 4h,
4.5h, 5.5h, 6h, 7h, 8h or 10h etc..
In the present invention, step carries out isolated solid slurry in (1) '.In described separation uses this area
Conventional separation means, includes but not limited to that centrifugation separates with filter pressing.
Preferably, the rotating speed of described centrifugation is 1000～10000rpm, for example, 1000rpm,
2000rpm, 3000rpm, 4000rpm, 5000rpm, 6000rpm, 7500rpm, 8500rpm or
10000rpm etc..
Preferably, the time of described centrifugation is preferably 5～60min, such as my 5min, 10min,
15min, 20min, 25min, 30min, 33min, 38min, 45min, 50min or 60min etc..
Preferably, solid slurry is dried in (1) ' by step, described dry temperature be 100～
900℃。
Preferably, the time being dried described in step (1) ' is preferably 4～20h, for example, 4h, 6h,
8h, 10h, 13h, 15h, 18h or 20h etc..
Preferably, after step (1) ' carries out remove impurity, the electrode material surface hydroxide after the remove impurity obtained
Gross mass content≤1% of lithium and lithium carbonate.
When carrying out step (1) ' before in step (1), correspondingly the electrode material in step (1) is
Electrode material after remove impurity.
As the another optimal technical scheme of surface coating method of the present invention, described method is additionally included in step
Suddenly (3) are after the second temperature has sintered, and carry out the step cooling down, pulverize and sieving.
Preferably, described in be cooled to temperature be 10～80 DEG C, for example, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C,
50 DEG C, 60 DEG C or 80 DEG C etc..
Preferably, the slot size selected when sieving in the present invention can come according to the performance requirement of prepared material
Determining, the mesh numerical example of the screen cloth used when sieving can be such as 200 mesh, 250 mesh or 300 mesh etc..
Second aspect, the present invention provides the purposes of a kind of surface coating method as above.
One of described purposes prepares jacketed electrode material, described jacketed electrode material for using above-mentioned method for coating
Comprise electrode material and be coated on the oxide skin(coating) of described electrode material surface, and described oxide skin(coating) is
In Li-Ti-O oxide, Li-Al-O compound or Li-Al-Ti-O compound any a kind.
Preferably, described oxide skin(coating) even compact and complete, the thickness of described oxide skin(coating) is preferably
1～50nm, can be such as 1nm, 3nm, 5nm, 7nm, 10nm, 13nm, 15nm, 18nm, 20nm,
25nm, 28nm, 33nm, 36nm, 40nm, 45nm or 50nm etc..
Preferably, described electrode material is positive electrode, preferably polynary positive pole material, more preferably
LiNixM1‐xO2, wherein 0.1≤x≤1, M is Co, Mn, Al, Mg, Ti, V, Cr, Zr, Nb,
Any a kind or the combination of at least 2 kinds in Ga or Sr.
The two of described purposes are for providing a kind of lithium ion battery comprising above-mentioned jacketed electrode material.
Compared with prior art, there is advantages that
(1) surface coating method of the present invention, by first sintering at a temperature of relatively low first, makes hydroxide
Lithium melts, and Lithium hydrate melted under driving force is evenly distributed in the surface of electrode material, then
Be increased at a temperature of higher second sinter a period of time, make the Lithium hydrate melted serve not only as reactant with
Titanium dioxide and/or aluminium oxide react with Lithium hydrate, and play as binding agent and increase the work of associativity
With, the oxide (oxide of LiTi, the oxide of LiAl or the oxide of LiAlTi) of generation by means of
Reaction power, the surface being uniformly coated on electrode material forms complete oxide skin(coating) state, and non-particulate
Shape material dispersity.The surface coating method of the present invention is simple to operate, be applicable to large-scale production.
(2) the oxide skin(coating) cladding polynary positive pole material using the present invention makes battery, shows extraordinary
Normal-temperature circulating performance and high temperature cyclic performance, 500 weeks capability retentions of room temperature more than 93.5%, high temperature 500
Week, capability retention was more than 89.2%；Convert in the reaction due to Lithium hydrate and stablize shape in order to anaerogenic
, in product, no longer there is LiOH in state, thus the electrode material of the oxide skin(coating) cladding of the present invention for lithium from
During sub-battery will not because LiOH reaction aerogenesis, security performance is good, has wide market prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electricity of the polynary positive pole material of the Li-Ti-O oxide skin(coating) cladding that embodiment 1 prepares
Mirror figure；
Fig. 2 is the Surface coating TiO that comparative example 1 prepares2The scanning electron microscope (SEM) photograph of polynary positive pole material.
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of the present invention is described in detail.It should be appreciated that this
Detailed description of the invention described by place is merely to illustrate and explains the present invention, is not limited to the present invention.
Embodiment 1
By water and polynary positive pole material LiNi0.8Co0.15Al0.05O2Mix for 10:1 in mass ratio, stir 5h,
Centrifugal, it is dried, the LiNi after the residual alkali that is removed0.8Co0.15Al0.05O2。
Take 10g LiOH H2O Yu 1000g removes the LiNi after residual alkali0.8Co0.15Al0.05O2Pour batch mixer into
In, with 1000r/min rotating speed mixing 10min, weigh 5g TiO2Pour in batch mixer, turn with 1000r/min
Speed continues mixing 10min；Taking out compound after having mixed, sinter at 500 DEG C, period leads to 6L/h
Entering oxygen, after sintering 3h, liter high-temperature is to 800 DEG C, is cooled to room temperature, mistake after crushing after continuing sintering 5h
200 mesh sieves, obtain the polynary positive pole material of Li-Ti-O oxide skin(coating) cladding, this Li-Ti-O oxide skin(coating) bag
The scanning electron microscope (SEM) photograph of the polynary positive pole material covered is as it is shown in figure 1, the Li-Ti-O oxide cladding layers on surface is bright
Aobvious, coating covers completely, equably on multicomponent material surface.
Embodiment 2
By water and polynary positive pole material LiNi0.85Co0.10Al0.05O2Mix for 0.5:1 in mass ratio, stirring
10h, centrifugal, it is dried, the LiNi after the residual alkali that is removed0.85Co0.10Al0.05O2。
Take 20g LiOH H2O Yu 1000g removes the LiNi after residual alkali0.85Co0.10Al0.05O2Pour batch mixer into
In, with 1000r/min rotating speed mixing 5h, weigh 2g TiO2Pour in batch mixer, continue with 800r/min rotating speed
Continuous mixing 1h；Taking out compound after having mixed, sinter at 400 DEG C, period is passed through oxygen with 20L/h,
After sintering 20h, liter high-temperature is to 1000 DEG C, is cooled to room temperature after continuing sintering 6h, crosses 200 mesh after crushing
Sieve, obtains the polynary positive pole material of Li-Ti-O oxide skin(coating) cladding, and it is polynary that this Li-Ti-O oxide is coated with
The scanning electron microscope (SEM) photograph of positive electrode as it is shown in figure 1, the Li-Ti-O oxide cladding layers on surface is obvious, coating
Completely, cover equably on multicomponent material surface.
Embodiment 3
By water and polynary positive pole material LiNi0.85Co0.10Al0.05O2Mix for 6:1 in mass ratio, stir 8h, from
The heart, is dried, the LiNi after the residual alkali that is removed0.85Co0.10Al0.05O2。
Take 5g LiOH H2O Yu 1000g removes the LiNi after residual alkali0.85Co0.10Al0.05O2Pour batch mixer into
In, with 2000r/min rotating speed mixing 15min, weigh 40g TiO2Pour in batch mixer, with 1500r/min
Rotating speed continues mixing 10min；Taking out compound after having mixed, sinter at 600 DEG C, period is with 5L/h
Being passed through oxygen, after sintering 2h, liter high-temperature is to 700 DEG C, is cooled to room temperature, after crushing after continuing sintering 30h
Cross 200 mesh sieves, obtain the polynary positive pole material of Li-Ti-O oxide skin(coating) cladding, this Li-Ti-O oxide bag
The scanning electron microscope (SEM) photograph of the polynary positive pole material covered shows, the Li-Ti-O oxide cladding layers on surface is obvious, cladding
Thing covers completely, equably on multicomponent material surface.
Embodiment 4
By water and polynary positive pole material LiNi0.8Co0.15Al0.05O2Mix for 5:1 in mass ratio, stir 3h, from
The heart, is dried, the LiNi after the residual alkali that is removed0.8Co0.15Al0.05O2。
Take 15g LiOH H2O Yu 1000g removes the LiNi after residual alkali0.8Co0.15Al0.05O2Pour batch mixer into
In, with 1200r/min rotating speed mixing 30min, weigh 10g TiO2Pour in batch mixer, with 1500r/min
Rotating speed continues mixing 1h；Taking out compound after having mixed, sinter at 500 DEG C, period is passed through with 8L/h
Oxygen, after sintering 5h, liter high-temperature is to 850 DEG C, is cooled to room temperature after continuing sintering 10h, crosses 200 after crushing
Mesh sieve, obtains the polynary positive pole material of Li-Ti-O oxide skin(coating) cladding, and this Li-Ti-O oxide cladding is many
The scanning electron microscope (SEM) photograph of unit's positive electrode shows, the Li-Ti-O oxide cladding layers on surface is obvious, and coating is complete
Whole, cover on multicomponent material surface equably.
Embodiment 5
By water and polynary positive pole material LiNi0.8Co0.15Al0.05O2Mix for 7.5:1 in mass ratio, stirring
6.5h, centrifugal, it is dried, the LiNi after the residual alkali that is removed0.8Co0.15Al0.05O2。
Take 6g LiOH H2O Yu 1000g removes the LiNi after residual alkali0.8Co0.15Al0.05O2Pour batch mixer into
In, with 1000r/min rotating speed mixing 45min, weigh the TiO that gross mass is 25g2And Al2O3Mixture
Pour in batch mixer, continue mixing 3h with 1250r/min rotating speed；Compound is taken out after having mixed,
Sintering at 550 DEG C, period is passed through oxygen with 10L/h, and after sintering 10h, liter high-temperature is to 900 DEG C, continues to burn
It is cooled to room temperature after knot 15h, after crushing, crosses 200 mesh sieves, obtain Li-Al-Ti-O oxide skin(coating) cladding many
Unit's positive electrode, the scanning electron microscope (SEM) photograph of the polynary positive pole material of this Li-Al-Ti-O oxide cladding shows, table
The Li-Al-Ti-O oxide cladding layers in face is obvious, and coating covers completely, equably at multicomponent material table
Face.
Embodiment 6
By water and polynary positive pole material LiNi0.85Co0.10Al0.05O2Mix for 4:1 in mass ratio, stir 10h,
Centrifugal, it is dried, the LiNi after the residual alkali that is removed0.85Co0.10Al0.05O2。
Take 20g LiOH H2O Yu 1000g removes the LiNi after residual alkali0.85Co0.15O2Pour in batch mixer,
With 1000r/min rotating speed mixing 3h, weigh the TiO that gross mass is 8g2And Al2O3Mixture pour batch mixing into
In machine, continue mixing 20min with 1600r/min rotating speed；Compound is taken out, at 600 DEG C after having mixed
Sintering, period is passed through oxygen with 15L/h, is incubated at 600 DEG C after sintering 5h, cools down after continuing sintering 18h
To room temperature, cross 200 mesh sieves after crushing, obtain the polynary positive pole material of Li-Al-Ti-O oxide skin(coating) cladding,
The scanning electron microscope (SEM) photograph of the polynary positive pole material of this Li-Al-Ti-O oxide cladding shows, the Li-Al-Ti-O on surface
Oxide cladding layers is obvious, and coating covers completely, equably on multicomponent material surface.
Comparative example 1
Except being added without LiOH H2Outside O, other preparation methoies and condition are same as in Example 1, prepare
Surface coating TiO2Polynary positive pole material；This Surface coating TiO2The scanning electron microscope (SEM) photograph of polynary positive pole material
As in figure 2 it is shown, the cladding in this material is not complete packet coating, coating is scattered in polynary material with graininess
Material surface, occurs without clad.
The electrode material of the present embodiment 1-6 and comparative example 1 is assembled into 18650EC as positive active material
Cylindrical battery:
The preparation of positive plate: in 5L blender, by positive active material, binding agent PVDF and conductive agent
Super-P carries out positive pole dispensing by 97:1:2 under oil system and vacuum condition, it is thus achieved that uniform anode sizing agent, will
The anode sizing agent prepared is uniformly coated on plus plate current-collecting body Al paper tinsel, it is thus achieved that positive plate.
The preparation of negative plate: by graphite, thickening agent CMC, binding agent SBR and conduction powdered carbon by weight
95:1:2:2 carries out cathode blending under water system, it is thus achieved that uniform cathode size, the cathode size that will prepare
It is uniformly coated on negative current collector Cu paper tinsel and cools down, it is thus achieved that negative plate.
The preparation of lithium ion battery: by the positive plate prepared according to above-mentioned technique, negative plate and membrane coil coiling
Standby lithium-ion electric core, injects nonaqueous electrolytic solution, prepares 18650EC cylindrical battery, wherein, nonaqueous electrolytic solution
Using concentration is the LiPF of 1.0mol/L6As electrolyte, using volume ratio is the ethylene carbonate of 1:1, carbon
The mixture of diethyl phthalate is as nonaqueous solvent.
The lithium ion battery preparing above-described embodiment 1-6 and comparative example 1 uses following methods to carry out electrical property survey
Examination:
Charge-discharge test: first lithium ion battery is melted into, at room temperature with 0.01C constant-current charge the most extremely
3.4V, then with 0.2C constant-current charge to 3.8V, the most at room temperature with 0.2C constant-current charge to 4.2V, then
Constant voltage, to 0.05C, after standing 5min, is discharged to 3V with 0.2C, circulates 500 weeks, records discharge capacity
With the discharge capacity after circulation in 500 weeks.
High temperature circulation is tested: be first melted into lithium ion battery, at room temperature first with 0.01C constant-current charge
To 3.4V, then with 0.2C constant-current charge to 3.8V, then at 60 DEG C with 0.2C constant-current charge to 4.2V,
Constant voltage is to 0.05C again, after standing 5min, is discharged to 3V with 0.2C, circulates 500 weeks, and record electric discharge is held
Discharge capacity after amount and circulation in 500 weeks.
Table 1
The performance of lithium ion battery result such as table of the positive electrode of embodiments of the invention 1-6 and comparative example 1 preparation
Shown in 1, as can be found from Table 1, the electrode material application that the oxide skin(coating) using the inventive method to prepare is coated with
In battery, show more preferable normal-temperature circulating performance and high temperature cyclic performance, this electricity being coated with oxide skin(coating)
Pole material surface has uniformly, complete packet coating is closely related.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed ability real
Execute.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention
The equivalence of each raw material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the guarantor of the present invention
Within the scope of protecting scope and disclosure.
Claims (10)
1. the surface coating method of an electrode material, it is characterised in that described method includes following step
Rapid:
(1) electrode material is mixed with Lithium hydrate；
(2) add by TiO in the mixture of step (1)2Or Al2O3Any a kind or 2 kinds composition
Oxide, continue mixing；
(3) mixture of step (2) is sintered in the first temperature, carries out in the second temperature the most again
Sintering, obtains the electrode material of oxide skin(coating) cladding；
Wherein, the second temperature >=the first temperature >=400 DEG C.
Surface coating method the most according to claim 1, it is characterised in that described electrode material is
Positive electrode, preferably polynary positive pole material, more preferably LiNixM1‐xO2, wherein 0.1≤x
≤ 1, M be in Co, Mn, Al, Mg, Ti, V, Cr, Zr, Nb, Ga or Sr any a kind or
The combination of at least 2 kinds.
Surface coating method the most according to claim 1 and 2, it is characterised in that step (1) institute
The mass ratio stating Lithium hydrate and described electrode material is 0.1～2:100, preferably 0.5:100；
Preferably, the mode of step (1) described mixing is for being placed in batch mixer mixing, and described batch mixer is preferred
For any a kind in ballmillmixer, VC mixer, fusion machine or three-dimensional mixer, further preferably
For VC mixer；
Preferably, during the described mixing of step (1), the rotating speed of mixer is 800～2000r/min, is preferably
1000r/min；
Preferably, the time of step (1) described mixing is 0.1～10h, preferably 1h.
4. according to the surface coating method described in any one of claim 1-3, it is characterised in that step (2)
Described oxide is 0.1～5:100 with the mass ratio of described electrode material, preferably 0.4:100；
Preferably, during step (2) described continuation mixing, the rotating speed of mixer is 800～2000r/min, excellent
Elect 1000r/min as；
Preferably, step (2) the described time continuing mixing is 0.1～5h, preferably 1h.
5. according to the surface coating method described in any one of claim 1-4, it is characterised in that step (3)
Described being sintered in sintering furnace is carried out；
Preferably, it is sintered in air atmosphere or oxygen atmosphere described in step (3) carrying out；
Preferably, in described air atmosphere or oxygen atmosphere, the flow of air or oxygen independently be 1～20
L/h。
6. according to the surface coating method described in any one of claim 1-5, it is characterised in that step (3)
Described first temperature is 400～600 DEG C, preferably 500 DEG C；
Preferably, step (3) is described is 2～20h in the time that the first temperature is sintered, preferably 5h；
Preferably, described second temperature of step (3) is 600～1000 DEG C, preferably 700 DEG C；
Preferably, step (3) is described is 6～30h in the time that the second temperature is sintered, preferably 8h；
Preferably, when second temperature ＞ the first temperature, it is warmed up to the intensification speed of the second temperature from the first temperature
Degree is 1～10 DEG C/min.
7. according to the surface coating method described in any one of claim 1-6, it is characterised in that described method
Step (1) ' is carried out so that electrode material is carried out remove impurity: by electrode material before being additionally included in step (1)
Mix with water, stirring, be then peeled off and be dried, obtain the electrode material after remove impurity；
Preferably, step (1) ' described in the mass ratio of water and electrode material be 0.5～10:1；
Preferably, step (1) ' described in stirring time be 1～10h；
Preferably, step (1) ' described in be separated into any a kind during centrifugation or filter pressing separate；
Preferably, the rotating speed of described centrifugation is 1000～10000rpm, and the time of described centrifugation is excellent
Elect 5～60min as；
Preferably, the temperature being dried described in step (1) ' is 100～900 DEG C, the described dry time
It is preferably 4～20h；
Preferably, step (1) ' after electrode material surface Lithium hydrate after the remove impurity that obtains and lithium carbonate
Gross mass content≤1%.
8. according to the surface coating method described in any one of claim 1-7, it is characterised in that described method
It is additionally included in step (3) after the second temperature has sintered, carries out the step cooling down, pulverize and sieving；
Preferably, being cooled to temperature described in is 10～80 DEG C.
9. the jacketed electrode material that the surface coating method as described in any one of claim 1-8 prepares,
It is characterized in that, described jacketed electrode material comprises electrode material and is coated on described electrode material surface
Oxide skin(coating), and described oxide skin(coating) is Li-Ti-O oxide, Li-Al-O compound or Li-Al-Ti-Oization
In compound any a kind；
Preferably, described oxide skin(coating) even compact and complete, the thickness of described oxide skin(coating) is preferably
1～50nm；
Preferably, described electrode material is positive electrode, preferably polynary positive pole material, more preferably
LiNixM1‐xO2, wherein 0.1≤x≤1, M is Co, Mn, Al, Mg, Ti, V, Cr, Zr, Nb,
Any a kind or the combination of at least 2 kinds in Ga or Sr.
10. a lithium ion battery, it is characterised in that described lithium ion battery includes described in claim 9
Jacketed electrode material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107154492A (en) * | 2017-05-22 | 2017-09-12 | 东北大学 | A kind of surface modification LATO LNMO electrode materials and preparation method |
| CN109950498A (en) * | 2019-03-29 | 2019-06-28 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof with uniform clad |
| CN110380022A (en) * | 2019-06-26 | 2019-10-25 | 荆门市格林美新材料有限公司 | A kind of high voltage monocrystalline nickel-cobalt-manganternary ternary anode material and preparation method |
| CN110649233A (en) * | 2018-06-26 | 2020-01-03 | Sk新技术株式会社 | Positive active material for lithium secondary battery and lithium secondary battery including the same |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901905A (en) * | 2009-05-27 | 2010-12-01 | 比亚迪股份有限公司 | Titanium composite, preparation method thereof and application thereof |
| CN104143639A (en) * | 2013-05-11 | 2014-11-12 | 周明炯 | Lithium battery electrode material and preparation method thereof |
| EP2814082A1 (en) * | 2013-06-06 | 2014-12-17 | Leclanché S.A. | Electrochemical cells with glass containing separators |
| US20150228970A1 (en) * | 2014-02-10 | 2015-08-13 | Samsung Sdi Co., Ltd. | Composite cathode active material, method of preparing the same, and cathode and lithium battery including the composite cathode active material |
-
2016
- 2016-07-28 CN CN201610614711.7A patent/CN105977476B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901905A (en) * | 2009-05-27 | 2010-12-01 | 比亚迪股份有限公司 | Titanium composite, preparation method thereof and application thereof |
| CN104143639A (en) * | 2013-05-11 | 2014-11-12 | 周明炯 | Lithium battery electrode material and preparation method thereof |
| EP2814082A1 (en) * | 2013-06-06 | 2014-12-17 | Leclanché S.A. | Electrochemical cells with glass containing separators |
| US20150228970A1 (en) * | 2014-02-10 | 2015-08-13 | Samsung Sdi Co., Ltd. | Composite cathode active material, method of preparing the same, and cathode and lithium battery including the composite cathode active material |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107154492B (en) * | 2017-05-22 | 2019-07-09 | 东北大学 | A kind of the LNMO electrode material and preparation method of surface modification LATO |
| CN107154492A (en) * | 2017-05-22 | 2017-09-12 | 东北大学 | A kind of surface modification LATO LNMO electrode materials and preparation method |
| US11764347B2 (en) | 2017-10-20 | 2023-09-19 | Lg Chem, Ltd. | Method of preparing positive electrode active material for secondary battery and secondary battery using the same |
| CN111201200A (en) * | 2017-10-20 | 2020-05-26 | 株式会社Lg化学 | Method of preparing positive electrode active material for secondary battery and secondary battery using the same |
| US11031590B2 (en) | 2018-06-26 | 2021-06-08 | Sk Innovation Co., Ltd. | Cathode active material for lithium secondary battery and lithium secondary battery including the same |
| CN112952062B (en) * | 2018-06-26 | 2024-03-19 | Sk新能源株式会社 | Positive active material for lithium secondary battery and lithium secondary battery including the same |
| CN110649233A (en) * | 2018-06-26 | 2020-01-03 | Sk新技术株式会社 | Positive active material for lithium secondary battery and lithium secondary battery including the same |
| CN112952062A (en) * | 2018-06-26 | 2021-06-11 | Sk新技术株式会社 | Positive active material for lithium secondary battery and lithium secondary battery including the same |
| CN111162249A (en) * | 2018-11-07 | 2020-05-15 | 天津国安盟固利新材料科技股份有限公司 | Positive electrode material for improving first discharge capacity and preparation method thereof |
| CN109950498A (en) * | 2019-03-29 | 2019-06-28 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof with uniform clad |
| CN110380022B (en) * | 2019-06-26 | 2022-06-10 | 荆门市格林美新材料有限公司 | High-voltage single-crystal nickel-cobalt-manganese ternary positive electrode material and preparation method thereof |
| CN110380022A (en) * | 2019-06-26 | 2019-10-25 | 荆门市格林美新材料有限公司 | A kind of high voltage monocrystalline nickel-cobalt-manganternary ternary anode material and preparation method |
| CN110726940A (en) * | 2019-09-19 | 2020-01-24 | 深圳市比克动力电池有限公司 | Method for rapidly evaluating cycle performance of high-nickel cathode material of lithium ion battery |
| CN110726940B (en) * | 2019-09-19 | 2021-10-01 | 深圳市比克动力电池有限公司 | Method for rapidly evaluating cycle performance of high-nickel cathode material of lithium ion battery |
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