CN109713262A - A kind of preparation method of cobalt/cobalt oxide cladding tertiary cathode material - Google Patents
A kind of preparation method of cobalt/cobalt oxide cladding tertiary cathode material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of cobalt/cobalt oxide cladding tertiary cathode material, belong to cell positive material technical field.Solve the problems, such as it is how to realize to reduce sintering temperature and low covering amount and there is high rate capability, a kind of preparation method of cobalt/cobalt oxide cladding tertiary cathode material, this method includes cobalt source and nickelic tertiary cathode material being put into container, then be mixed to get corresponding mixed material to be stirred under the speed conditions of≤700rpm；Under the atmosphere of air or oxygen, mixed material is subjected to Low Temperature Solid-Phase sintering processes under conditions of 250 DEG C~550 DEG C, obtains corresponding cobalt/cobalt oxide cladding tertiary cathode material；The covering amount of cobalt/cobalt oxide is 0.1wt%~1.0wt% of tertiary cathode material quality.It can effectively realize the effect of low cobalt oxide cladding, realize material multiplying power under high pressure and cycle performance.
Description
Technical field
The present invention relates to a kind of preparation methods of cobalt/cobalt oxide cladding tertiary cathode material, belong to cell positive material technology
Field.
Background technique
Lithium ion battery is by feat of high-energy density, long circulation life, higher operating voltage, low self-discharge and to environment
The advantages that friendly, is widely used in new-energy automobile field.New-energy automobile continues as a kind of novel vehicles
Boat ability, charge efficiency, safety and cost etc. are consumer's problems of concern, everything is all electric with lithium ion power
The performance in pond is closely bound up.With the extensive application of new-energy automobile, market proposes more the performance of lithium-ion-power cell
High requirement.
Core component of the battery electrode material as lithium-ion-power cell, directly determines its chemical property.Commercially
The negative electrode material of change mainly has graphite and silicon-carbon, and performance has met present needs.And lithium ion power is really restricted at present
The principal element of battery development is positive electrode, also becomes the bottleneck that lithium-ion-power cell energy density improves instantly.City
Positive electrode on field mainly has LiFePO4, cobalt acid lithium, LiMn2O4, nickel cobalt manganese and nickel cobalt aluminium etc..In existing positive electrode
In system, in order to pursue the lithium-ion-power cell of high-energy density, market has turned one's attention to the positive electrode of nickelic system.
However, such material still suffers from many problems in practical applications: cationic mixing causes material irreversible capacity to become larger；It is non-
The generation of electro-chemical activity NiO causes the rapid decaying of battery capacity；The dissolution of metal ion is so that the material circulation lost of life；
The cell safety problem that oxygen release causes；Surface impurity prevents lithium ion from spreading with interface charge transmission, and the circulation for destroying material is steady
Qualitative and high rate performance.In order to improve nickelic system positive electrode performance, also have by being modified with raising property
Can, as Chinese patent application (publication number: CN106532006A) discloses a kind of preparation of cobalt oxide cladding tertiary cathode material
Method, the chemical general formula of the positive electrode are Li (NixCoMn1-x-y)O2,0.5≤x≤0.9,0<y≤0.3,0<1-x-y≤
0.2, this method includes first processing nickeliferous ternary positive electrode, then by tertiary cathode material and nanometre grade cobalt compound mixed at high speed
Uniformly, high temperature sintering prepares cobalt oxide cladding tertiary cathode material under the atmospheric condition of air or oxygen.But it needs to use
High-speed stirred, and the mixing speed of generally conventional high-speed stirred is in 1000rpm or more, and nickelic positive electrode is in such height
Speed stirs lower pattern and can be destroyed, to influence performance；It is since the additive amount of cobalt compound is higher, and mole covering amount is 2%
In the range of~6%, the temperature being sintered in this way is higher, is unfavorable for energy conservation and control cost, and covering amount is excessive also affects height
The performance of nickel positive electrode need to use nanoscale material, high to the particle requirement of cobalt compound, be unfavorable for commercial exploitation.
Summary of the invention
The present invention is directed to the above defect existing in the prior art, provides a kind of cobalt/cobalt oxide cladding tertiary cathode material
Preparation method solves the problems, such as it is how to realize low-temperature sintering and propose high-multiplying power discharge specific capacity using low covering amount.
The purpose of the present invention is what is be achieved by the following technical programs, a kind of cobalt/cobalt oxide cladding tertiary cathode material
Preparation method, method includes the following steps:
A, cobalt source and nickelic tertiary cathode material are put into container, then to be stirred under the speed conditions of≤700rpm
It is mixed to get corresponding mixed material；
B, under the atmosphere of air or oxygen, mixed material is subjected to Low Temperature Solid-Phase burning under conditions of 250 DEG C~550 DEG C
Knot processing obtains corresponding cobalt/cobalt oxide cladding tertiary cathode material；The covering amount of the cobalt/cobalt oxide is tertiary cathode material
0.1wt%~1.0wt% of quality.
The present invention is in order to avoid destroying nickelic ternary just by being stirred mixing under the revolving speed not higher than 700rpm
The pattern of pole material makes the primary characteristic that material is kept during mixing；And find in the course of the research, by 250
DEG C~550 DEG C of cryogenic conditions under carry out solid-phase sintering processing, be in order to make to be sintered under the decomposition temperature of cobalt source, and
Under the atmosphere of air or oxygen, advantageously forms unbodied cobalt/cobalt oxide and coated on a small quantity on the surface of tertiary cathode material
Cobalt/cobalt oxide improves the ability of ion transmission, avoids influence of the existing high temperature sintering to the form of material and reduces circulation
High rate performance；Meanwhile it can make the clad to be formed that can be effectively relieved between material and electrolyte by Low Temperature Solid-Phase sintering
Interfacial reaction reduces the surface impurity of material and improves the transmission of lithium ion and reduce polarization, realizes that the multiplying power for improving material is followed
It ring performance and can be used under high-voltage state；And energy consumption also can preferably be reduced using low-temperature sintering, improve energy
Utilization.On the other hand, discovery table face covering amount is affected to the performance of material in the course of the research, by making using a small amount of
Cobalt/cobalt oxide covering amount be tertiary cathode material quality 0.1wt%~1.0wt%, can more effectively improve material times
Rate cycle performance by changing covering amount makes that a small amount of cobalt/cobalt oxide is only needed to can be obtained material under high-voltage state here
Excellent properties, think that covering amount increases the better prejudice of high rate performance improvement different from conventional.Cobalt mentioned here
Oxide includes CoO, Co2O3Or Co3O4, it is also possible to their any ingredient mixing, cobalt/cobalt oxide can also use Co-O system oxygen
Compound expression etc..
In the preparation method of above-mentioned cobalt/cobalt oxide cladding tertiary cathode material, preferably, cobalt oxidation described in step B
The covering amount of object is 0.1wt%~0.5wt% of tertiary cathode material quality.Material can be made by leading to too small amount of cobalt/cobalt oxide cladding
Material has better circulation performance.As further preferably, the covering amount of the cobalt/cobalt oxide is tertiary cathode material
Expect 0.12wt%~0.35wt% of quality.
In the preparation method of above-mentioned cobalt/cobalt oxide cladding tertiary cathode material, preferably, stirring described in step A is mixed
It closes and uses magnetic agitation；The revolving speed is 100rpm~600rpm.Here unit rpm is rev/min, and by using magnetic force
Stirring has lower mixing speed, is mixed using low mixing speed, can make have the effect of low-shearing force, be conducive to
Better nickelic tertiary cathode material is destroyed in whipping process and changes its pattern, influences the circulation performance of material.
As further preferably, the mixing speed is 150rpm~400rpm.
In the preparation method of above-mentioned cobalt/cobalt oxide cladding tertiary cathode material, preferably, cobalt source described in step A is selected
From cobalt oxalate, cobalt acetate, cobalt carbonate, cobalt hydroxide, CoO, Co (OH)2, cobalt naphthenate, one in cobaltous octadecanate and new cobalt decanoate
Kind is a variety of.It is easy to get using these cobalt sources with raw material, advantage at low cost, can more be had using these cobalt sources more importantly
Effect is decomposed to form corresponding cobalt/cobalt oxide under cryogenic, coats conducive to being formed on the surface of nickelic tertiary cathode material.
In the preparation method of above-mentioned cobalt/cobalt oxide cladding tertiary cathode material, preferably, nickelic ternary described in step A
Positive electrode is the nickelic tertiary cathode material of mole >=0.5 of nickel.Material has high-energy density, and preferably guarantees material
Expect performance.As a further preference, the nickelic tertiary cathode material is LiNi0.8Co0.15Al0.05O2Material.This ternary is just
Pole material and a small amount of cobalt oxide form facilitation, can effectively improve the circulation performance of base material.And in mesh
In preceding research, the covering amount generallyd use is the several times in the present invention, and the present invention has not only reached and utilized a small amount of cobalt oxidation
It closes object and improves material property, and synthetic method is simply controllable, be conducive to control cost.
In the preparation method of above-mentioned cobalt/cobalt oxide cladding tertiary cathode material, preferably, of cobalt source described in step A
Grain partial size is micron order.Due to combining low-temperature sintering processing to combine by using stirring at low speed, that is, it is equivalent to and makes to be sintered
Temperature is handled in the decomposition temperature or so of cobalt source, reduces the requirement to cobalt source material, need to only use micron-sized particle
Better circulating ratio performance can be realized.Compared to using for nano-scale particle, the requirement to raw material does not need too severe
It carves, has been more convenient in actual production process to advantageously reduce production cost to the selection of raw material and demand.As further excellent
Choosing, the grain diameter of the cobalt source are 100 μm~300 μm.
In the preparation method of above-mentioned cobalt/cobalt oxide cladding tertiary cathode material, preferably, low-temperature solid described in step B
The temperature of phase sintering processing is 300 DEG C~400 DEG C.Under low-temperature sintering, preferable material property can not only be realized, and have
The effect that low energy consumption.
In conclusion compared with prior art, the present invention having the advantage that
It is that raw material is incorporated in and stirs at low speed and Low Temperature Solid-Phase is sintered phase by using a small amount of cobalt source and nickelic ternary material
In conjunction with treatment process, can effectively realize the effect of low cobalt oxide cladding, can be effectively relieved material and electrolyte it
Between interfacial reaction, reduce the surface impurity of material and improve the transmission of lithium ion and reduce polarization, the multiplying power for improving material follows
Ring performance, and still be able to keep the performance under high pressure.
Detailed description of the invention
Fig. 1 is the Co that the present invention obtains3O4Coat LiNi0.8Co0.15Al0.05O2Material and raw material Li Ni0.8Co0.15Al0.05O2
The XRD diagram of material.
Fig. 2 is the Co that the present invention obtains3O4Coat LiNi0.8Co0.15Al0.05O2Material and raw material Li Ni0.8Co0.15Al0.05O2
The SEM of material schemes.
Fig. 3 is the Co that the present invention obtains3O4Coat LiNi0.8Co0.15Al0.05O2Material circulation high rate performance figure.
Specific embodiment
Below by specific embodiments and the drawings, the technical solutions of the present invention will be further described, but this
Invention is not limited to these examples.
Embodiment 1
Weigh the cobalt oxalate of 0.0115g and the LiNi of 10g0.8Co0.15Al0.05O2Material is into beaker, the particle of cobalt oxalate
Partial size is 100 μm~300 μm, then, is uniformly mixed with carrying out magnetic agitation 30min under the revolving speed of 300rpm (rev/min), it
Object phase transfer after mixing to ceramic material boat is moved into material boat in tube furnace again afterwards, under the atmosphere of air, heating will
Temperature is raised to 350 DEG C or so progress Low Temperature Solid-Phase calcination processing 3h, after, a small amount of Co is obtained after natural cooling3O4Cladding
LiNi0.8Co0.15Al0.05O2Material, here for Co in obtained material3O4Covering amount is LiNi0.8Co0.15Al0.05O2's
0.1wt% or so, can also be indirectly from the cobalt oxalate of addition and raw material Li Ni0.8Co0.15Al0.05O2The usage ratio of material, base
This can also illustrate in material that the present embodiment obtains only a small amount of Co3O4The effect of cladding.
By Co obtained above3O4Coat LiNi0.8Co0.15Al0.05O2Material carries out corresponding test analysis, specific as schemed
Shown in 1-3:
It further says, wherein a small amount of Co of the present embodiment from Fig. 13O4Coat LiNi0.8Co0.15Al0.05O2Material
With raw material pure phase LiNi0.8Co0.15Al0.05O2The XRD spectrum of material, it can be found that there is no apparent Co in XRD spectrum3O4
Diffraction maximum, this is to illustrate that the covering amount of the corresponding cobalt/cobalt oxide of the present invention is less.Meanwhile as shown in connection with fig. 2, Fig. 2 (b) is this
A small amount of Co of embodiment3O4Coat LiNi0.8Co0.15Al0.05O2The SEM of material schemes, which is spheric granules, with pure phase
Fig. 2 (a) is compared, and the present invention adds a small amount of cobalt/cobalt oxide Co3O4Pattern is not influenced significantly.
And CR2023 button cell is made in material prepared by the present embodiment as follows: by obtained sample with
Conductive agent acetylene black and the binder Kynoar ratio of 8:1:1 in mass ratio are uniformly mixed, and are with N-Methyl pyrrolidone
Slurry is made in solvent, is coated uniformly on the aluminium foil of LITHIUM BATTERY, and the dry 12h at 85 DEG C, being cut into diameter later is 14cm's
Disk, the dry 12h in 120 DEG C of vacuum drying oven.Positive plate is transferred to (H in argon gas glove box after natural cooling2O<10,O2
<10ppm).It is to electrode with lithium metal, Celgard film is diaphragm, solute LiPF6(1mol/L) and solvent are EC+DEC+
The solution of DMC (1:1:1, voL) is electrolyte.12h is stood after the completion of battery assembly, using LT2001A battery test system into
Row electrochemical property test, test voltage range be 3.0V~4.5V high voltage condition under, respectively by 0.1C, 0.5C, 1C,
Charge and discharge (recycling respectively 5 times under per same current density), circulation times are carried out under the different current densities of 5C, 0.5C and 0.1C
Rate performance is as shown in Figure 3: Fig. 3 Co3O4Coat LiNi0.8Co0.15Al0.05O2The high rate performance figure of positive electrode, says as a comparison
It is bright, while comparative (accordingly being produced adding raw materials 0.0575g cobalt oxalate in embodiment 2 obtained in embodiment 2 to increase
Object) and do not add the positive electrode LiNi of cobalt oxalate0.8Co0.15Al0.05O2Chemical property analyzed together in Fig. 3
Compare.Show a small amount of Co from the data result in Fig. 33O4Coat LiNi0.8Co0.15Al0.05O2Anode can obviously improve it again
Rate performance, raw material positive electrode LiNi0.8Co0.15Al0.05O2High rate performance want far short of what is expected.Corresponding 0.1% or so covering amounts
LiNi0.8Co0.15Al0.05O2Discharge capacity reaches about 210mAh/g or so for the first time, and pass through respectively 0.1C, 0.5C, 1C, 5C,
After recycling 30 times under 0.5C with 0.1C difference current density, it still is able to be maintained at about 200mAh/g；To can also be seen that in Fig. 3
Performance is taken second place when the covering amount of cladding 0.5% or so, after recycling 30 times especially under different current densities, is still able to maintain preferably
Level, without add cobalt oxalate positive electrode LiNi0.8Co0.15Al0.05O2(the corresponding data of raw material shown in Fig. 3) are steady
It is qualitative then far short of what is expected, it is seen then that the present invention can effectively improve material property by cladding on a small quantity；Meanwhile it is of the invention forthright again
Can test is carried out under 3.0V~4.5V high voltage condition, also illustrates that material of the invention can be realized in high-voltage state
Under still be able to keep preferable circulation performance.
Embodiment 2
Weigh the cobalt oxalate of 0.0575g and the LiNi of 10g0.8Co0.15Al0.05O2Material is into beaker, the particle of cobalt oxalate
Partial size is 100 μm~300 μm, then, is uniformly mixed with carrying out magnetic agitation 30min under the revolving speed of 300rpm (rev/min), it
Object phase transfer after mixing to ceramic material boat is moved into material boat in tube furnace again afterwards, under the atmosphere of air, heating will
Temperature is raised to 350 DEG C or so progress Low Temperature Solid-Phase calcination processing 3h, after, a small amount of Co is obtained after natural cooling3O4Cladding
LiNi0.8Co0.15Al0.05O2Material, here for Co in obtained material3O4Covering amount is LiNi0.8Co0.15Al0.05O2's
0.5wt% or so.
Equally, a small amount of Co obtained in the present embodiment3O4Coat LiNi0.8Co0.15Al0.05O2Material does not have under XRD spectrum
There is apparent cobalt/cobalt oxide diffraction maximum, illustrates the few characteristic of its covering amount；And the pattern of display material is spherical in SEM figure
Grain influences there is no apparent, also illustrates the few characteristic of its covering amount, and the pattern of display material is spherical in SEM figure
Grain, pattern are destroyed there is no apparent.For its electrochemical property test with identical in embodiment 1, test voltage range is 3.0V
~4.5V, respectively by carrying out charge and discharge (each electric current under the different current densities of 0.1C, 0.5C, 1C, 5C, 0.5C and 0.1C
Recycled 5 times under density), the concrete analysis explanation that specific test result carries out in Fig. 3 is (corresponding when covering amount 0.5% in Fig. 3
Analysis chart).
Embodiment 3
Weigh the cobalt acetate of 0.0221g, the LiNi of 10g0.8Co0.15Al0.05O2Material is into beaker, the particle of cobalt acetate
Diameter is 100 μm~200 μm, then, is uniformly mixed with the revolving speed magnetic agitation 60min of 200rpm, later again will after mixing
Object phase transfer to ceramic material boat, material boat is moved into tube furnace, 300 DEG C of calcining 4h under the atmosphere of air, after, naturally
Cobalt/cobalt oxide is obtained after cooling coats LiNi0.8Co0.15Al0.05O2Material, the covering amount of cobalt/cobalt oxide is cobalt/cobalt oxide packet here
Cover LiNi0.8Co0.15Al0.05O2The about 0.2wt% of the quality of material.
Equally, cobalt/cobalt oxide obtained in the present embodiment coats LiNi0.8Co0.15Al0.05O2Material, under XRD spectrum
There is no apparent cobalt/cobalt oxide diffraction maximum, illustrates the few characteristic of its covering amount yet, and the pattern of display material is ball in SEM figure
Shape particle is influenced there is no apparent.For its electrochemical property test with identical in embodiment 1, test voltage range is 3.0V
~4.5V, respectively by carrying out charge and discharge (each electric current under the different current densities of 0.1C, 0.5C, 1C, 5C, 0.5C and 0.1C
Recycled 5 times under density), the corresponding discharge capacity for the first time of the present embodiment reaches about 202mAh/g or so, and is passing through above-mentioned difference
After recycling 30 times under current density, it still is able to be maintained at about 195mAh/g, meanwhile, high rate performance test of the invention is in high electricity
It is carried out under the conditions of pressure, equally illustrates that material of the invention can be realized and still be able to keep preferable multiplying power under high-voltage state
Cycle performance.
Embodiment 4
Weigh the cobalt carbonate of 0.0741g and the LiNi of 10g0.8Co0.15Al0.05O2Material is into beaker, the particle of cobalt carbonate
Partial size is 200 μm~300 μm, then, is uniformly mixed with carrying out magnetic agitation 80min under the revolving speed of 400rpm.It later will mixing
Object phase transfer after uniformly moves into material boat in tube furnace, 400 DEG C of calcining 6h under the atmosphere of air to ceramic material boat.It is natural
Cobalt/cobalt oxide is obtained after cooling coats LiNi0.8Co0.15Al0.05O2Material.Here the covering amount of cobalt/cobalt oxide is cobalt/cobalt oxide packet
Cover LiNi0.8Co0.15Al0.05O2The about 0.7wt% of the quality of material.Equally, the present embodiment cobalt/cobalt oxide coats
LiNi0.8Co0.15Al0.05O2Material also illustrates that its covering amount is few also without apparent cobalt/cobalt oxide diffraction maximum under XRD spectrum
Characteristic, and the pattern of display material is spheric granules in SEM figure, is influenced there is no apparent.Its electrochemical property test
With identical in embodiment 1, test voltage range is 3.0V~4.5V, respectively by 0.1C, 0.5C, 1C, 5C, 0.5C and
Charge and discharge (recycling 5 times under each current density) is carried out under the different current densities of 0.1C, the present embodiment is corresponding to discharge for the first time
Capacity reaches about 206mAh/g or so, and after being recycled 30 times under above-mentioned different current densities, it still is able to be maintained at about
200mAh/g, meanwhile, high rate performance test of the invention is carried out under high voltage condition, also illustrates material energy of the invention
Enough realize keeps preferable circulation performance under high-voltage state.
Embodiment 5
Weigh a certain amount of cobalt naphthenate and the LiNi of 10g0.8Co0.15Al0.05O2Material is into beaker, cobalt naphthenate here
Additive amount according to the covering amount of cobalt/cobalt oxide in the material eventually formed be 1.0% to be added, the particle of cobalt naphthenate
Diameter is micron order, then, is uniformly mixed with carrying out magnetic agitation 20min under the revolving speed of 700rpm.It will be uniformly mixed later
Object phase transfer afterwards moves into material boat in tube furnace, 550 DEG C of calcining 3h under the atmosphere of air to ceramic material boat.Natural cooling
Cobalt/cobalt oxide is obtained afterwards coats LiNi0.8Co0.15Al0.05O2Material.Here the covering amount of cobalt/cobalt oxide is cobalt/cobalt oxide cladding
LiNi0.8Co0.15Al0.05O2The about 1.0wt% of the quality of material.Equally, cobalt/cobalt oxide obtained in the present embodiment coats
LiNi0.8Co0.15Al0.05O2Material also illustrates that its covering amount is few also without apparent cobalt/cobalt oxide diffraction maximum under XRD spectrum
Characteristic, and the pattern of display material is spheric granules in SEM figure, is influenced there is no apparent.Its electrochemical property test
With identical in embodiment 1, test voltage range is 3.0V~4.5V, respectively by 0.1C, 0.5C, 1C, 5C, 0.5C and
Charge and discharge (recycling 5 times under each current density) is carried out under the different current densities of 0.1C, the present embodiment is corresponding to discharge for the first time
Capacity reaches about 203mAh/g or so, and after being recycled 30 times under above-mentioned different current densities, it still is able to be maintained at about
196mAh/g, meanwhile, high rate performance test of the invention is carried out under high voltage condition, also illustrates material energy of the invention
Enough realize keeps preferable circulation performance under high-voltage state.
Embodiment 6
Weigh a certain amount of new cobalt decanoate and the LiNi of 10g0.8Co0.15Al0.05O2Material is into beaker, new cobalt decanoate here
Additive amount according to the covering amount of cobalt/cobalt oxide in the material eventually formed be 0.4% to be added, the particle of new cobalt decanoate
Diameter is 200 μm or so, then, is uniformly mixed with carrying out magnetic agitation 50min under the revolving speed of 600rpm.It later will after mixing
Object phase transfer to ceramic material boat, material boat is moved into tube furnace, carries out Low Temperature Solid-Phase calcining at 250 DEG C under the atmosphere of oxygen
3h, after, cobalt/cobalt oxide is obtained after natural cooling coats LiNi0.8Co0.15Al0.05O2Material.Here the cladding of cobalt/cobalt oxide
Amount is that cobalt/cobalt oxide coats LiNi0.8Co0.15Al0.05O2The about 0.4wt% of the quality of material.
Equally, cobalt/cobalt oxide obtained in the present embodiment coats LiNi0.8Co0.15Al0.05O2Material, under XRD spectrum
There is no apparent cobalt/cobalt oxide diffraction maximum, illustrates the few characteristic of its covering amount yet, and the pattern of display material is ball in SEM figure
Shape particle is influenced there is no apparent.For its electrochemical property test with identical in embodiment 1, test voltage range is 3.0V
~4.5V is carrying out charge and discharge (recycling 5 times under each current density) by 0.1C, 0.5C, 1C, 5C, 0.5C and 0.1C respectively,
The corresponding discharge capacity for the first time of the present embodiment reaches about 205mAh/g, and recycles 30 times under by above-mentioned different current densities
Afterwards, it still is able to be maintained at about 196mAh/g, meanwhile, high rate performance test of the invention is carried out under high voltage condition, is also said
It material of the invention is illustrated can be realized and keep preferable circulation performance under high-voltage state.
Embodiment 7
Weigh the cobalt oxalate of 0.0115g and the LiNi of 10g0.8Co0.15Al0.05O2Material is into beaker, the particle of cobalt oxalate
Partial size is 150 μm or so, then, is uniformly mixed with carrying out magnetic agitation 90min under the revolving speed of 100rpm (rev/min), later
Again by object phase transfer after mixing to ceramic material boat, material boat is moved into tube furnace, under the atmosphere of air, heating will be warm
Degree is raised to 255 DEG C or so progress Low Temperature Solid-Phase calcination processing 8h, after, a small amount of Co is obtained after natural cooling3O4Cladding
LiNi0.8Co0.15Al0.05O2Material, here for Co in obtained material3O4Covering amount is LiNi0.8Co0.15Al0.05O2's
0.1wt% or so, can also be indirectly from the cobalt oxalate of addition and raw material Li Ni0.8Co0.15Al0.05O2The usage ratio of material, base
This can also illustrate in material that the present embodiment obtains only a small amount of Co3O4The effect of cladding.
Equally, cobalt/cobalt oxide obtained in the present embodiment coats LiNi0.8Co0.15Al0.05O2Material, under XRD spectrum
There is no apparent cobalt/cobalt oxide diffraction maximum, illustrates the few characteristic of its covering amount yet, and the pattern of display material is ball in SEM figure
Shape particle is influenced there is no apparent.For its electrochemical property test with identical in embodiment 1, test voltage range is 3.0V
~4.5V carries out charge and discharge (each electricity under the different current densities by 0.1C, 0.5C, 1C, 5C, 0.5C and 0.1C respectively
Recycled 5 times under current density), the corresponding discharge capacity for the first time of the present embodiment reaches about 215mAh/g, and by above-mentioned different electricity
After current density recycles 30 times, it still is able to be maintained at about 205mAh/g, meanwhile, high rate performance test of the invention is in high voltage item
It is carried out under part, also illustrates that material of the invention can be realized and keep preferable circulation performance under high-voltage state.
Embodiment 8
That the preparation method is the same as that of Example 1 is consistent for the cobalt/cobalt oxide cladding tertiary cathode material of the present embodiment specific, and difference is only
It is, wherein by the raw material tertiary cathode material LiNi in embodiment 10.8Co0.15Al0.05O2Using LiNi0.7Co0.1Mn0.2O2
Instead of making a small amount of Co3O4Covering amount is 0.1wt%.Obtained material is subjected to corresponding performance test, the results showed that a small amount of
Co3O4Coat LiNi0.7Co0.1Mn0.2O2Material, a small amount of Co obtained in the present embodiment3O4Coat LiNi0.7Co0.1Mn0.2O2Material
Material, also also illustrates the few characteristic of its covering amount without apparent cobalt/cobalt oxide diffraction maximum under XRD spectrum, and shows in SEM figure
The pattern for showing material is spheric granules, is influenced there is no apparent.Its electrochemical property test is the same as identical in embodiment 1, survey
Examination voltage range be 3.0V~4.5V, respectively by 0.1C, 0.5C, 1C, 5C, 0.5C and 0.1C different current densities under into
Row charge and discharge (recycle 5 times) under each current density, and the corresponding discharge capacity for the first time of the present embodiment reaches about 208mAh/g, and
After above-mentioned different current densities recycle 30 times, it still is able to be maintained at about 198mAh/g, there is preferable capacity retention ratio；Together
When, high rate performance test of the invention is carried out under high voltage condition, also illustrates that material of the invention can be realized in height
It still is able to keep preferable circulation performance under voltage status.
Certainly, the tertiary cathode material LiNi in the present embodiment0.7Co0.1Mn0.2O2Other nickelic ternarys can equally be used
Positive electrode replaces, and makes the tertiary cathode material of molar content >=0.5 of nickelic tertiary cathode material nickel, such as with
LiNi0.7Co0.1Mn0.2O2For, make the LiNi of 1mol0.7Co0.1Mn0.2O2The mole of middle nickel is 0.5mol.
Specific embodiment described in the present invention only illustrate the spirit of the present invention by way of example.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.
Claims (9)
1. a kind of preparation method of cobalt/cobalt oxide cladding tertiary cathode material, which is characterized in that method includes the following steps:
A, cobalt source and nickelic tertiary cathode material are put into container, then to be stirred mixing under the speed conditions of≤700rpm
Obtain corresponding mixed material；
B, under the atmosphere of air or oxygen, mixed material is carried out at Low Temperature Solid-Phase sintering under conditions of 250 DEG C~550 DEG C
Reason obtains corresponding cobalt/cobalt oxide cladding tertiary cathode material；The covering amount of the cobalt/cobalt oxide is tertiary cathode material quality
0.1wt%~1.0wt%.
2. the preparation method of cobalt/cobalt oxide cladding tertiary cathode material according to claim 1, which is characterized in that in step B
The covering amount of the cobalt/cobalt oxide is 0.1wt%~0.5wt% of tertiary cathode material quality.
3. the preparation method of cobalt/cobalt oxide cladding tertiary cathode material according to claim 1, which is characterized in that in step A
It is described to be stirred using magnetic agitation；The revolving speed is 100rpm~600rpm.
4. the preparation method of the according to claim 1 or 2 or 3 cobalt/cobalt oxide cladding tertiary cathode materials, which is characterized in that step
Cobalt source described in rapid A is selected from cobalt oxalate, cobalt acetate, cobalt carbonate, cobalt hydroxide, CoO, Co (OH)2, cobalt naphthenate, cobaltous octadecanate
With one of new cobalt decanoate or a variety of.
5. the preparation method of the according to claim 1 or 2 or 3 cobalt/cobalt oxide cladding tertiary cathode materials, which is characterized in that step
Nickelic tertiary cathode material described in rapid A is the nickelic tertiary cathode material of mole >=0.5 of nickel.
6. the preparation method of cobalt/cobalt oxide cladding tertiary cathode material according to claim 5, which is characterized in that described nickelic
Tertiary cathode material is LiNi0.8Co0.15Al0.05O2Material.
7. the preparation method of the according to claim 1 or 2 or 3 cobalt/cobalt oxide cladding tertiary cathode materials, which is characterized in that step
The grain diameter of cobalt source described in rapid A is micron order.
8. the preparation method of cobalt/cobalt oxide cladding tertiary cathode material according to claim 7, which is characterized in that the cobalt source
Grain diameter be 100 μm~300 μm.
9. the preparation method of the according to claim 1 or 2 or 3 cobalt/cobalt oxide cladding tertiary cathode materials, which is characterized in that step
The temperature of Low Temperature Solid-Phase sintering processes described in rapid B is 300 DEG C~400 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518209A (en) * | 2019-08-27 | 2019-11-29 | 广东风华新能源股份有限公司 | Method for preparing anode material and the positive electrode of preparation |
| CN111640928A (en) * | 2020-06-30 | 2020-09-08 | 蜂巢能源科技有限公司 | NCMA quaternary system material, preparation method thereof, lithium battery positive electrode material and lithium battery |
| CN112018341A (en) * | 2019-05-28 | 2020-12-01 | 天津国安盟固利新材料科技股份有限公司 | High-capacity high-nickel cathode material and preparation method thereof |
| CN113428912A (en) * | 2021-08-26 | 2021-09-24 | 蜂巢能源科技有限公司 | Quaternary positive electrode material and preparation method and application thereof |
| CN113707851A (en) * | 2020-05-21 | 2021-11-26 | 天津国安盟固利新材料科技股份有限公司 | Surface-coated lithium ion battery positive electrode material and preparation method thereof |
| CN114122379A (en) * | 2021-11-09 | 2022-03-01 | 远景动力技术(江苏)有限公司 | Positive electrode material and preparation method and application thereof |
| CN114261995A (en) * | 2021-12-22 | 2022-04-01 | 远景动力技术(江苏)有限公司 | Positive active material and preparation method and application thereof |
| CN114583102A (en) * | 2022-02-21 | 2022-06-03 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226256A (en) * | 2015-10-26 | 2016-01-06 | 河南师范大学 | For modified cathode material and the lithium titanate battery of lithium titanate battery |
| CN106356509A (en) * | 2016-09-29 | 2017-01-25 | 华东理工大学 | Cobaltosic oxide coated and modified nickel-doped lithium manganate and preparation method thereof |
| CN106532006A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method of cobaltous oxide coated ternary anode material |
| CN108258224A (en) * | 2018-01-22 | 2018-07-06 | 华南理工大学 | A kind of tertiary cathode material of surface clad oxide and preparation method thereof |
-
2018
- 2018-12-17 CN CN201811543950.3A patent/CN109713262A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226256A (en) * | 2015-10-26 | 2016-01-06 | 河南师范大学 | For modified cathode material and the lithium titanate battery of lithium titanate battery |
| CN106356509A (en) * | 2016-09-29 | 2017-01-25 | 华东理工大学 | Cobaltosic oxide coated and modified nickel-doped lithium manganate and preparation method thereof |
| CN106532006A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method of cobaltous oxide coated ternary anode material |
| CN108258224A (en) * | 2018-01-22 | 2018-07-06 | 华南理工大学 | A kind of tertiary cathode material of surface clad oxide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOXIA YAN 等: "The effect of Co3O4 & LiCoO2 cladding layer on the high rate and storage property of high nickel material LiNi0.8Co0.15Al0.05O2 by simple one-step wet coating method", 《ELECTROCHIMICA ACTA》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112018341A (en) * | 2019-05-28 | 2020-12-01 | 天津国安盟固利新材料科技股份有限公司 | High-capacity high-nickel cathode material and preparation method thereof |
| CN110518209B (en) * | 2019-08-27 | 2022-04-22 | 广东风华新能源股份有限公司 | Preparation method of anode material and prepared anode material |
| CN110518209A (en) * | 2019-08-27 | 2019-11-29 | 广东风华新能源股份有限公司 | Method for preparing anode material and the positive electrode of preparation |
| CN113707851A (en) * | 2020-05-21 | 2021-11-26 | 天津国安盟固利新材料科技股份有限公司 | Surface-coated lithium ion battery positive electrode material and preparation method thereof |
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| CN113428912B (en) * | 2021-08-26 | 2022-02-18 | 蜂巢能源科技有限公司 | Quaternary positive electrode material and preparation method and application thereof |
| CN114122379A (en) * | 2021-11-09 | 2022-03-01 | 远景动力技术(江苏)有限公司 | Positive electrode material and preparation method and application thereof |
| CN114122379B (en) * | 2021-11-09 | 2023-09-05 | 远景动力技术(江苏)有限公司 | Positive electrode material, preparation method and application thereof |
| CN114261995A (en) * | 2021-12-22 | 2022-04-01 | 远景动力技术(江苏)有限公司 | Positive active material and preparation method and application thereof |
| CN114261995B (en) * | 2021-12-22 | 2023-12-08 | 远景动力技术(江苏)有限公司 | Positive electrode active material, preparation method and application thereof |
| CN114583102A (en) * | 2022-02-21 | 2022-06-03 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
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Application publication date: 20190503 |