CN109638258A - A kind of positive electrode and its preparation method and application - Google Patents
A kind of positive electrode and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of positive electrodes and its preparation method and application, the positive electrode is titanium dioxide and the co-modified tertiary cathode material of lithium fluoride, total mass percentage of titanium dioxide and lithium fluoride is 0.17-3.4% in the positive electrode, it passes through the modification of titanium dioxide and lithium fluoride to tertiary cathode material, solve the hygroscopic formation lithium hydroxide in tertiary cathode material surface and lithium carbonate, the problem for causing alkalinity excessively high, significantly improve its security performance and cycle performance, the ratio of its high rate performance 10C/1C is 0.85-0.91, specific capacity is 174-184mAh/g under the conditions of the charge and discharge that current density is 0.2C, capacity retention rate >=97.8% after 50 circulations.
Description
Technical field
The present invention relates to cell positive materials more particularly to a kind of positive electrode and its preparation method and application.
Background technique
It is influenced by policy driving, dynamic lithium battery positive electrode industry is rapidly developed, and electric vehicle requires battery to have
Specific energy is high, specific power is big, self discharge is few, long service life, price are cheap and the characteristics such as safety is good.
Ternary material is able to satisfy that specific energy is high, specific power is big, the lower requirement of price, but presently, there are main problem be
Surface alkali content is excessively high, and the easy deoxidation of material surface causes capacitance loss.The general means for improving ternary material include cladding, doping
With surface modification etc., such as oxide cladding, carbon material cladding, Fluorin doped, Coated with Organic Matter, hydrochlorate containing lithium coated etc..
CN108682795A discloses a kind of ternary cathode material of lithium ion battery surface acid-washing cladding TiO2Method, will
Tertiary cathode material is added in saturation titanium sulfate acyl solution, and ultrasonic mixing forms suspension, suspension persistently stirred to get brown
Color precipitating filters, washing, dry, calcining, obtains TiO2The tertiary cathode material of cladding.Pass through controllable pickling cladding process
Surface is carried out to tertiary cathode material to be modified, and while reducing ternary material surface residual alkali, forms uniform TiO on surface2Packet
Coating.But pickling solution acidity is stronger in this method, will lead to metal ion dissolution, reduces the capacity of material, while sulfate radical is not
It is easy to wash to remove, also influence the performance of material capacity.
CN107302086A discloses a kind of preparation method of titanium-oxide-coated sodium ion tertiary cathode material, covering material
Solid solution is formed with contact agent, is easy to be evenly coated, and is tightly combined after firing, clad is not easily to fall off, and covering material can also
To form ideal glassy state cladding by high temperature, the performance of material is improved.The titanium-oxide-coated amount that this method needs
Larger, accounting in electrode material is relatively high, reduces the specific capacity of material.
CN108232131A discloses a kind of metal fluoride cladding ternary material and preparation method thereof, with the side of multiple ball milling
Formula makes ternary material in conjunction with metal fluoride, forms metal fluoride and coats ternary material.Work is coated using solid phase method mixing
Skill does not need to reduce the requirement for anticorrosion to equipment using fluoride precipitating reagent.But the uniformity of solid phase method cladding is poor, packet
The granularity for covering particle is big, and covering amount is higher.
Although above-mentioned document provides the method for some modification tertiary cathode materials, but still there is three that modification obtains
The specific capacity of first positive electrode is insufficient, poor circulation, and preparation method is complicated, at high cost and have the defects that secondary pollution,
Therefore it develops a kind of tertiary cathode material excellent with high specific capacity and cycle performance and preparation method thereof still and has and is important
Meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of positive electrode and its preparation method and application, the positive electrode is dioxy
Change titanium and the co-modified tertiary cathode material of lithium fluoride, total quality percentage of titanium dioxide and lithium fluoride in the positive electrode
Content is 0.17-3.4%, by the modification of titanium dioxide and lithium fluoride to tertiary cathode material, solves tertiary cathode material
Expect the hygroscopic formation lithium hydroxide in surface and lithium carbonate, the problem for causing alkalinity excessively high keeps its security performance and cycle performance equal
It significantly improves, the ratio of high rate performance 10C/1C is 0.85-0.91, specific capacity under the conditions of the charge and discharge that current density is 0.2C
For 174-184mAh/g, capacity retention rate >=97.8% after 50 circulations.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
The present invention relates to a kind of positive electrode, the positive electrode is titanium dioxide and the co-modified tertiary cathode of lithium fluoride
Material.
Positive electrode of the present invention is titanium dioxide and the co-modified tertiary cathode material of lithium fluoride, passes through dioxy
Change the modification of titanium and lithium fluoride to tertiary cathode material, solves the hygroscopic formation lithium hydroxide in tertiary cathode material surface and carbon
Sour lithium, the problem for causing alkalinity excessively high, significantly improves its security performance and cycle performance, the ratio of high rate performance 10C/1C
Value is 0.85-0.91 (illustratively including 0.85,0.88,0.9 or 0.91 etc.), under the conditions of current density is the charge and discharge of 0.2C
Specific capacity is 174-184mAh/g, capacity retention rate >=97.8% after 50 circulations.
Preferably, total mass percentage of titanium dioxide and lithium fluoride is 0.17-3.4% in the positive electrode,
Such as 0.17%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 3%, 3.4% etc..
Preferably, the tertiary cathode material includes nickel-cobalt-manganternary ternary anode material and/or nickel cobalt aluminium tertiary cathode material.
Second aspect, the present invention provides the preparation method of positive electrode as described in relation to the first aspect, the preparation method
Including with TiF4The tertiary cathode material containing lithium is handled, the positive electrode is obtained.
Tertiary cathode material of the present invention containing lithium refers to that surface includes the tertiary cathode of water, lithia and lithium carbonate
The reason of material, surface includes water, lithia and lithium carbonate, which is that tertiary cathode material surface metal ion valence state is higher, to be easy
Water is adsorbed, lithia is formed, and further forms lithium carbonate, the tertiary cathode of the present invention containing lithium with carbon dioxide reaction
The lithia of material surface and the mass percentage of lithium carbonate are 0.1-2%.
The method of the invention passes through TiF4Handle the tertiary cathode material containing lithium, the TiF4With tertiary cathode material table
Water, lithia and the lithium carbonate reaction in face generate titanium dioxide and lithium fluoride；Due to tertiary cathode material surface lithia and
The uniformity that lithium carbonate is distributed on tertiary cathode material surface, the titanium dioxide and lithium fluoride that ensure that generation are in tertiary cathode material
Material surface is evenly distributed, while the generation of lithium fluoride can be corroded to avoid tertiary cathode material by electrolyte, the life of titanium dioxide
At the ionic conductivity and high rate performance for improving tertiary cathode material.
Preferably, it the described method comprises the following steps:
(1) by TiF4It is added in high-temperature generator, heating volatilization is to obtain TiF4Gas；
(2) TiF for being obtained step (1) using dry carrier gas4Gas is sent into fluidized bed reaction, TiF4Gas and stream
The tertiary cathode material reaction containing lithium in fluidized bed reaction device generates the positive electrode；
(3) the gas-solid phase mixture comprising reaction product for obtaining step (2) carry out gas-solid it is mutually isolated it is described just
Pole material and gaseous component.
Preferably, the granularity of the tertiary cathode material of the present invention containing lithium is 5-15 μm, such as 5 μm, 6 μm, 7 μm, 8 μ
M, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm etc..
The method of the invention passes through TiF4Gas-solid phase reaction between gas and tertiary cathode material containing lithium, utilizes ternary
The lithia and lithium carbonate on positive electrode surface are realized using nano-titanium dioxide and nano-lithium fluoride as raw material to ternary
The pointed decoration on positive electrode surface, more traditional dry method cladding and wet process cladding, the uniformity of cladding significantly improve, simultaneously
Material and equipment will not be caused to corrode.
Preferably, step (3) is described carries out the device that gas-solid mutually separates as cyclone separator.
It preferably, further include that gaseous component progress cooling treatment is obtained into TiF after step (3)4。
Preferably, the cooling treatment carries out in cooling recover.
It preferably, further include being filled using dry gas to high-temperature generator, fluidized-bed reaction before carrying out step (1)
It sets, cyclone separator and cooling recover start the cleaning processing.
Cleaning treatment of the present invention can remove high-temperature generator, fluidized bed reaction, cyclone separator and cooling
Moisture in recover prevents the moisture in air from causing TiF4Hydrolysis, and the influence to tertiary cathode material.
Preferably, the dry gas include in oxygen, nitrogen or argon gas any one or at least two mixing
Object, the mixture illustratively include the mixture of oxygen and nitrogen, the mixture of oxygen and argon gas or nitrogen and argon gas
Mixture etc..
Preferably, the temperature of the dry gas be 120-350 DEG C, such as 120 DEG C, 150 DEG C, 180 DEG C, 210 DEG C,
240 DEG C, 270 DEG C, 300 DEG C or 350 DEG C etc., preferably 180-240 DEG C, further preferably 210 DEG C.
The present invention can be by high-temperature generator, fluidized bed reaction, cyclonic separation using the temperature of above-mentioned dry gas
99% or more moisture removal in device and cooling recover.
Preferably, the temperature of step (1) described heating be 284-350 DEG C, such as 284 DEG C, 295 DEG C, 300 DEG C, 310 DEG C,
330 DEG C or 350 DEG C etc., preferably 295-310 DEG C, further preferably 300 DEG C.
The method of the invention can guarantee TiF using the temperature range of above-mentioned heating4Gas will not be solidified as solid, together
When be unlikely to that temperature is excessively high to be decomposed again.
Preferably, step (2) described fluidized bed reaction includes gas distributor and fluidized-bed reactor.
Preferably, step (2) TiF for being obtained step (1) using dry carrier4Gas is sent into fluidized-bed reaction dress
The TiF that the step of setting obtains step (1) including the use of dry carrier4Gas is sent into gas distributor, enters fluidized bed later
Reactor.
Preferably, drying carrier gas described in step (2) includes any one in oxygen, nitrogen or argon gas or at least two
Mixture, the mixture illustratively include the mixture of oxygen and nitrogen, the mixture of oxygen and argon gas or nitrogen and
The mixture etc. of argon gas.
Preferably, the temperature of drying carrier gas described in step (2) be 284-350 DEG C, such as 284 DEG C, 295 DEG C, 300 DEG C,
310 DEG C, 330 DEG C or 350 DEG C etc., preferably 295-310 DEG C, further preferably 300 DEG C.
Preferably, the pressure of drying carrier gas described in step (2) be 0.2-0.8MPa, such as 0.2MPa, 0.4MPa,
0.6MPa or 0.8MPa etc..
Preferably, the gas flow rate of drying carrier gas described in step (2) be 20-100m/s, such as 20m/s, 30m/s,
40m/s, 50m/s, 60m/s, 70m/s, 80m/s, 90m/s or 100m/s etc..
Preferably, TiF described in step (2)4Gas and tertiary cathode material containing lithium in a fluidized bed reactor anti-
Answer the residence time be 0.5-60s, such as 0.5s, 1s, 4s, 5s, 7s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s,
55s or 60s etc., preferably 2-5s, further preferably 4s.
The present invention, which can guarantee material in a fluidized bed reactor using above-mentioned reaction time, sufficient time hair
Raw mixing and reaction, while being unlikely to the too small material of air velocity again and being difficult to fluidization.
Preferably, the temperature of the cooling treatment be 20-150 DEG C, such as 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C,
130 DEG C or 150 DEG C etc., preferably 40-80 DEG C, further preferably 60 DEG C.
The present invention can guarantee the TiF not reacted using the temperature of above-mentioned cooling treatment4Gas can sublimate completely
Recycling, and it is unlikely to the big heat exchange amount of the too low needs of temperature, cause the raising of energy consumption.
As currently preferred technical solution, the described method comprises the following steps:
(I) dry gas for being 120-350 DEG C using temperature is to high-temperature generator, fluidized bed reaction, cyclonic separation
Device and cooling recover start the cleaning processing；The dry gas include in oxygen, nitrogen or argon gas any one or extremely
Few two kinds of mixture；
(II) by TiF4It is added in high-temperature generator, heating volatilization is under the conditions of 284-350 DEG C to obtain TiF4Gas；
(III) TiF for being obtained step (II) using the drying carrier gas that temperature is 284-350 DEG C4Gas is sent into gas distribution
In device, enter fluidized-bed reactor, TiF later4Gas reacts life with the tertiary cathode material containing lithium in fluidized-bed reactor
At the positive electrode, the drying carrier gas includes the mixing of any one or at least two in oxygen, nitrogen or argon gas
Object, the pressure of the drying carrier gas are 0.2-0.8MPa, and the gas flow rate of the drying carrier gas is 20-100m/s, described
TiF4Gas and the reaction time of tertiary cathode material in a fluidized bed reactor containing lithium are 0.5-60s；
(IV) the gas-solid phase mixture comprising reaction product for obtaining step (III), which is sent into cyclone separator, carries out gas
The isolated positive electrode of solid phase and gaseous component；
(V) positive electrode that step (IV) obtains enters in material collector, and the gaseous component is recycled through cooling
Device carries out cooling treatment recycling TiF under the conditions of 20-150 DEG C4。
The third aspect, the present invention provides a kind of battery, the battery is using positive electrode as described in relation to the first aspect.
Compared with the existing technology, the invention has the following advantages:
(1) positive electrode of the present invention is titanium dioxide and the co-modified tertiary cathode material of lithium fluoride, more single
TiO2The tertiary cathode material of modification, cycle performance and storage performance significantly improve, the ratio of high rate performance 10C/1C
For 0.85-0.91, specific capacity is 174-184mAh/g under the conditions of the charge and discharge that current density is 0.2C, and capacity is protected after 50 circulations
Stay rate >=97.8%；
(2) preparation method of positive electrode of the present invention, using TiF4With the gas-solid of the tertiary cathode material containing lithium
The lithia on tertiary cathode material surface, lithium carbonate are converted lithium fluoride by phase reaction, while it is converted into TiO2, this process
Tertiary cathode material will not be caused to corrode, and TiF4Occur with the lithia and lithium carbonate of tertiary cathode material surface residual special
Property reaction, realize and carry out surface to tertiary cathode material with nanometer grade lithium fluoride and Nano titanium dioxide and uniformly modify to change
Property；
(3) preparation method of positive electrode of the present invention, do not introduce during the preparation process any other ion and
Ion cluster avoids impacting material property；
(4) preparation process of the preparation method of positive electrode of the present invention is simple, has operability, is suitble to industry
Metaplasia produces.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The preparation method of positive electrode:
(1) using temperature be 270 DEG C drying argon gas to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 320 DEG C4Gas；
(3) TiF for being obtained step (2) using the drying nitrogen that temperature is 284 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the drying nitrogen are 0.5MPa, and the flow velocity of the drying nitrogen is 60m/s, the TiF4
Gas and LiNi0.7Co0.15Mn0.15O2The average response residence time in a fluidized bed reactor is 4s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component exists through cooling recover
Cooling treatment is carried out under the conditions of 100 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of positive electrode obtained by the present embodiment is 0.86, and current density is the charge and discharge of 0.2C
Specific capacity is 183.4mAh/g under electric condition, and capacity retention rate is 97.8% after 50 circulations.
Embodiment 2
The preparation method of positive electrode:
(1) using temperature be 330 DEG C dry oxygen to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 290 DEG C4Gas；
(3) TiF for being obtained step (2) using the drying nitrogen that temperature is 290 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the drying nitrogen are 0.4MPa, and the gas flow rate of the drying nitrogen is 70m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 2s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component is through cooling recover
Cooling treatment is carried out under the conditions of 80 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of positive electrode obtained by the present embodiment is 0.91, and current density is the charge and discharge of 0.2C
Specific capacity is 178.7mAh/g under electric condition, and capacity retention rate is 98% after 50 circulations.
Embodiment 3
The preparation method of positive electrode:
(1) using temperature be 120 DEG C drying nitrogen to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 310 DEG C4Gas；
(3) TiF for being obtained step (2) using the drying nitrogen that temperature is 295 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the drying nitrogen are 0.6MPa, and the gas flow rate of the drying nitrogen is 40m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 5s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component is through cooling recover
Cooling treatment is carried out under the conditions of 60 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of positive electrode obtained by the present embodiment is 0.86, and current density is the charge and discharge of 0.2C
Specific capacity is 182.1mAh/g under electric condition, and capacity retention rate is 97.9% after 50 circulations.
Embodiment 4
The preparation method of positive electrode:
(1) using temperature be 180 DEG C dry oxygen to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 350 DEG C4Gas；
(3) TiF for being obtained step (2) using the drying argon gas that temperature is 300 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the drying carrier gas are 0.8MPa, and the gas flow rate of the drying carrier gas is 20m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 60s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component is through cooling recover
Cooling treatment is carried out under the conditions of 40 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of the first material of anode obtained by the present embodiment is 0.86, and current density is filling for 0.2C
Specific capacity is 177.2mAh/g under discharging condition, and capacity retention rate is 98.7% after 50 circulations.
Embodiment 5
The preparation method of positive electrode:
(1) using temperature be 210 DEG C drying nitrogen to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 330 DEG C4Gas；
(3) TiF for being obtained step (2) using the drying argon gas that temperature is 310 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the drying argon gas are 0.6MPa, and the gas flow rate of the drying argon gas is 40m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 2s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component is through cooling recover
Cooling treatment is carried out under the conditions of 30 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of positive electrode obtained by the present embodiment is 0.85, and current density is the charge and discharge of 0.2C
Specific capacity is 174.6mAh/g under electric condition, and capacity retention rate is 98.8% after 50 circulations.
Embodiment 6
The preparation method of positive electrode:
(1) using temperature be 300 DEG C drying nitrogen to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 295 DEG C4Gas；
(3) TiF for being obtained step (2) using the drying argon gas that temperature is 320 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the drying argon gas are 0.7MPa, and the gas flow rate of the drying argon gas is 30m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 10s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component exists through cooling recover
Cooling treatment is carried out under the conditions of 120 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of positive electrode obtained by the present embodiment is 0.89, and current density is the charge and discharge of 0.2C
Specific capacity is 176.1mAh/g under electric condition, and capacity retention rate is 98.6% after 50 circulations.
Embodiment 7
The preparation method of positive electrode:
(1) using temperature be 240 DEG C drying argon gas to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 340 DEG C4Gas；
(3) TiF for being obtained step (2) using the dry oxygen that temperature is 330 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the dry oxygen are 0.2MPa, and the gas flow rate of the dry oxygen is 100m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 0.5s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component is through cooling recover 20
Cooling treatment is carried out under the conditions of DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of positive electrode obtained by the present embodiment is 0.87, and current density is the charge and discharge of 0.2C
Specific capacity is 182.6mAh/g under electric condition, and capacity retention rate is 97.9% after 50 circulations.
Embodiment 8
The preparation method of positive electrode:
(1) using temperature be 350 DEG C drying argon gas to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 300 DEG C4Gas；
(3) TiF for being obtained step (2) using the dry oxygen that temperature is 340 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the dry oxygen are 0.65MPa, and the gas flow rate of the dry oxygen is 40m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 20s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component is through cooling recover
Cooling treatment is carried out under the conditions of 140 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of positive electrode obtained by the present embodiment is 0.90, and current density is the charge and discharge of 0.2C
Specific capacity is 180.7mAh/g under electric condition, and capacity retention rate is 97.9% after 50 circulations.
Embodiment 9
The preparation method of positive electrode:
(1) using temperature be 150 DEG C dry oxygen to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；
(2) by TiF4It is added in high-temperature generator, heating volatilization obtains TiF under the conditions of 284 DEG C4Gas；
(3) TiF for being obtained step (2) using the dry oxygen that temperature is 350 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4LiNi in gas and fluidized-bed reactor0.7Co0.15Mn0.15O2Described in reaction generates
Positive electrode, the pressure of the dry oxygen are 0.25MPa, and the gas flow rate of the dry oxygen is 90m/s, described
TiF4Gas and LiNi0.7Co0.15Mn0.15O2Reaction time in a fluidized bed reactor is 1s；
(4) the gas-solid phase mixture comprising reaction product for obtaining step (3), which is sent into cyclone separator, carries out gas-solid
The mutually isolated positive electrode and gaseous component；
(5) positive electrode that step (4) obtains enters in material collector, and the gaseous component is through cooling recover
Cooling treatment is carried out under the conditions of 150 DEG C recycles TiF4。
The ratio of the high rate performance 10C/1C of the co-modified ternary material of titanium dioxide and lithium fluoride obtained by the present embodiment is
0.89, specific capacity is 178.6mAh/g under the conditions of the charge and discharge that current density is 0.2C, and capacity retention rate is after 50 circulations
98.4%.
Comparative example 1
A kind of ternary cathode material of lithium ion battery surface acid-washing cladding TiO2Method, comprising the following steps:
(1) 1 part of titanium sulfate acyl and 60 parts of 1mol/L sulfuric acid are dissolved in the titanium sulfate that saturation is equipped in 2000 parts of deionized waters
Acyl solution；
(2) by 5 parts of tertiary cathode material LiNi0.7Co0.15Mn0.15O2It is added in saturation titanium sulfate acyl solution, ultrasonic mixing
30min is uniformly mixed, and forms suspension, and suspension is continued to stir 4h, until suspension lighter, obtains tan precipitate,
It filters, with ethanol wash 3 times, is dried in vacuo 6h at 70 DEG C, obtains dried material；
(3) dried material is placed on porcelain boat, is put into Muffle furnace and is heat-treated, in air atmosphere, with 2 DEG C/min
150 DEG C are warming up to, 1.5h is kept the temperature, then be warming up to 500 DEG C with 5 DEG C/min, keeps the temperature 5h, furnace cooling obtains TiO2The three of cladding
First positive electrode.
The ratio of the high rate performance 10C/1C of positive electrode obtained by this comparative example is 0.77, and current density is the charge and discharge of 0.2C
Specific capacity is 173.2mAh/g under electric condition, and capacity retention rate is 96.3% after 50 circulations.
The ratio of the high rate performance 10C/1C of positive electrode of the present invention is 0.85- it can be seen from embodiment 1-9
0.91, specific capacity is 174-184mAh/g under the conditions of the charge and discharge that current density is 0.2C, capacity retention rate after 50 circulations >=
97.8%, and the TiO that comparative example 1 obtains2The ratio of the high rate performance 10C/1C of the tertiary cathode material of cladding is 0.77, electric current
Specific capacity is only 173.2mAh/g under the conditions of the charge and discharge that density is 0.2C, and capacity retention rate is only 96.3% after 50 circulations,
It can thus be seen that positive electrode of the present invention is titanium dioxide and the co-modified tertiary cathode material of lithium fluoride, multiplying power
Performance, specific capacity and cycle performance are superior to the tertiary cathode material of single titanium dioxide modification used by comparative example 1.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of positive electrode, which is characterized in that the positive electrode is titanium dioxide and the co-modified tertiary cathode of lithium fluoride
Material.
2. positive electrode as described in claim 1, which is characterized in that titanium dioxide and lithium fluoride is total in the positive electrode
Mass percentage be 0.17-3.4%；
Preferably, the tertiary cathode material includes nickel-cobalt-manganternary ternary anode material and/or nickel cobalt aluminium tertiary cathode material.
3. the preparation method of positive electrode as claimed in claim 1 or 2, which is characterized in that the method includes with TiF4Processing
Tertiary cathode material containing lithium obtains the positive electrode.
4. preparation method as claimed in claim 3, which is characterized in that the described method comprises the following steps:
(1) by TiF4It is added in high-temperature generator, heating volatilization is to obtain TiF4Gas；
(2) TiF for being obtained step (1) using dry carrier gas4Gas is sent into fluidized bed reaction, TiF4Gas and fluidized bed
The tertiary cathode material reaction containing lithium in reaction unit generates the positive electrode；
(3) the gas-solid phase mixture comprising reaction product for obtaining step (2) carries out the mutually isolated positive material of gas-solid
Material and gaseous component；
Preferably, step (3) is described carries out the device that gas-solid mutually separates as cyclone separator；
It preferably, further include that gaseous component progress cooling treatment is obtained into TiF after step (3)4；
Preferably, the cooling treatment carries out in cooling recover.
5. such as the described in any item preparation methods of claim 3 or 4, which is characterized in that before carrying out step (1) further include benefit
High-temperature generator, fluidized bed reaction, cyclone separator and cooling recover are started the cleaning processing with dry gas；
Preferably, the dry gas include in oxygen, nitrogen or argon gas any one or at least two mixture；
Preferably, the temperature of the dry gas is 120-350 DEG C, preferably 180-240 DEG C, further preferably 210 DEG C.
6. such as the described in any item preparation methods of claim 3-5, which is characterized in that the temperature of step (1) described heating is
284-350 DEG C, preferably 295-310 DEG C, further preferably 300 DEG C.
7. such as the described in any item preparation methods of claim 3-6, which is characterized in that step (2) described fluidized bed reaction
Including gas distributor and fluidized-bed reactor；
Preferably, step (2) TiF for being obtained step (1) using dry carrier4Gas is sent into fluidized bed reaction
The TiF that step obtains step (1) including the use of dry carrier4Gas is sent into gas distributor, enters fluidized-bed reaction later
Device；
Preferably, drying carrier gas described in step (2) include in oxygen, nitrogen or argon gas any one or at least two it is mixed
Close object；
Preferably, the temperature of drying carrier gas described in step (2) be 284-350 DEG C, preferably 295-310 DEG C, further preferably
It is 300 DEG C；
Preferably, the pressure of drying carrier gas described in step (2) is 0.2-0.8MPa；
Preferably, the gas flow rate of drying carrier gas described in step (2) is 20-100m/s；
Preferably, TiF described in step (2)4The reaction of gas and tertiary cathode material containing lithium in a fluidized bed reactor stops
Time is 0.5-60s, preferably 2-5s, further preferably 4s.
8. such as the described in any item preparation methods of claim 3-7, which is characterized in that the temperature of the cooling treatment is 20-
150 DEG C, preferably 40-80 DEG C, further preferably 60 DEG C.
9. such as the described in any item preparation methods of claim 3-8, which is characterized in that the described method comprises the following steps:
(I) using temperature be 120-350 DEG C dry gas to high-temperature generator, fluidized bed reaction, cyclone separator and
Cooling recover starts the cleaning processing；The dry gas includes any one or at least two in oxygen, nitrogen or argon gas
The mixture of kind；
(II) by TiF4It is added in high-temperature generator, heating volatilization is under the conditions of 284-350 DEG C to obtain TiF4Gas；
(III) TiF for being obtained step (II) using the drying carrier gas that temperature is 284-350 DEG C4Gas is sent into gas distributor,
Enter fluidized-bed reactor, TiF later4Gas is reacted with the tertiary cathode material containing lithium in fluidized-bed reactor described in generation
Positive electrode, the drying carrier gas includes the mixture of any one or at least two in oxygen, nitrogen or argon gas, described
The pressure of drying carrier gas be 0.2-0.8MPa, the gas flow rate of the drying carrier gas is 20-100m/s, the TiF4Gas
Body and the reaction time of tertiary cathode material in a fluidized bed reactor containing lithium are 0.5-60s；
(IV) the gas-solid phase mixture comprising reaction product for obtaining step (III), which is sent into cyclone separator, carries out gas-solid phase
The isolated positive electrode and gaseous component；
(V) positive electrode that step (IV) obtains enters in material collector, and the gaseous component exists through cooling recover
Cooling treatment is carried out under the conditions of 20-150 DEG C recycles TiF4。
10. a kind of battery, which is characterized in that the battery uses positive electrode as claimed in claim 1 or 2.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773763A (en) * | 2004-11-08 | 2006-05-17 | 深圳市比克电池有限公司 | Lithium ion secondary cell with nickel-base anode active material and producing method thereof |
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| CN101510608A (en) * | 2008-02-13 | 2009-08-19 | Tdk株式会社 | Active material, electrode, and methods of manufacture thereof |
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| CN102569775A (en) * | 2011-12-23 | 2012-07-11 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and positive electrode active material thereof |
| CN102598372A (en) * | 2009-11-11 | 2012-07-18 | 安维亚***公司 | Coated positive electrode materials for lithium ion batteries |
| CN102610822A (en) * | 2012-03-07 | 2012-07-25 | 宁德新能源科技有限公司 | Lithium ion secondary battery and anode material thereof |
| WO2012153487A1 (en) * | 2011-05-06 | 2012-11-15 | 株式会社豊田自動織機 | Negative active material for rechargeable lithium ion battery and manufacturing method for same, and rechargeable lithium ion battery and manufacturing method for same |
| CN103456946A (en) * | 2013-09-12 | 2013-12-18 | 刘志航 | Anode material for lithium ion battery |
| CN102086032B (en) * | 2009-12-07 | 2014-09-24 | 深圳市比克电池有限公司 | Preparation method and application of micro/nano structured LiFePO4 compound |
| CN104584284A (en) * | 2013-08-29 | 2015-04-29 | 株式会社Lg化学 | Lithium transition metal composite particles, method for preparing same, and positive active materials comprising same |
| KR20160083818A (en) * | 2015-01-02 | 2016-07-12 | 주식회사 엘 앤 에프 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN106356507A (en) * | 2015-07-13 | 2017-01-25 | 三星电子株式会社 | Composite cathode active material for lithium battery, cathode for lithium battery including the same, and lithium battery including the cathode |
| CN106711414A (en) * | 2016-12-16 | 2017-05-24 | 江南大学 | 811-type ternary positive modified material for lithium ion batteries and preparation method thereof |
| CN107910543A (en) * | 2017-12-13 | 2018-04-13 | 江南大学 | A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof |
| CN108431994A (en) * | 2015-08-11 | 2018-08-21 | 工业研究与发展基金会有限公司 | The intercalation materials of li ions and Its Preparation Method And Use of metal fluoride coating |
| CN109216687A (en) * | 2018-10-16 | 2019-01-15 | 桑顿新能源科技有限公司 | A kind of preparation method of monocrystalline trielement composite material and a kind of lithium ion battery |
-
2018
- 2018-12-18 CN CN201811551175.6A patent/CN109638258B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773763A (en) * | 2004-11-08 | 2006-05-17 | 深圳市比克电池有限公司 | Lithium ion secondary cell with nickel-base anode active material and producing method thereof |
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| CN101510608A (en) * | 2008-02-13 | 2009-08-19 | Tdk株式会社 | Active material, electrode, and methods of manufacture thereof |
| CN102598372A (en) * | 2009-11-11 | 2012-07-18 | 安维亚***公司 | Coated positive electrode materials for lithium ion batteries |
| CN102086032B (en) * | 2009-12-07 | 2014-09-24 | 深圳市比克电池有限公司 | Preparation method and application of micro/nano structured LiFePO4 compound |
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| WO2012153487A1 (en) * | 2011-05-06 | 2012-11-15 | 株式会社豊田自動織機 | Negative active material for rechargeable lithium ion battery and manufacturing method for same, and rechargeable lithium ion battery and manufacturing method for same |
| CN102569775A (en) * | 2011-12-23 | 2012-07-11 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and positive electrode active material thereof |
| CN102610822A (en) * | 2012-03-07 | 2012-07-25 | 宁德新能源科技有限公司 | Lithium ion secondary battery and anode material thereof |
| CN104584284A (en) * | 2013-08-29 | 2015-04-29 | 株式会社Lg化学 | Lithium transition metal composite particles, method for preparing same, and positive active materials comprising same |
| CN103456946A (en) * | 2013-09-12 | 2013-12-18 | 刘志航 | Anode material for lithium ion battery |
| KR20160083818A (en) * | 2015-01-02 | 2016-07-12 | 주식회사 엘 앤 에프 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN106356507A (en) * | 2015-07-13 | 2017-01-25 | 三星电子株式会社 | Composite cathode active material for lithium battery, cathode for lithium battery including the same, and lithium battery including the cathode |
| CN108431994A (en) * | 2015-08-11 | 2018-08-21 | 工业研究与发展基金会有限公司 | The intercalation materials of li ions and Its Preparation Method And Use of metal fluoride coating |
| CN106711414A (en) * | 2016-12-16 | 2017-05-24 | 江南大学 | 811-type ternary positive modified material for lithium ion batteries and preparation method thereof |
| CN107910543A (en) * | 2017-12-13 | 2018-04-13 | 江南大学 | A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof |
| CN109216687A (en) * | 2018-10-16 | 2019-01-15 | 桑顿新能源科技有限公司 | A kind of preparation method of monocrystalline trielement composite material and a kind of lithium ion battery |
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Address after: 065001 No. 1 Fenghua Road, Science and Technology Valley, Langfang Development Zone, Langfang City, Hebei Province Patentee after: Langfang green industry technology service center Patentee after: Institute of Process Engineering, Chinese Academy of Sciences Address before: 065001 No. 1 Fenghua Road, Science and Technology Valley, Langfang Development Zone, Langfang City, Hebei Province Patentee before: LANGFANG INSTITUTE OF PROCESS ENGINEERING, CAS Patentee before: Institute of Process Engineering, Chinese Academy of Sciences |