CN109119624A - A kind of preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material - Google Patents
A kind of preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material Download PDFInfo
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Abstract
A kind of preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material, comprising the following steps: (1) lithium-rich manganese-based presoma with lithium source mixed, ground, calcined in air atmosphere, it is cooling；(2) it disperses lithium-rich manganese-based anode material in anhydrous organic solvent I, stirs evenly；Titanium source is added, is stirred evenly, black suspension a is obtained；(3) lithium source and phosphorus source are weighed, lithium source and phosphorus source are added in anhydrous organic solvent II, stirs evenly, obtains mixing suspension b；(4) mixing suspension b is added in black suspension a and is reacted, oil bath is evaporated, and obtains dry gel powder；(5) dry gel powder is placed under reducing atmosphere and is calcined,.Titanium phosphate lithium of the present invention is as surface coating layer, the rupture and layered-spinel phase transformation of second particle can not only be alleviated, and anode-electrolyte interface dynamics can be improved, make titanium phosphate lithium cladding lithium-rich manganese-based anode material composite material that there is excellent cyclical stability.
Description
Technical field
The present invention relates to a kind of preparation methods of positive electrode, and in particular to a kind of titanium phosphate lithium cladding lithium-rich manganese-based anode
The preparation method of material.
Background technique
Lithium ion battery have specific energy density height, charge discharge life length, memory-less effect, environmental pollution is small, puts certainly
The electric low advantage of rate, since the advent of the world capture always the high-end market of portable battery.
Lithium-rich manganese-based anode material is a kind of material of greatest concern in current Study on Li-ion batteries, can use general formulaxLi2MnO3·(1-x)LiMO2(M=Ni, Co, Mn, 0 <x< 1) it indicates；It possesses high capacity, high thermal stability, high-energy density
Many advantages, such as, but its problems such as there is also serious voltage attenuation and low conductivity.This is because in charge and discharge process, Mn
Ion is migrated from octahedral interstice to tetrahedral interstice, leads to Li2MnO3Mutually change from monocline to spinel structure, thus
Serious voltage attenuation is shown as on chemical property.Surface coating technology can inhibit the volume change of basis material, subtract
Few parasitic reaction etc. generated by material and electrolyte contacts.Therefore choosing suitable surface covering material is to reduce Li2MnO3
The effective means of phase transition.
Fast-ionic conductor titanium phosphate lithium (LiTi2(PO4)3) spacing and Li+Radius matches the most, and it is with three-dimensional space
Between frame crystal structure, facilitate Li+Quick deintercalation, have good chemical property.
CN107591529A, which is disclosed, a kind of by titanium phosphate lithium is coated on nickel-cobalt-manganternary ternary anode material using hydrothermal method
Synthetic method, still, under resulting materials 0.1C, discharge capacity is only 173 .7mAh/g for the first time, and chemical property is to be improved；
Also, hydrothermal method has certain uncontrollability, and yield is lower, is not suitable for large-scale production.
Summary of the invention
The technical problem to be solved by the present invention is to it is rich to overcome the deficiencies of the prior art and provide a kind of titanium phosphate lithium cladding
The preparation method of lithium manganese-based anode material prepares titanium phosphate lithium cladding lithium-rich manganese-based anode material using sol-gal process, improves
The cyclical stability of material.
The technical solution adopted by the present invention to solve the technical problems is: a kind of titanium phosphate lithium cladding lithium-rich manganese-based anode material
The preparation method of material, comprising the following steps:
(1) lithium-rich manganese-based presoma mixed with lithium source, ground, calcined in air atmosphere, it is cooling to get to it is lithium-rich manganese-based just
Pole material；
(2) it disperses lithium-rich manganese-based anode material obtained by step (1) in anhydrous organic solvent I, stirs evenly；Add titanium
Source stirs evenly, and obtains black suspension a；
(3) it is calculated with the amount of the substance of the titanium in titanium source in step (2), by the ratio of the ratio between the amount of substance Li:Ti:P=1:2:3
Example weighs lithium source and phosphorus source, and lithium source and phosphorus source are added in anhydrous organic solvent II, stirs evenly, obtains mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2) and is reacted, oil bath is evaporated, and is obtained dry
Gel powder；
(5) dry gel powder obtained by step (4) is placed under reducing atmosphere and is calcined,.
Preferably, in step (1), lithium-rich manganese-based presoma is Mn0.674Ni0.163Co0.163CO3、Mn0.674Ni0.163Co0.163
(OH)2、Mn4/6Ni1/6Co1/6CO3、 Mn4/6Ni1/6Co1/6 (OH)2、Mn0.75Ni0.25 (OH)2、Mn0.75Ni0.25CO3In at least
It is a kind of.
Preferably, in step (1), the lithium source is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide.
Its hydrate can also be used in lithium source.
Preferably, in step (1), calcining is carried out in two steps, first in 400 ~ 550 DEG C of calcining 4-8h, then at 700 ~ 1100 DEG C
Calcine 8 ~ 20h.
Preferably, in step (1), in lithium source the amount of the substance of contained lithium in lithium-rich manganese-based presoma Ni, Co, Mn it is total
The ratio of the amount of substance is 1.5 ~ 1.6 ︰ 1.
Preferably, in step (1), milling time is 0.5 ~ 4h；Milling time is too short, and mixing is uneven, and milling time is too
Long, material air is long, has an impact to material property.
Preferably, in step (2), the titanium source is one of butyl titanate, titanium tetrachloride, isopropyl titanate or several
Kind.
Preferably, in step (2), the anhydrous organic solvent I is one in anhydrous methanol, dehydrated alcohol or anhydrous propyl alcohol
Kind is several.
Preferably, in step (2), the molar ratio of the titanium elements in lithium-rich manganese-based anode material and titanium source be 337.8 ︰ 10 ~
40。
Preferably, in step (3), the lithium source is lithium acetate, Lithium acetate dihydrate, lithium hydroxide, lithium carbonate or lithium nitrate
One or more of.
Preferably, in step (3), phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid.
Preferably, in step (3), the anhydrous organic solvent II is in anhydrous methanol, dehydrated alcohol or anhydrous propyl alcohol
It is one or more of.
Preferably, in step (4), reaction temperature is 50 ~ 80 DEG C, and the reaction time is 2 ~ 10 hours.
Preferably, in step (4), oil bath evaporated temperature is 50~80 DEG C.
Preferably, in step (4), a length of 10~40h when being evaporated.
Preferably, in step (5), the temperature of calcining is 400~950 DEG C.
Preferably, in step (5), the time of calcining is 6~30h.
Preferably, in step (5), the reducing atmosphere is the gaseous mixture of helium, nitrogen or argon gas or argon gas and hydrogen
Atmosphere.
Gained titanium phosphate lithium coats in lithium-rich manganese-based anode material, the molar ratio of lithium-rich manganese-based anode material and titanium phosphate lithium
For 100:0.5 ~ 10.
The titanium phosphate lithium that first passage sol-gal process of the present invention prepares In-situ reaction coats rich lithium manganese anode material.Wherein
Composite material includes three parts: kernel is lithium-rich manganese-based anode material, and shell is 3-D nano, structure titanium phosphate lithium material, with
And two-phase even transition gradient layer.Titanium phosphate lithium can not only alleviate the rupture and stratiform-of second particle as surface coating layer
Spinelle phase transformation, and anode-electrolyte interface dynamics can be improved, keep titanium phosphate lithium cladding lithium-rich manganese-based anode material compound
Material has excellent cyclical stability.
Compared with prior art, the present invention has the beneficial effect that:
(1) present invention has the lithium-rich manganese-based composite material of in-stiu coating titanium phosphate lithium by sol-gal process synthesis.It is wherein multiple
Condensation material includes three parts: kernel is lithium-rich manganese-based anode material, and shell is 3-D nano, structure titanium phosphate lithium material, and
Two-phase even transition gradient layer.
(2) titanium phosphate lithium can not only alleviate the rupture and layered-spinel phase transformation of second particle as surface coating layer,
And anode-electrolyte interface dynamics can be improved, there is titanium phosphate lithium cladding lithium-rich manganese-based anode material composite material excellent
Different cyclical stability.
(3) titanium phosphate lithium ionic conductivity with higher, facilitates Li+Quick deintercalation, be effectively improved lithium-rich manganese-based
The defects of materials conductive ability is poor, high rate performance is bad.
Detailed description of the invention
Fig. 1 is the SEM figure that titanium phosphate lithium prepared by the embodiment of the present invention 1 coats lithium-rich manganese-based anode material；
Fig. 2 is the SEM figure of the lithium-rich manganese-based anode material of comparative example 1 of the present invention preparation；
Fig. 3 is the TEM figure that titanium phosphate lithium prepared by the embodiment of the present invention 1 coats lithium-rich manganese-based anode material；
Fig. 4 is titanium phosphate lithium cladding lithium-rich manganese-based anode material and 1 lithium-rich manganese-based anode of comparative example prepared by the embodiment of the present invention 1
The button cell of material assembling cycle performance figure under 0.2C discharge-rate；
Fig. 5 is titanium phosphate lithium cladding lithium-rich manganese-based anode material filling after recycling different circle numbers prepared by the embodiment of the present invention 1
Discharge curve；
Fig. 6 is the structural schematic diagram of the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the present invention.
Specific embodiment
In order to be further understood to the present invention, the preferred embodiment of the invention is made below with reference to embodiment further
Description, protection scope of the present invention is not limited to the examples, and protection scope of the present invention is determined by claims
It is fixed.
Embodiment 1
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol4/6Ni1/6Co1/6CO3With 0.1302molLiOH ﹒ H2O carries out hand mill mixing
(crossing lithium amount is 5%), milling time 2h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, first 500 DEG C of pre-sinterings
6h, then in 900 DEG C of sintering 10h, heating rate is 5 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode
Material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
(2) lithium-rich manganese-based anode material (337.8mmol) obtained by 3.0000g step (1) is dissolved in 90mLCH3CH2In OH, stirring
Uniformly, 20.0000mmol C is added16H36O4Ti(density is 0.9660g/cm3), it stirs evenly, obtains black suspension a；
(3) by 30.0000mmolH3PO4、10.0000mmol CH3COOLi·2H2O is dissolved in 10mLCH3CH2In OH, stirring is equal
It is even, obtain mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2), stirring is sealed at 55 DEG C
3h is reacted, that is, has uniform gel to be precipitated；Wet gel is steamed to 20h in 75 DEG C of oil bath pan to get dry gel powder；
(5) dry gel powder obtained by step (4) is placed under argon atmosphere, in 700 DEG C, is sintered 5h to get titanium phosphate lithium and coats richness
Lithium manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@ 1%LiTi2(PO4)3。
The assembling of battery: weighing the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.4000g embodiment of the present invention,
0.0500g conductive carbon black is added and makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in after mixing
Positive plate is made on aluminium foil, using metal lithium sheet as cathode in vacuum glove box, using Celgard2300 as diaphragm, 1mol/L
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
As shown in figure 4, the battery assembled in 2.0~4.8V voltage range, recycles 25 under 0.2C charge-discharge magnification
Circle, capacity retention ratio 86.7%.
Embodiment 2
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.1680mol4/6Ni1/6Co1/6CO3With 0.1310molLi2CO3Carry out hand mill mixing (mistake
Lithium amount is 6%) milling time 3h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, is first pre-sintered at 500 DEG C
6h, then in 950 DEG C of sintering 15h, heating rate is 5 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode
Material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
(2) lithium-rich manganese-based anode material obtained by 1.5000g(168.9mmol) step (1) is dissolved in 90mLCH3CH2In OH, stirring
Uniformly, 20.0000mmol C is added16H36O4Ti(density is 0.9660g/cm3), it stirs evenly, obtains black suspension a；
(3) by 30.0000mmolH3PO4、10.0000mmol CH3COOLi·2H2O is dissolved in 10mlCH3CH2In OH, stirring is equal
It is even, obtain mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2) and is reacted, sealed at 55 DEG C
It is stirred to react 3h, that is, has uniform gel to be precipitated, wet gel is evaporated for 24 hours in 75 DEG C of oil bath pan to get dry gel powder.
(5) dry gel powder obtained by step (4) is placed under argon atmosphere, in 750 DEG C, is sintered 5h to get titanium phosphate lithium packet
Cover lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@ 2%LiTi2(PO4)3。
The assembling of battery: weighing the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.8000g embodiment of the present invention,
0.1000g conductive carbon black is added and makees conductive agent and 0.1000g PVDF(Kynoar) make binder, it is coated in after mixing
Positive plate is made on aluminium foil, using metal lithium sheet as cathode in vacuum glove box, using Celgard2300 as diaphragm, 1mol/L
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles in 2.0~4.8V voltage range under 0.2C charge-discharge magnification, and capacity is protected
Holdup is 86.1%.
Embodiment 3
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.1680mol4/6Ni1/6Co1/6CO3With 0.1302molLi2CO3Carry out hand mill mixing (mistake
Lithium amount is 5%) milling time 2h；Raw material is put into crucible, Muffle furnace is placed in, first in 500 DEG C of pre-sintering 5h, then at 900 DEG C
It is sintered 12h, heating rate is 3 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode material
0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
(2) lithium-rich manganese-based anode material (337.8mmol) obtained by 3.0000g step (1) is dissolved in 40mLCH3CH2In OH, stirring
Uniformly, 20.0000mmol C is added16H36O4Ti(density is 0.9660g/cm3), it stirs evenly, obtains black suspension a；
(3) by 30.0000mmolH3PO4、10.0000mmol CH3COOLi·2H2O is dissolved in 5mlCH3CH2In OH, stir evenly,
Obtain mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2) and is reacted, sealed at 55 DEG C
It is stirred to react 3h, that is, has uniform gel to be precipitated；Wet gel is steamed to 25h in 85 DEG C of oil bath pan to get dry gel powder；
(5) dry gel powder obtained by step (4) is placed under argon atmosphere, in 700 DEG C, is sintered 7h to get titanium phosphate lithium and coats richness
Lithium manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@ 1%LiTi2(PO4)3。
The assembling of battery: weighing the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.4000g embodiment of the present invention,
0.0500g conductive carbon black is added and makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in after mixing
Positive plate is made on aluminium foil, is diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles, conservation rate in 2.0~4.8V voltage range under 0.2C charge-discharge magnification
It is 85.2%.
Embodiment 4
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol0.674Ni0.163Co0.163CO3With 0.1293molLi (NO3) carry out hand mill
Mixing (crossing lithium amount is 4%), milling time 2h；Raw material is put into crucible, is placed in Muffle furnace, first in 500 DEG C of pre-sintering 5h, then
In 900 DEG C of sintering 12h, heating rate is 5 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode material
0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
(2) lithium-rich manganese-based anode material (337.8mmol) obtained by 1.0000g step (1) is dissolved in 40mLCH3CH2In OH, stirring
Uniformly, 20.0000mmolTiCl is added4, stir evenly, obtain black suspension a；
(3) by 30.0000mmol (NH4)2H(PO4), 10.0000mmolLiOH ﹒ H2O is dissolved in 5mlCH3CH2In OH, stirring is equal
It is even, obtain mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2) and is reacted, sealed at 55 DEG C
It is stirred to react 3h, that is, has uniform gel to be precipitated；Wet gel is steamed to 22h in 85 DEG C of oil bath pan to get dry gel powder；
(5) dry gel powder obtained by step (4) is placed in the mixed atmosphere of argon gas and hydrogen (argon gas and hydrogen volume ratio is 1 ratio
1), in 700 DEG C, 8h is sintered to get titanium phosphate lithium and coats lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/ 3Mn1/3)O2@ 3%LiTi2(PO4)3。
The assembling of battery: weighing the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.4000g embodiment of the present invention,
0.0500g conductive carbon black is added and makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in after mixing
Positive plate is made on aluminium foil, is diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles, conservation rate in 2.0~4.8V voltage range under 0.2C charge-discharge magnification
It is 84.8%.
Embodiment 5
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol0.674Ni0.163Co0.163(OH)2With 0.1285molCH3COOLi carries out hand
Mill mixing (crossing lithium amount is 3%), milling time 2h；Raw material is put into crucible, is placed in Muffle furnace, first in 500 DEG C of pre-sintering 5h, so
Afterwards in 900 DEG C of sintering 10h, heating rate is 5 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode material
0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
(2) lithium-rich manganese-based anode material (337.8mmol) obtained by 3.0000g step (1) is dissolved in 40mLCHCOCH3In, stirring
Uniformly, 20.0000mmolTi { OCH (CH3) 2 } 4 is added, stirs evenly, obtains black suspension a；
(3) by 30.0000mmol (NH4)2H(PO4)、5.0000mmol Li2CO3It is dissolved in 5mlCHCOCH3In, it stirs evenly, obtains
Mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2) and is reacted, sealed at 55 DEG C
It is stirred to react 3h, that is, has uniform gel to be precipitated；Wet gel is steamed to 20h in 85 DEG C of oil bath pan to get dry gel powder；(5)
Dry gel powder obtained by step (4) is placed under helium atmosphere, in 750 DEG C, it is lithium-rich manganese-based just to get titanium phosphate lithium cladding to be sintered 5h
Pole material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@ 1%LiTi2(PO4)3。
The assembling of battery: the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.4000g embodiment of the present invention is weighed, is added
Enter 0.0500g conductive carbon black and make conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in aluminium after mixing
Positive plate is made on foil, is diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles in 2.0~4.8V voltage range under 0.2C charge-discharge magnification, and conservation rate is
85.9%。
Embodiment 6
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol0.75Ni0.25 (OH)2With 0.0659mol Li2CO3Carry out hand mill mixing
(crossing lithium amount is 7%), milling time 3h；Raw material is put into crucible, Muffle furnace is placed in, first in 500 DEG C of pre-sintering 5h, then 900
DEG C sintering 12h, heating rate is 5 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode material
0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
(2) lithium-rich manganese-based anode material (337.8mmol) obtained by 1.0000g step (1) is dissolved in 40mLCH3CH2In OH, stirring
Uniformly, 20.0000mmol Ti { OCH (CH is added3)2}4, stir evenly, obtain black suspension a；
(3) by 30.0000mmol (NH4)H2(PO4)、10.0000mmol LiNO3It is dissolved in 5mlCH3CH2It in OH, stirs evenly, obtains
Mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2) and is reacted, sealed at 55 DEG C
It is stirred to react 3h, that is, has uniform gel to be precipitated；Wet gel is steamed to 25h in 85 DEG C of oil bath pan to get dry gel powder；
(5) dry gel powder obtained by step (4) is placed under nitrogen atmosphere, in 700 DEG C, is sintered 10h to get titanium phosphate lithium cladding
Lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@ 3%LiTi2(PO4)3。
The assembling of battery: the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.4000g embodiment of the present invention is weighed, is added
Enter 0.0500g conductive carbon black and make conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in aluminium after mixing
Positive plate is made on foil, is diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles in 2.0~4.8V voltage range under 0.2C charge-discharge magnification, and conservation rate is
86.7%。
Comparative example 1
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol4/6Ni1/6Co1/6CO3With 0.1302molLiOH ﹒ H2O carries out hand mill mixing
(crossing lithium amount is 5%), milling time 2h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, first 500 DEG C of pre-sinterings
6h, then in 900 DEG C of sintering 10h, heating rate is 5 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode
Material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
The assembling of battery: the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.4000g embodiment of the present invention is weighed, is added
0.0500g conductive carbon black makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles in 2.0~4.8V voltage range under 0.2C charge-discharge magnification, and capacity is kept
Rate is 66.7%.
Comparative example 2
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.1680mol4/6Ni1/6Co1/6CO3With 0.1310molLi2CO3Carry out hand mill mixing (mistake
Lithium amount is 6%) milling time 3h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, is first pre-sintered at 500 DEG C
6h, then in 950 DEG C of sintering 15h, heating rate is 5 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode
Material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
The assembling of battery: the cladding lithium-rich manganese-based anode material of titanium phosphate lithium obtained by the 0.4000g embodiment of the present invention is weighed, is added
0.0500g conductive carbon black makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in aluminium foil after mixing
On positive plate is made, using metal lithium sheet as cathode in vacuum glove box, using Celgard2300 as diaphragm, 1mol/L LiPF6/
EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles in 2.0~4.8V voltage range under 0.2C charge-discharge magnification, and capacity is kept
Rate is 61.9%.
Comparative example 3
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.1680mol4/6Ni1/6Co1/6CO3With 0.1302molLi2CO3Carry out hand mill mixing (mistake
Lithium amount is 5%) milling time 2h；Raw material is put into crucible, Muffle furnace is placed in, first in 500 DEG C of pre-sintering 5h, then at 900 DEG C
It is sintered 12h, heating rate is 3 DEG C/min, until furnace temperature is cooled to after room temperature to get lithium-rich manganese-based anode material
0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2；
The assembling of battery: the cladding nickel-cobalt-manganternary ternary anode material of titanium phosphate lithium obtained by the 0.8000g embodiment of the present invention is weighed, is added
0.1000g conductive carbon black makees conductive agent and 0.1000g PVDF(Kynoar) make binder, it is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled recycles 25 circles in 2.0~4.8V voltage range under 0.2C charge-discharge magnification, and conservation rate is
65.7%。
Claims (9)
1. a kind of preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material, which comprises the following steps:
(1) lithium-rich manganese-based presoma mixed with lithium source, ground, calcined in air atmosphere, it is cooling to get to it is lithium-rich manganese-based just
Pole material；
(2) it disperses lithium-rich manganese-based anode material obtained by step (1) in anhydrous organic solvent I, stirs evenly；Add titanium
Source stirs evenly, and obtains black suspension a；
(3) it is calculated with the amount of the substance of the titanium in titanium source in step (2), by the ratio of the ratio between the amount of substance Li:Ti:P=1:2:3
Example weighs lithium source and phosphorus source, and lithium source and phosphorus source are added in anhydrous organic solvent II, stirs evenly, obtains mixing suspension b；
(4) mixing suspension b obtained by step (3) is added in black suspension a obtained by step (2) and is reacted, oil bath is evaporated, and is obtained dry
Gel powder；
(5) dry gel powder obtained by step (4) is placed under reducing atmosphere and is calcined,.
2. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1, which is characterized in that step
Suddenly in (1), lithium-rich manganese-based presoma is Mn0.674Ni0.163Co0.163CO3、Mn0.674Ni0.163Co0.163(OH)2、Mn4/6Ni1/6Co1/ 6CO3、 Mn4/6Ni1/6Co1/6 (OH)2、Mn0.75Ni0.25 (OH)2、Mn0.75Ni0.25CO3At least one of；The lithium source is carbon
At least one of sour lithium, lithium nitrate, lithium acetate, lithium hydroxide or its hydrate.
3. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1 or 2, feature exist
In in step (1), calcining is carried out in two steps, first in 400 ~ 550 DEG C of 4 ~ 8h of calcining, then in 700 ~ 1100 DEG C of 8 ~ 20h of calcining；Lithium
The ratio of the amount of the total material of Ni, Co, Mn is 1.5 ~ 1.6 ︰ 1 in the amount of the substance of contained lithium and lithium-rich manganese-based presoma in source；
Milling time is 0.5 ~ 4h.
4. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1 or 2, feature exist
In in step (2), the titanium source is one or more of butyl titanate, titanium tetrachloride, isopropyl titanate；Described anhydrous have
Solvent I is one or more of anhydrous methanol, dehydrated alcohol or anhydrous propyl alcohol；In lithium-rich manganese-based anode material and titanium source
The molar ratio of titanium elements is 337.8 ︰ 10 ~ 40.
5. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1 or 2, feature exist
In in step (3), the lithium source is one of lithium acetate, Lithium acetate dihydrate, lithium hydroxide, lithium carbonate or lithium nitrate or several
Kind；Phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid；The anhydrous organic solvent II is nothing
One or more of water methanol, dehydrated alcohol or anhydrous propyl alcohol.
6. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1 or 2, feature exist
In in step (4), reaction temperature is 50 ~ 80 DEG C, and the reaction time is 2 ~ 10 hours；Oil bath evaporated temperature is 50~80 DEG C；It is evaporated
10~40h of Shi Changwei.
7. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1 or 2, feature exist
In, it is preferred that in step (5), the temperature of calcining is 400~950 DEG C.
8. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1 or 2, feature exist
In in step (5), the time of calcining is 6~30h.
9. the preparation method of titanium phosphate lithium cladding lithium-rich manganese-based anode material according to claim 1 or 2, feature exist
In in step (5), the reducing atmosphere is the mixed atmosphere of helium, nitrogen or argon gas or argon gas and hydrogen.
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| CN110957478A (en) * | 2019-11-12 | 2020-04-03 | 中南大学 | Titanium yttrium lithium phosphate modified high-nickel cathode composite material and preparation method thereof |
| CN111987297A (en) * | 2020-08-26 | 2020-11-24 | 北京理工大学重庆创新中心 | Lithium-rich manganese-based positive electrode material with aluminum-doped surface and coated with lithium aluminum titanium phosphate and preparation method thereof |
| CN111987311A (en) * | 2020-08-12 | 2020-11-24 | 中南大学 | Titanium indium lithium phosphate modified positive electrode material and preparation method thereof |
| CN112002898A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | Titanium lanthanum lithium phosphate coated and modified ternary cathode material and preparation method thereof |
| CN113451569A (en) * | 2021-06-28 | 2021-09-28 | 福州大学 | LATP-coated high-voltage spinel LNMO positive electrode material and preparation method thereof |
| WO2021196732A1 (en) * | 2020-03-31 | 2021-10-07 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method therefor, lithium-ion battery, and electric vehicle |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110957478A (en) * | 2019-11-12 | 2020-04-03 | 中南大学 | Titanium yttrium lithium phosphate modified high-nickel cathode composite material and preparation method thereof |
| CN110957478B (en) * | 2019-11-12 | 2021-03-16 | 中南大学 | Titanium yttrium lithium phosphate modified high-nickel cathode composite material and preparation method thereof |
| WO2021196732A1 (en) * | 2020-03-31 | 2021-10-07 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method therefor, lithium-ion battery, and electric vehicle |
| CN111987311A (en) * | 2020-08-12 | 2020-11-24 | 中南大学 | Titanium indium lithium phosphate modified positive electrode material and preparation method thereof |
| CN112002898A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | Titanium lanthanum lithium phosphate coated and modified ternary cathode material and preparation method thereof |
| CN111987297A (en) * | 2020-08-26 | 2020-11-24 | 北京理工大学重庆创新中心 | Lithium-rich manganese-based positive electrode material with aluminum-doped surface and coated with lithium aluminum titanium phosphate and preparation method thereof |
| CN113451569A (en) * | 2021-06-28 | 2021-09-28 | 福州大学 | LATP-coated high-voltage spinel LNMO positive electrode material and preparation method thereof |
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