CN107591529A - A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof - Google Patents
A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof Download PDFInfo
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Abstract
A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof, in the material, the weight/mass percentage composition of the titanium phosphate lithium is 1~10wt%, forms 1~2nm of thickness uniform clad；For 5~15 μm of spheric granules of particle diameter.Methods described is：（1）Titanium source is disperseed, stirred, water is added dropwise, stirring, obtains milky suspension；（2）Lithium source and phosphorus source are added, stirring, obtains mixing suspension；（3）Hydro-thermal reaction, centrifuge washing, drying, obtain titanium phosphate lithium presoma；（4）Ground with nickel-cobalt-manganternary ternary anode material, sintering,.The battery of material assembling of the present invention, under 2.5~4.3V, 0.1C, the gram volume that discharges first reaches 173.7mAh/g, and the circle of circulation 50, capacity is 168 mAh/g, and capability retention is up to 96.7%, and the electrochemical performance under big multiplying power；The inventive method is simple, and cost is low, suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of positive electrode and preparation method thereof, and in particular to a kind of titanium phosphate lithium coats nickel-cobalt-manganese ternary
Positive electrode and preparation method thereof.
Background technology
Nickel-cobalt-manganternary ternary anode material is big due to having the advantages that high-energy-density, relatively low cost, theoretical energy density,
Become the main flow positive electrode of 21 century commercial Li-ion batteries positive electrode application.The theory of nickel-cobalt-manganternary ternary anode material
Specific capacity is 278mAh/g, voltage platform 3.6V so that nickel-cobalt-manganternary ternary anode material has high energy density.But
It is, because the relatively low lithium ion diffusion coefficient of the nickel-cobalt-manganternary ternary anode material of stratiform and perveance cause times of material
Rate performance still has much room for improvement.On the other hand, nickel-cobalt-manganternary ternary anode material causes nickel-cobalt-manganese ternary positive pole during removal lithium embedded
Material occurs from layer structure to the phase transformation of fused salt structure, deteriorates the cycle performance of nickel-cobalt-manganternary ternary anode material.
CN106025254 A disclose a kind of surface coating modification method of nickel lithium manganate cathode material, including following step
Suddenly：（1）Mixture is matched according to following mass percent：Lithium salts 0.1~5%, alkyl titanate 3~7%, nickel ion doped 90~
95%；First lithium salts and tetrabutyl titanate are dissolved in ethanol solution, then add nickel ion doped, stirs lower heating, a constant temperature
Reacted under degree, then solvent flashing, until being evaporated, obtain the nickel ion doped of lithium salts-coated by titanium dioxide；（2）According to matter
Measure ratio 0.1:99.9~7:93, by ammonium dihydrogen phosphate and step（1）The nickel ion doped mixing of lithium salts-coated by titanium dioxide of preparation
It is scattered in deionized water, mass percent is 10~20%, stirring heating, is reacted, then dried again molten under certain temperature
Liquid, obtain lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped；（3）By step（2）Obtained lithium salts-titanium dioxide
Titanium-ammonium dihydrogen phosphate compound coating nickel ion doped is put into alumina crucible, and 650~750 DEG C of progress are heated under air atmosphere
It is heat-treated for the first time, is incubated 3~8 hours, then cools to 400~600 DEG C and be heat-treated for the second time, be incubated 3~8 hours,
After being cooled to room temperature, positive electrode product is obtained.But its preparation method is complicated, and resulting materials putting under 0.1C multiplying powers
Capacitance is only 135mAh/g, and chemical property is bad.
CN101807696A discloses a kind of preparation method of titanium phosphate lithium material, comprises the following steps：1）Raw material forerunner
The preparation and mixing of body：By lithium-containing compound, titanium dioxide and phosphorus-containing compound by lithium, titanium, phosphorus stoichiometric proportion 1~
1.05:2:3 ratio weighs；By ball material mass ratio 5:1 batch mixing is on planetary ball mill with 150~300r/min rotating speed ball
Mill 6~24 hours；2）High-temperature roasting is handled：By step 1）The powdery precursor of gained constant temperature at a temperature of 800 DEG C~1000 DEG C
Roasting 8~20 hours, natural cooling obtain the titanium phosphate lithium salts of white；3）Secondary ball milling：By step 2）The titanium phosphate lithium of gained
Salt and organic matter in mass ratio 1:0.2~0.02 weighs mixing；By ball material mass ratio 5:1 batch mixing on planetary ball mill with
150~300r/min rotating speed ball milling obtains the presoma of powdery in 6~24 hours；4）After baking：Secondary ball milling is obtained
Powdery precursor is put into the high temperature furnace for being connected with inert atmosphere, and throughput is 10~60mL/min, at a temperature of 500~750 DEG C
Constant temperature calcining 6~12 hours；Titanium phosphate lithium-carbon material is obtained after natural cooling.But its preparation method is complicated, and gained
Discharge capacity of the material under 0.1C and 1C multiplying powers is only 131mAh/g and 91.3mAh/g, and chemical property is bad.
CN106744776A discloses a kind of preparation method of pure phase titanium phosphate lithium anode material, comprises the following steps：（1）
Acetone and ethanol are added in reactor, magnetic agitation is sufficiently mixed to obtain uniform mixed solution；（2）Metatitanic acid fourth vinegar is instilled
Step（1）In gained mixed solution, stir 10~20 minutes, obtain light yellow transparent solution；（3）To step（2）What is obtained is light
Yellow transparent solution instills deionized water dropwise, and magnetic agitation obtains white suspension in 2~4 hours；（4）To step（3）Gained
Ammonium dihydrogen phosphate and acetic acid dihydrate lithium are added in white suspension, is reacted 2~5 hours under magnetic agitation and obtains white suspension
Liquid；（5）By step（4）Gained white suspension is placed in autoclave, and temperature control is reacted 4 hours at 150~220 DEG C
More than；（6）By step（5）Gained white depositions and golden yellow supernatant stir, and then add absolute ethyl alcohol, obtain Huang
Color suspension；（7）By step（6）Gained yellow suspension moves into normal pressure reactor, and 60~100 DEG C are stirred more than 5 hours, are obtained
Yellow presoma；（8）By step（7）Gained yellow presoma, which is placed in tube furnace, to be calcined, that is, obtains titanium phosphate lithium.But its
Method is cumbersome, and resulting materials are under 0.5C, first discharge specific capacity only 135mAh/g, and chemical property is bad.
CN104779392 A disclose a kind of titanium phosphate lithium doping lithium titanate electrode material and its preparation method, including following step
Suddenly：1）Lithium-containing compound, titanium phosphate lithium and titanium source are well mixed to obtain presoma, wherein, lithium-containing compound, mole of titanium phosphate lithium
Than for 21:1~5, Li are 0.6~1 with Ti mol ratios:2）By step 1）The presoma of gained at 600~1100 DEG C, air or
Under inert atmosphere, it is heat-treated 1~72 hour, titanium phosphate lithium doping lithium titanate electrode material is made.But resulting materials 1C holds
Amount is only 148 every gram of MAHs, and chemical property is bad.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of times forthright
Can, particularly big good rate capability, the excellent titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material of cycle performance.
Further technical problems to be solved of the invention are to overcome drawbacks described above existing for prior art, there is provided one kind system
Standby flow is simple, and cost is low, and the preparation method of nickel-cobalt-manganternary ternary anode material is coated suitable for the titanium phosphate lithium of industrialized production.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of titanium phosphate lithium cladding nickel-cobalt-manganese ternary is just
Pole material, the weight/mass percentage composition of the titanium phosphate lithium is 1~10wt%, and titanium phosphate lithium forms 1~2nm of thickness with unformed shape
Uniform clad；The positive electrode is the spheric granules of 5~15 μm of particle diameter.
Technical scheme is used by the present invention further solves its technical problem：A kind of titanium phosphate lithium coats nickel cobalt manganese three
The preparation method of first positive electrode, comprises the following steps：
（1）Titanium source is dispersed in anhydrous organic solvent, stirs to titanium source and dissolves transparent homogeneous solution, then water is added dropwise, is stirred
Mix so that titanium source hydrolysis, obtains milky suspension；
（2）In step（1）In gained milky suspension, by n（Li:Ti:P）=1:2:3 ratio adds lithium source and phosphorus source, holds
It is continuous to be stirred until homogeneous, obtain mixing suspension；
（3）By step（2）Gained mixing suspension is transferred in reactor, is carried out hydro-thermal reaction, centrifuge washing precipitation, is dried,
Obtain titanium phosphate lithium presoma；
（4）By step（3）Gained titanium phosphate lithium presoma is ground with nickel-cobalt-manganternary ternary anode material, is burnt in air atmosphere
Knot, obtain titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material.
Preferably, step（1）In, the volume ratio of the titanium source and anhydrous organic solvent is 1:2~10（More preferably 1:3~
8）.
Preferably, step（1）In, the titanium source be one kind in butyl titanate, titanium tetrachloride or isopropyl titanate etc. or
It is several.It is further preferred that the titanium source is butyl titanate.
Preferably, step（1）In, the anhydrous organic solvent is in absolute methanol, absolute ethyl alcohol or anhydrous propyl alcohol etc.
It is one or more of.
Preferably, step（1）In, the water of the dropwise addition and the volume ratio of titanium source are 0.5~8.0:1（More preferably 1~5:
1）.
Preferably, step（1）In, the speed of the dropwise addition is 10~30mL/min.Under the rate of addition, it can guarantee that
The uniform hydrolysis of titanium source, reduce because hydrolyze it is uneven and caused by disperse it is uneven the problem of.
Preferably, step（1）In, the mixing time before dropwise addition water is 20~40min.The purpose of stirring is in order that titanium
Source is dispersed in organic solvent, scattered uneven if the time is too short, if overlong time, increases energy consumption.
Preferably, step（1）In, the mixing time after dropwise addition water is 2~4h.Water is can ensure that under the mixing time
Solution is complete.
Preferably, step（2）In, the lithium source is the one or more in lithium hydroxide, lithium carbonate or lithium nitrate etc..
Preferably, step（2）In, phosphorus source is one kind or several in ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid etc.
Kind.
Preferably, step（2）In, the time of the stirring is 20~40min.Lithium source and phosphorus can be caused under the time
Source is dispersed in a solvent.
Preferably, step（3）In, the temperature of the hydro-thermal reaction is 150~300 DEG C（More preferably 180~250 DEG C）, instead
The time answered is 6~12h.
Preferably, step（3）In, the rotating speed of the centrifuge washing is 5000~10000 turns/min, the time is 5~
10min。
Preferably, step（4）In, the mass ratio of the titanium phosphate lithium presoma and nickel-cobalt-manganternary ternary anode material is 1:5
~50（More preferably 1:8~40）.
Preferably, step（4）In, the mol ratio of nickel cobalt manganese is 6 in the nickel-cobalt-manganternary ternary anode material:2:2、5:2:3、
4:2:2 or 1:1:1.
Preferably, step（4）In, the grinding refers to add in titanium phosphate lithium presoma and nickel-cobalt-manganternary ternary anode material
Enter equivalent to 0.5~1.5 times of its quality（More preferably 0.8~1.2 times）Ethanol, 0.5~4.0h of wet-milling.
Preferably, step（4）In, the temperature of the sintering is 400~950 DEG C（More preferably 700~900 DEG C）, sintering
Time is 6~30h（More preferably 12~24h）.
Titanium phosphate lithium of the present invention coats nickel-cobalt-manganternary ternary anode material by using with three-dimensional lithium ion diffusion admittance
Titanium phosphate lithium carries out coating modification to nickel-cobalt-manganternary ternary anode material, improves the cycle performance and high rate performance of material.Although
The theoretical gram volume of titanium phosphate lithium is only 138mAh/g, far away from the theoretical gram volume 274mAh/g of tertiary cathode material, still
Due to the structural advantage of titanium phosphate lithium, in the clad as ternary material, can be provided for ternary material more lithiums from
Sub- transmission channels, and titanium phosphate lithium is coated on ternary surface, prevents the side reaction of electrolyte and ternary material, enhances material
Stability.It may be said that on the one hand the high power capacity of ternary material in itself can have been given play to by coating ternary material using titanium phosphate lithium
Advantage, on the other hand also utilize titanium phosphate lithium Stability Analysis of Structures and with advantages such as three-dimensional lithium ion tunnels.
Beneficial effects of the present invention are as follows：
（1）In titanium phosphate lithium of the present invention cladding nickel-cobalt-manganternary ternary anode material, titanium phosphate lithium with unformed shape formed thickness 1~
2nm uniform clad, the positive electrode are the spheric granules of 5~15 μm of particle diameter；
（2）Titanium phosphate lithium of the present invention cladding nickel-cobalt-manganternary ternary anode material is assembled into battery, it is first under 2.5~4.3V, 0.1C
Secondary electric discharge gram volume reaches 173.7mAh/g, and the circle of circulation 50, capacity is 168 mAh/g, and capability retention is up to 96.7%；And respectively
Under 0.5C, 1C, 2C, 5C multiplying power, first discharge capacity be respectively 168mAh/g, 164.5 mAh/g, 159.9 mAh/g,
153.5mAh/g, illustrate that titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material of the present invention has preferable cyclical stability and big times
Rate discharge performance；
（3）The inventive method preparation flow is simple, and cost is low, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the SEM figures of the gained titanium phosphate lithium of the embodiment of the present invention 1 cladding nickel-cobalt-manganternary ternary anode material；
Fig. 2 is the TEM figures of the gained titanium phosphate lithium of the embodiment of the present invention 1 cladding nickel-cobalt-manganternary ternary anode material；
Fig. 3 is the XRD of the gained titanium phosphate lithium of the embodiment of the present invention 1 cladding nickel-cobalt-manganternary ternary anode material；
Fig. 4 is the titanium phosphate lithium of the embodiment of the present invention 1 cladding nickel-cobalt-manganternary ternary anode material and the nickel-cobalt-manganese ternary positive pole material of comparative example 1
Expect the cyclic curve comparison diagram under 0.1C discharge-rates；
Fig. 5 is the titanium phosphate lithium of the embodiment of the present invention 2 cladding nickel-cobalt-manganternary ternary anode material and the nickel-cobalt-manganese ternary positive pole material of comparative example 1
Expect the first charge-discharge curve comparison figure under 0.1C charge-discharge magnifications；
Fig. 6 is the SEM figures of the gained titanium phosphate lithium of the embodiment of the present invention 3 cladding nickel-cobalt-manganternary ternary anode material；
Fig. 7 is the titanium phosphate lithium of the embodiment of the present invention 3 cladding nickel-cobalt-manganternary ternary anode material and the nickel-cobalt-manganese ternary positive pole material of comparative example 1
Expect the discharge curve comparison diagram under the conditions of 0.1C, 0.5C, 1C, 2C, 5C multiplying power.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
The model of nickle cobalt lithium manganate tertiary cathode material is 622 used in the embodiment of the present invention（Ni:Co:Mn=6:2:
2）, it is purchased from Qingdao Zhejiang Pa Wa limited companies；Chemical reagent used in the embodiment of the present invention, unless otherwise specified,
Obtained by routine business approach.
Embodiment 1
A kind of titanium phosphate lithium coats nickel-cobalt-manganternary ternary anode material：
The weight/mass percentage composition of the titanium phosphate lithium is 3wt%, and titanium phosphate lithium forms thickness 1.2nm uniform bag with unformed shape
Coating；The positive electrode is the spheric granules of 8~12 μm of particle diameter.
As shown in figure 1, titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material is 8~12 μm of particle diameter obtained by the embodiment of the present invention
Spheric granules, there is titanium phosphate lithium on surface with unformed morphogenetic clad.
As shown in Fig. 2 titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material surface phosphoric acid titanium lithium obtained by the embodiment of the present invention
The thickness of clad is 1.2nm.
As shown in figure 3, contain titanium phosphate in titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention
Lithium composition, and be pure phase.
A kind of preparation method of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material：
（1）By 5.2683g butyl titanates（Density is 0.966g/cm3, volume 5.45mL, Ti 15.48mmol）It is dispersed in
In 40mL absolute ethyl alcohols, stirring 30min to titanium source dissolves transparent homogeneous solution, then 10mL deionizations are added dropwise with 30mL/min
Water, stirring 3h cause titanium source to hydrolyze, obtain milky suspension；
（2）In step（1）In gained milky suspension, 0.286g lithium carbonates are added（Li is 7.74mmol）With 2.6710g phosphorus
Acid dihydride ammonium（P is 23.22mmol）, 30min is persistently stirred to uniform, obtains mixing suspension；
（3）By step（2）Gained mixing suspension is transferred in reactor, at 180 DEG C, hydro-thermal reaction 12h is carried out, in rotating speed
Under 8000 turns/min, after centrifuge washing 8min, precipitate, drying, obtain titanium phosphate lithium presoma 3g；
（4）Take 3g steps（3）Gained titanium phosphate lithium presoma is placed in mortar with 97g nickel-cobalt-manganternary ternary anode materials, is added
100mL ethanol, 0.5h is ground, in air atmosphere, at 800 DEG C, sinter 12h, obtaining titanium phosphate lithium cladding nickel-cobalt-manganese ternary just
Pole material.
The assembling of battery：Titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material obtained by the 0.4g embodiment of the present invention is weighed, is added
Enter 0.05g conductive carbon blacks and make conductive agent and 0.05g PVDF（Kynoar）Make binding agent, be coated in after well mixed on aluminium foil
Positive plate is made, is barrier film with Celgard 2300 using metal lithium sheet as negative pole in vacuum glove box, 1mol/L LiPF6/
EC:DMC（Volume ratio 1:1）For electrolyte, CR2025 button cell is assembled into.
As shown in figure 4, the battery assembled, in 2.5~4.3V voltage ranges, under 0.1C multiplying powers, discharge gram volume first
For 173.7mAh/g, after circulation 50 is enclosed, electric discharge gram volume can still reach 168mAh/g, capability retention 96.7%.
Embodiment 2
A kind of titanium phosphate lithium coats nickel-cobalt-manganternary ternary anode material：
The weight/mass percentage composition of the titanium phosphate lithium is 5wt%, and titanium phosphate lithium forms thickness 1.5nm uniform bag with unformed shape
Coating；The positive electrode is the spheric granules of 10~15 μm of particle diameter.
After testing, titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material is 10~15 μm of particle diameter obtained by the embodiment of the present invention
There is titanium phosphate lithium on spheric granules, surface with unformed morphogenetic clad.
After testing, titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material surface phosphoric acid titanium lithium cladding obtained by the embodiment of the present invention
The thickness of layer is 1.5nm.
After testing, in titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention containing titanium phosphate lithium into
Point, and be pure phase.
A kind of preparation method of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material：
（1）By 8.7805g butyl titanates（Density is 0.966g/cm3, volume 9.09mL, Ti 25.8mmol）It is dispersed in
In 30mL absolute ethyl alcohols, stirring 30min to titanium source dissolves transparent homogeneous solution, then 40mL deionizations are added dropwise with 15mL/min
Water, stirring 3h cause titanium source to hydrolyze, obtain milky suspension；
（2）In step（1）In gained milky suspension, 0.4766g lithium carbonates are added（Li is 12.9mmol）With 4.4516g phosphorus
Acid dihydride ammonium（P is 38.7mmol）, 30min is persistently stirred to uniform, obtains mixing suspension；
（3）By step（2）Gained mixing suspension is transferred in reactor, at 200 DEG C, hydro-thermal reaction 6h is carried out, in rotating speed
Under 6000 turns/min, after centrifuge washing 10min, precipitate, drying, obtain titanium phosphate lithium presoma 5g；
（4）By 5g steps（3）Gained titanium phosphate lithium presoma is placed in mortar with 95g nickel-cobalt-manganternary ternary anode materials, is added
80mL ethanol, 2h is ground, in air atmosphere, at 900 DEG C, sinter 15h, obtain titanium phosphate lithium cladding nickel-cobalt-manganese ternary positive pole material
Material.
The assembling of battery：Titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material obtained by the 0.4g embodiment of the present invention is weighed, is added
Enter 0.05g conductive carbon blacks and make conductive agent and 0.05g PVDF（Kynoar）Make binding agent, be coated in after well mixed on aluminium foil
Positive plate is made, is barrier film with Celgard 2300 using metal lithium sheet as negative pole in vacuum glove box, 1mol/L LiPF6/
EC:DMC（Volume ratio 1:1）For electrolyte, CR2025 button cell is assembled into.
As shown in figure 5, the battery assembled, in 2.5~4.3V voltage ranges, under 0.1C multiplying powers, discharge gram volume first
For 170.7mAh/g.
Embodiment 3
A kind of titanium phosphate lithium coats nickel-cobalt-manganternary ternary anode material：
The weight/mass percentage composition of the titanium phosphate lithium is 10wt%, and titanium phosphate lithium forms thickness 1.8nm uniform bag with unformed shape
Coating；The positive electrode is the spheric granules of 8~15 μm of particle diameter.
As shown in fig. 6, titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material is 8~15 μm of particle diameter obtained by the embodiment of the present invention
Spheric granules, there is titanium phosphate lithium on surface with unformed morphogenetic clad.
After testing, titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material surface phosphoric acid titanium lithium cladding obtained by the embodiment of the present invention
The thickness of layer is 1.8nm.
After testing, in titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material obtained by the embodiment of the present invention containing titanium phosphate lithium into
Point, and be pure phase.
A kind of preparation method of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material：
（1）By 17.5610g butyl titanates（Density is 0.966g/cm3, volume 18.18mL, Ti 51.6mmol）It is scattered
In 80mL anhydrous propyl alcohols, stirring 40min to titanium source dissolves transparent homogeneous solution, then with 30mL/min be added dropwise 50mL go from
Sub- water, stirring 2h cause titanium source to hydrolyze, obtain milky suspension；
（2）In step（1）In gained milky suspension, 1.7789g lithium nitrates are added（Li is 25.8mmol）And 10.2211g
Diammonium hydrogen phosphate（P is 77.4mmol）, 40min is persistently stirred to uniform, obtains mixing suspension；
（3）By step（2）Gained mixing suspension is transferred in reactor, at 180 DEG C, hydro-thermal reaction 12h is carried out, in rotating speed
Under 10000 turns/min, after centrifuge washing 6min, precipitate, drying, obtain titanium phosphate lithium presoma 10g；
（4）By 10g steps（3）Gained titanium phosphate lithium presoma is placed in mortar with 90g nickel-cobalt-manganternary ternary anode materials, is added
120mL ethanol, 4h is ground, in air atmosphere, at 900 DEG C, sinter 24h, obtain titanium phosphate lithium cladding nickel-cobalt-manganese ternary positive pole
Material.
The assembling of battery：Titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material obtained by the 0.4g embodiment of the present invention is weighed, is added
Enter 0.05g conductive carbon blacks and make conductive agent and 0.05g PVDF（Kynoar）Make binding agent, be coated in after well mixed on aluminium foil
Positive plate is made, is barrier film with Celgard 2300 using metal lithium sheet as negative pole in vacuum glove box, 1mol/L LiPF6/
EC:DMC（Volume ratio 1:1）For electrolyte, CR2025 button cell is assembled into.
As shown in fig. 7, the battery assembled is in 2.5~4.3V voltage ranges, respectively in 0.1C, 0.5C, 1C, 2C, 5C
Under multiplying power, electric discharge gram volume is 170.7mAh/g, 168mAh/g, 164.5 mAh/g, 159.9 mAh/g, 153.5mAh/g；
After each multiplying power respectively circulates 10 circles above, under 0.1C multiplying powers, electric discharge gram volume can still reach 160 mAh/g, after circulating 50 circles,
Electric discharge gram volume can still reach 152 mAh/g, conservation rate 95%.
Comparative example 1
Assembled using the tertiary cathode material of nickel cobalt manganese 622 as anode.
The assembling of battery：Weigh the tertiary cathode material of 0.4g nickel cobalt manganeses 622, add 0.05g conductive carbon blacks make conductive agent and
0.05g PVDF（Kynoar）Make binding agent, be coated in after well mixed on aluminium foil and positive plate is made, in vacuum glove box
It is barrier film with Celgard 2300 using metal lithium sheet as negative pole, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For electrolyte,
It is assembled into CR2025 button cell.
As shown in figure 4, the battery assembled, in 2.5~4.3V voltage ranges, under 0.1C multiplying powers, discharge capacity is first
176.8 mAh/g, after circulation 50 is enclosed, capacity attenuation to 152.3 mAh/g, capability retention is only 86.1%.
As shown in figure 5, the battery assembled, in 2.5~4.3V voltage ranges, under 0.1C multiplying powers, discharge gram volume first
For 176.8mAh/g.
As shown in fig. 6, the battery assembled is in 2.5~4.3V voltage ranges, under 0.1C, 0.5C, 1C, 2C, 5C multiplying power,
The gram volume that discharges is 173.7mAh/g, 163mAh/g, 152.5mAh/g, 142.6mAh/g, 130.4mAh/g；Each multiplying power more than
After each circle of circulation 10, under 0.1C multiplying powers, electric discharge gram volume is 155 mAh/g, and after the circle of circulation 50, electric discharge gram volume decays to only
130 mAh/g, conservation rate are only 83.9%.
To sum up, the nickle cobalt lithium manganate tertiary cathode material coated by titanium phosphate lithium is equal on cycle performance and high rate performance
Larger improvement is obtained.
Claims (10)
1. a kind of titanium phosphate lithium coats nickel-cobalt-manganternary ternary anode material, it is characterised in that：The quality percentage of the titanium phosphate lithium contains
Measure and 1~2nm of thickness uniform clad is formed with unformed shape for 1~10wt%, titanium phosphate lithium；The positive electrode is particle diameter 5
~15 μm of spheric granules.
A kind of 2. preparation method of the cladding nickel-cobalt-manganternary ternary anode material of titanium phosphate lithium as claimed in claim 1, it is characterised in that
Comprise the following steps：
（1）Titanium source is dispersed in anhydrous organic solvent, stirs to titanium source and dissolves transparent homogeneous solution, then water is added dropwise, is stirred
Mix so that titanium source hydrolysis, obtains milky suspension；
（2）In step（1）In gained milky suspension, by n（Li:Ti:P）=1:2:3 ratio adds lithium source and phosphorus source, holds
It is continuous to be stirred until homogeneous, obtain mixing suspension；
（3）By step（2）Gained mixing suspension is transferred in reactor, is carried out hydro-thermal reaction, centrifuge washing precipitation, is dried,
Obtain titanium phosphate lithium presoma；
（4）By step（3）Gained titanium phosphate lithium presoma is ground with nickel-cobalt-manganternary ternary anode material, is burnt in air atmosphere
Knot, obtain titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material.
3. the preparation method of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material according to claim 2, it is characterised in that：Step
Suddenly（1）In, the volume ratio of the titanium source and anhydrous organic solvent is 1:2~10；The titanium source is butyl titanate, titanium tetrachloride
Or the one or more in isopropyl titanate；The anhydrous organic solvent is one in absolute methanol, absolute ethyl alcohol or anhydrous propyl alcohol
Kind is several.
4. the preparation method of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material, its feature exist according to Claims 2 or 3
In：Step（1）In, the water of the dropwise addition and the volume ratio of titanium source are 0.5~8.0:1；The speed of the dropwise addition is 10~30mL/
min；Mixing time before dropwise addition water is 20~40min；Mixing time after dropwise addition water is 2~4h.
5. the preparation method of nickel-cobalt-manganternary ternary anode material, its feature are coated according to one of claim 2~4 titanium phosphate lithium
It is：Step（2）In, the lithium source is the one or more in lithium hydroxide, lithium carbonate or lithium nitrate；Phosphorus source is phosphoric acid
One or more in ammonium dihydrogen, diammonium hydrogen phosphate or phosphoric acid；The time of the stirring is 20~40min.
6. the preparation method of nickel-cobalt-manganternary ternary anode material, its feature are coated according to one of claim 2~5 titanium phosphate lithium
It is：Step（3）In, the temperature of the hydro-thermal reaction is 150~300 DEG C, and the time of reaction is 6~12h.
7. the preparation method of nickel-cobalt-manganternary ternary anode material, its feature are coated according to one of claim 2~6 titanium phosphate lithium
It is：Step（3）In, the rotating speed of the centrifuge washing is 5000~10000 turns/min, and the time is 5~10min.
8. the preparation method of nickel-cobalt-manganternary ternary anode material, its feature are coated according to one of claim 2~7 titanium phosphate lithium
It is：Step（4）In, the mass ratio of the titanium phosphate lithium presoma and nickel-cobalt-manganternary ternary anode material is 1:5~50；The nickel
The mol ratio of nickel cobalt manganese is 6 in cobalt-manganese ternary positive electrode:2:2、5:2:3、4:2:2 or 1:1:1.
9. the preparation method of nickel-cobalt-manganternary ternary anode material, its feature are coated according to one of claim 2~8 titanium phosphate lithium
It is：Step（4）In, the grinding refers to add equivalent to it in titanium phosphate lithium presoma and nickel-cobalt-manganternary ternary anode material
The ethanol that 0.5~1.5 times of quality, 0.5~4.0h of wet-milling.
10. coating the preparation method of nickel-cobalt-manganternary ternary anode material according to one of claim 2~9 titanium phosphate lithium, it is special
Sign is：Step（4）In, the temperature of the sintering is 400~950 DEG C, and the time of sintering is 6~30h.
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