CN106960955A - Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof - Google Patents
Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof, the material is made up of following methods：（1）Vanadium sulfide is scattered in organic solvent, ultrasonic disperse, obtains vanadium sulfide dispersion liquid；（2）Ternary cathode material of lithium ion battery is added in vanadium sulfide dispersion liquid, stirring, the heating response in sealed reactor is cooled down, and is washed, and is filtered, and is dried, is obtained mixing presoma；（3）It is heat-treated, grinds after cooling in reducing atmosphere, obtains the ternary cathode material of lithium ion battery of vanadium sulfide cladding.The battery that material of the present invention is made is in 2.7~4.3V, and first 10 times are 0.1C, are set under 1C for the 11st~100 time, first discharge specific capacity is up to 195.6mAh/g, capacity is up to 136mAh/g after the circle of circulation 100, and capability retention is up to 77.27%, with excellent multiplying power and cycle performance；The inventive method is simple, with low cost, it is easy to promote.
Description
Technical field
The present invention relates to a kind of ternary cathode material of lithium ion battery and preparation method thereof, and in particular to a kind of vanadium sulfide
Ternary cathode material of lithium ion battery of cladding and preparation method thereof.
Background technology
At present, anode material for lithium-ion batteries mainly has LiFePO4, cobalt acid lithium, LiMn2O4 and ternary material.But,
There is certain defect in these four materials.The conductance of LiFePO4 is low, and tap density is low, and energy density is low；Due to cobalt acid
The limitation of lithium ion deintercalation ratio in lithium, Capacity Ratio is relatively low, and cobalt resource is very expensive and poisonous；Although and LiMn2O4 safety
Property it is high, but due in charge and discharge process crystal structure it is unstable, cycle performance is poor；Although ternary material has energy density
It is high, have extended cycle life, it is environment-friendly and the advantages of have a safety feature, be a kind of lithium ion battery most with prospects at present
Positive electrode, but its high rate performance and cycle performance are poor.Above technological deficiency is all serious to constrain the lithium ion battery
The extensive use of positive electrode, particularly, the defect of ternary material make it that it is difficult in electric automobile and hybrid-electric car neck
The use and popularization in domain.
The poor restriction lithium ion ternary electrokinetic cell of high rate performance and cycle performance of ternary material further develops
Key issue.
At present, improving the method for ternary material chemical property mainly has：The measures such as ion doping, Surface coating.Material
Surface coating is a kind of simple, with low cost method of the most frequently used, technique at present.The surface coated material of ternary material mainly has
Metal oxide, metal fluoride and metal phosphate.
CN106384815A discloses a kind of high-temperature stability nickle cobalt lithium manganate combination electrode and preparation method and application,
It is to be formed in nanoscale nickle cobalt lithium manganate surface one layer of two-dimensional layer material of pre-coated, then in outer one layer of LiFePO4 of Surface coating
Nickle cobalt lithium manganate combination electrode with high-temperature stability, effectively inhibits the reaction between electrode and electrolyte, improves material
The structural stability of material.But, because its inner nuclear material selects nanoscale nickle cobalt lithium manganate, tap density step-down reduces nickel
The energy density of cobalt lithium manganate material.Preparation technology is complicated simultaneously, and cost is higher, restricts its commercialization and uses.
CN103794753A discloses a kind of lithium ion battery composite cathode material and preparation method thereof, is in lithium-ion electric
One layer of barium oxide of pond positive electrode Surface coating, this layer of oxide reduces the contact surface between positive electrode and electrolyte
Product, it is suppressed that both improve the chemical property of positive electrode due to the side reaction for directly contacting and occurring.The system of the material
Preparation Method is to add organic solvent into deionized water in a heated condition, ammonium metavanadate is separated out from water, is coated on ternary
On material, still, the surface coated uniformity is not ensured that.
CN104134796A discloses a kind of method of modifying of ternary cathode material of lithium ion battery, is in lithium ion battery
One layer of VOPO of tertiary cathode material Surface coating4, it is to avoid tertiary cathode material is directly contacted with electrolyte, is suppressed in electrolyte
Corrosion of the HF to tertiary cathode material, to reach modified purpose, and VOPO4Insert lithium characteristic with superior, layer and layer it
Between allow lithium ion transmission, air storage performance, high-temperature storage performance and the cycle performance of material can be improved.But, should
Tertiary cathode material is scattered in deionized water by the method for modifying of material, and the knot of moisture meeting heavy damage tertiary cathode material
Structure, reduces chemical property；And it is big using spray drying technology difficulty, process costs are high.
Therefore, conventional covering material such as metal oxide, fluoride electric conductivity is poor, suppresses lithium ion transport, limitation
The performance of ternary material capacity.Need badly at present and develop a kind of use vanadium sulfide cladding commercial li-ion battery three simple and easy to apply
The method of first material.
The content of the invention
The technical problems to be solved by the invention are that the drawbacks described above for overcoming prior art to exist effectively drops there is provided a kind of
The residual content of low ternary material surface lithium, while electrolyte can be prevented for the erosion of electrode surface, significantly improves ternary
The ternary cathode material of lithium ion battery and its preparation side of the high rate performance of positive electrode and the vanadium sulfide cladding of cycle performance
Method.
The technical solution adopted for the present invention to solve the technical problems is as follows：The lithium ion battery ternary of vanadium sulfide cladding
Positive electrode, is made up of following methods：
（1）Vanadium sulfide is scattered in organic solvent, then carries out ultrasonic disperse, vanadium sulfide dispersion liquid is obtained；
（2）Ternary cathode material of lithium ion battery is added into step（1）In gained vanadium sulfide dispersion liquid, stir, then
Heating response is carried out in sealed reactor, then natural cooling, washed, filtered, dried, obtain mixing presoma；
（3）By step（2）Gained mixing presoma is heat-treated in reducing atmosphere, is ground after cooling, obtains vanadium sulfide cladding
Ternary cathode material of lithium ion battery.
Preferably, step（1）In, control vanadium sulfide is scattered in after organic solvent, and the concentration of vanadium ion is 0.8~100
mmol/L（More preferably 0.9~50.0 mmol/L, still more preferably 1~15 mmol/L）.Vanadium ion in organic solvent is dense
Degree is than more relatively low in aqueous, if vanadium ion concentration is too high, easily occurs agglomeration, influences covered effect, but
Being can not be too low, can cause the waste of organic solvent.
Preferably, step（1）In, the vanadium sulfide is one in vanadium disulfide, four vanadic sulfides or eight five vanadium of vulcanization etc.
Plant or several.Vanadium sulfide is a kind of typical transient metal sulfide, the two-dimensional layered structure with similar graphene.According to
, there is the materials such as vanadium disulfide, four vanadic sulfides and eight five vanadium of vulcanization in the difference that sulphur is matched with vanadium, wherein, lead in curing vanadium layers
Cross S-V-S covalent bonds and be connected to form sandwich structure, and interlayer is connected by weaker Van der Waals force, interlamellar spacing is 5.76；Eight
Vulcanizing five vanadium has 3-D solid structure, and its structure is that, in vanadium disulfide Intercalation reaction room vanadium atom, interlamellar spacing can reach
11.32 Å.Due to this special construction of vanadium sulfide, interlayer can store less atom, molecule and ion, can effectively improve
The chemical property of tertiary cathode material.
Preferably, step（1）In, the organic solvent is one kind or several in methanol, ethanol, normal propyl alcohol or isopropanol etc.
Kind.Due to the especially nickelic tertiary cathode material of tertiary cathode material, such as LiNi0.8Co0.1Mn0.1O2Or
LiNi0.8Co0.15Al0.05O2It is of the invention to use organic solvent to replace water as dispersed phase Deng to moisture rdativery sensitive, three can be avoided
The destruction of first cathode material structure.
Preferably, step（1）In, the frequency of the ultrasonic disperse is 40~60kHz, and the temperature of ultrasonic disperse is 20~40
DEG C, the time of ultrasonic disperse is 2~10h（More preferably 5~8h）.Ultrasonic disperse may be such that vanadium sulfide disperses in organic solvent
Uniformly, the ultrasonic disperse time is unsuitable too short, can cause scattered uneven and then reunite.
Preferably, step（2）In, the ternary cathode material of lithium ion battery and vanadium sulfide in vanadium sulfide dispersion liquid
Mass ratio be 1:8~100（More preferably 1:9~30）.If vanadium testing sulphide is too low for tertiary cathode material consumption, vanadium sulphur
Compound is not enough to coat the spherical second particle of tertiary cathode material, it is difficult to play preferable covered effect；If vanadium testing sulphide
Too high for tertiary cathode material consumption, then clad is blocked up, limits the speed of the embedded abjection of lithium ion, can cause ternary
Positive electrode high rate performance is deteriorated.
Preferably, step（2）In, the ternary cathode material of lithium ion battery is LiNi1/3Co1/3Mn1/3O2、
LiNi0.4Co0.2Mn0.4O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Or
LiNi0.8Co0.15Al0.05O2One or more in.
Preferably, step（2）In, the preparation method of the ternary cathode material of lithium ion battery is：By lithium ion battery
Ternary anode material precursor and lithium salts ground and mixed, after aerobic calcining, are cooled down, grinding,.The lithium ion battery ternary
Positive electrode is also commercially available.
Preferably, the elemental lithium in the lithium salts and metallic element total amount in ternary cathode material of lithium ion battery presoma
Mol ratio be 1.0~1.2:1（More preferably 1.02~1.10:1）.
Preferably, the temperature of the calcining is 700~1000 DEG C, and the time of calcining is 5~22h（More preferably 15~20h）.
During calcining, if calcining heat is too low, lithium ion can not enter in the lattice of ternary material well；If calcining heat is too high,
Burn-off phenomenon can be then caused, the primary particle of tertiary cathode material becomes thick, and the transmission path of lithium ion is elongated, can cause three
First positive electrode high rate performance is deteriorated, and controls suitable calcination condition to obtain the good tertiary cathode material of crystal property.
Preferably, the ternary cathode material of lithium ion battery presoma is Ni1/3Co1/3Mn1/3(OH)2、
Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2Or Ni0.8Co0.15Al0.05(OH)2In
One or more.
Preferably, the lithium salts is lithium carbonate, lithium nitrate or lithium hydroxide etc., and one kind in the hydrate of above-mentioned lithium salts
Or it is several.
Preferably, when ternary cathode material of lithium ion battery presoma is the higher Ni of nickel content0.8Co0.1Mn0.1(OH)2
And Ni0.8Co0.15Al0.05(OH)2When, calcined at 700~750 DEG C；When ternary cathode material of lithium ion battery presoma is nickel
The medium Ni of content0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2When, calcined at 800~850 DEG C；Work as lithium-ion electric
Pond ternary anode material precursor is the relatively low Ni of nickel content1/3Co1/3Mn1/3(OH)2And Ni0.4Co0.2Mn0.4(OH)2When, 900
Calcined at~950 DEG C.
Preferably, the atmosphere of the aerobic calcining is oxygen or air atmosphere.The oxygen has high-purity gas, and purity is
99.99%。
Preferably, the time of the ground and mixed is 0.5~1.5h.
Preferably, after the calcining grind 0.5~1.0h to particle diameter be 8~12 μm.
Preferably, step（2）In, the time of the stirring is 1~4h.
Preferably, step（2）In, the temperature of the heating response is 120~220 DEG C（More preferably 150~180 DEG C）, plus
The time of thermal response is 3~24h（More preferably 10~20h）.By the heating response in the sealed reactor, to manufacture high temperature
The atmosphere of high pressure, promotes vanadium sulfide to be uniformly coated on tertiary cathode material surface.
Preferably, step（2）In, the washing and filtering process is used and step（1）Identical organic solvent.
Preferably, step（3）In, the temperature of the heat treatment is 200~600 DEG C, and the time of heat treatment is 4~8h.Step
Suddenly（2）After middle heating response, vanadium sulfide is to be coated on tertiary cathode material surface with more loose state, by step
Suddenly（3）It is heat-treated under the temperature and time, vanadium sulfide clad can be made more close, it is good to obtain crystal property
The close vanadium sulfide cladding tertiary cathode material of good, clad, therefore heat treatment temperature can not be too high.
Preferably, step（3）In, the reducing atmosphere is helium, nitrogen, argon gas or argon/hydrogen gaseous mixture etc., wherein, argon/
The volume fraction of hydrogen is 1~10% in hydrogen gaseous mixture（More preferably 4~8%）.
The surface coated vanadium sulfurized layer of ternary cathode material of lithium ion battery of the present invention has preferable cyclical stability,
Vanadium sulfide material Stability Analysis of Structures in the electrolytic solution, moisture, carbon dioxide and the electrolyte that can completely cut off well in air
Corrosion, prevents the generation of side reaction in electrode, suppresses the phenomenon of nickel lithium mixing in electrode, the stratiform knot of stable tertiary cathode material
Structure, lithium ion can stably be embedded in, deviate from, and improve the cyclical stability of tertiary cathode material, and ensure its electrochemistry
Can give full play to.Vanadium sulfide has two-dimensional layered structure, and itself can also be used as electrode material, and interlayer can store lithium
Ion, can improve the overall discharge capacity of material, and China's vanadium resource is abundant, and covering material low cost is used as using vanadium sulfide
It is honest and clean.
Beneficial effects of the present invention are as follows：
（1）There is uniform vanadium sulfide to coat on the ternary cathode material of lithium ion battery surface of vanadium sulfide cladding of the present invention
Layer, can prevent corrosion of the electrolyte to electrode, the remaining lithium content of reduction electrode surface；The battery that material of the present invention is made
Charge and discharge electric test is carried out, is as a result shown, in 2.7~4.3V, charging current is 0.1C（1C=180mAh/g）, 10 before discharge current
Secondary to be set to 0.1C, in the case that the 11st~100 time is set to 1C, first discharge specific capacity reaches as high as 195.6mAh/g, follows
Capacity reaches as high as 136mAh/g after ring 100 is enclosed, and capability retention reaches as high as 77.27%, illustrates that material of the present invention has excellent
High rate performance and cycle performance；
（2）Preparation technology of the present invention is simple, and vanadium sulfidic materials and process costs are cheap, it is easy to promote.
Brief description of the drawings
Fig. 1 is the SEM figures of the ternary cathode material of lithium ion battery of the gained vanadium sulfide of the embodiment of the present invention 1 cladding；
Fig. 2 is the SEM figures of the uncoated ternary cathode material of lithium ion battery of the gained of comparative example 1；
Fig. 3 is the discharge cycles specific capacity curve of the embodiment of the present invention 1 and the gained ternary cathode material of lithium ion battery of comparative example 1
Figure；
Fig. 4 is the discharge cycles specific capacity curve of the embodiment of the present invention 2 and the gained ternary cathode material of lithium ion battery of comparative example 1
Figure；
Fig. 5 is the discharge cycles specific capacity curve of the embodiment of the present invention 3 and the gained ternary cathode material of lithium ion battery of comparative example 1
Figure；Fig. 6 is the discharge cycles specific capacity curve of the embodiment of the present invention 4 and the gained ternary cathode material of lithium ion battery of comparative example 1
Figure.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
It is 99.99% that the embodiment of the present invention, which uses the purity of high purity oxygen gas,；Raw material used in the embodiment of the present invention or change
Reagent is learned, unless otherwise specified, is obtained by routine business approach.
Li in the embodiment of the present invention:M represents elemental lithium and ternary cathode material of lithium ion battery forerunner in the lithium salts
The mol ratio of metallic element total amount in body.
Reference example 1
The preparation method of ternary cathode material of lithium ion battery：Precise 1g Ni0.8Co0.15Al0.05(OH)2Tertiary cathode material
Material precursor and the hydronium(ion) lithias of 0.484g mono-（Li:M=1.05:1）, grind 1h and be well mixed, be put into tube type resistance furnace,
In high purity oxygen gas atmosphere, at 750 DEG C, 15h is calcined, after cooling, grinding 1h to particle diameter is 8~12 μm, obtains lithium-ion electric
Pond tertiary cathode material LiNi0.8Co0.15Al0.05O2, it is put into standby in baking oven.
Reference example 2
The preparation method of ternary cathode material of lithium ion battery：Precise 1g Ni0.8Co0.15Al0.05(OH)2Tertiary cathode material
Material precursor and 0.426g lithium carbonates（Li:M=1.05:1）, grind 1h and be well mixed, be put into tube type resistance furnace, in high pure oxygen
In gas atmosphere, at 700 DEG C, 20h is calcined, after cooling, grinding 0.5h to particle diameter is 8~12 μm, obtains lithium ion battery ternary
Positive electrode LiNi0.8Co0.15Al0.05O2Tertiary cathode material, is put into standby in baking oven.
Reference example 3
The preparation method of ternary cathode material of lithium ion battery：Precise 1g Ni0.6Co0.2Mn0.2(OH)2Tertiary cathode material
Presoma and the hydronium(ion) lithias of 0.469g mono-（Li:M=1.03:1）, grind 1h and be well mixed, be put into tube type resistance furnace,
In high purity oxygen gas atmosphere, at 800 DEG C, 15h is calcined, after cooling, grinding 0.5h to particle diameter is 8~12 μm, obtains lithium-ion electric
Pond tertiary cathode material LiNi0.6Co0.2Mn0.2O2, it is put into standby in baking oven.
Embodiment 1
（1）Precise 0.05g vanadium disulfides, are scattered in 80mL absolute ethyl alcohols, at 40kHz, 20 DEG C, ultrasonic disperse
6h, obtains vanadium disulfide dispersion liquid；
（2）Take the gained LiNi of 0.95g reference examples 10.8Co0.15Al0.05O2Positive pole tertiary cathode material adds step（1）The sulphur of gained two
Change in vanadium dispersion liquid, after magnetic agitation 4h, mixed liquor is added in ptfe autoclave, after sealing, 180 DEG C of bakings are placed in
In case, 12h is reacted, is taken out after after natural cooling, after absolute ethanol washing, filter 23 time, is dried, obtain mixing presoma；
（3）By step（2）Gained mixing presoma is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture（The volume fraction of hydrogen is
5%）Reducing atmosphere in, at 400 DEG C, calcine 6h, grind after cooling, obtain vanadium disulfide cladding
LiNi0.8Co0.15Al0.05O2Tertiary cathode material.
As shown in figure 1, vanadium disulfide coats LiNi0.8Co0.15Al0.05O2Tertiary cathode material coated with uniform has one layer
The coarse vanadium disulfide coating of appearance.
By the LiNi of vanadium disulfide cladding obtained by the present embodiment0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to CR
2025 type button cells.Charge-discharge procedures set as follows：The voltage range of discharge and recharge is 2.7~4.3V, and charging current is 0.1C
（1C=180mAh/g）, 0.1C is set to 10 times before discharge current, 1C is set to the 11st~100 time, measures first discharge specific capacity
For 183.1mAh/g, capacity is 132.1mAh/g after circulation 100 is enclosed, and capability retention is 72.15%.It can be seen that, add vanadium sulfide
Lithium ion battery prepared by material has good cyclical stability, and capability retention is higher.
Embodiment 2
（1）Precise 0.01g vanadium disulfides, are scattered in 80mL anhydrous isopropyl alcohols, at 60kHz, 40 DEG C, ultrasound point
8h is dissipated, vanadium disulfide dispersion liquid is obtained；
（2）Take the gained LiNi of 0.99g reference examples 20.8Co0.15Al0.05O2Tertiary cathode material adds step（1）Gained vanadium disulfide
In dispersion liquid, after magnetic agitation 2h, mixed liquor is added in ptfe autoclave, after sealing, 150 DEG C of baking ovens are placed in
In, 20h is reacted, natural cooling is treated in taking-up, washed with anhydrous isopropyl alcohol, after filter 23 time, dry, obtain mixing presoma；
（3）By step（2）Gained mixing presoma is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture（The volume fraction of hydrogen is
8%）Reducing atmosphere in, at 200 DEG C, calcine 6h, grind after cooling, obtain vanadium disulfide cladding
LiNi0.8Co0.15Al0.05O2Tertiary cathode material.
By the LiNi of vanadium disulfide cladding obtained by the present embodiment0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to CR2025
Type button cell.Charge-discharge procedures set as follows：The voltage range of discharge and recharge is 2.7~4.3V, and charging current is 0.1C（1C=
180mAh/g）, 0.1C is set to 10 times before discharge current, 1C is set to the 11st~100 time, and measuring first discharge specific capacity is
Capacity is 111mAh/g after 184.9mAh/g, the circle of circulation 100, and capability retention is 60%.It can be seen that, add vanadium sulfide material system
Standby lithium ion battery has good cyclical stability, and capability retention is higher.
Embodiment 3
（1）Precise 0.10g vanadium disulfides, are scattered in 80mL absolute ethyl alcohols, at 40kHz, 20 DEG C, ultrasonic disperse
8h, obtains vanadium disulfide dispersion liquid；
（2）Take the gained LiNi of 0.90g reference examples 30.6Co0.2Mn0.2O2Tertiary cathode material adds step（1）Gained vanadium disulfide
In dispersion liquid, after magnetic agitation 4h, mixed liquor is added in ptfe autoclave, after sealing, 160 DEG C of baking ovens are placed in
In, 12h is reacted, natural cooling is treated in taking-up, after absolute ethanol washing, filter 23 time, dry, obtain mixing presoma；
（3）By step（2）Gained mixing presoma is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture（The volume fraction of hydrogen is
5%）Reducing atmosphere in, at 400 DEG C, calcine 8h, grind after cooling, obtain vanadium disulfide cladding
LiNi0.6Co0.2Mn0.2O2Tertiary cathode material.
By the LiNi of vanadium disulfide cladding obtained by the present embodiment0.6Co0.2Mn0.2O2Tertiary cathode material is fabricated to CR2025
Type button cell.Charge-discharge procedures set as follows：The voltage range of discharge and recharge is 2.7~4.3V, and charging current is 0.1C（1C=
175mAh/g）, 0.1C is set to 10 times before discharge current, 1C is set to the 11st~100 time, and measuring first discharge specific capacity is
Capacity is 136mAh/g after 176mAh/g, the circle of circulation 100, and capability retention is 77.27%.It can be seen that, add vanadium sulfide material system
Standby lithium ion battery has good cyclical stability, and capability retention is higher.
Embodiment 4
（1）Precise 0.05g eight vulcanizes five vanadium, is scattered in 80mL absolute ethyl alcohols, at 40kHz, 20 DEG C, ultrasound point
6h is dissipated, the vanadium dispersion liquid of eight vulcanization five is obtained；
（2）Take 0.95g Li Ni0.8Co0.15Al0.05O2Tertiary cathode material（It is purchased from long-range lithium section, product type LY308）Add
To step（1）Gained eight vulcanizes in five vanadium dispersion liquids, and after magnetic agitation 1h, mixed liquor is added into ptfe autoclave
In, after sealing, it is placed in 180 DEG C of baking ovens, reacts 12h, takes out after after natural cooling, after absolute ethanol washing, filter 23 time,
Dry, obtain mixing presoma；
（3）By step（2）Gained mixing presoma is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture（The volume fraction of hydrogen is
5%）Reducing atmosphere in, at 400 DEG C, calcine 8h, grind after cooling, obtain the vanadium of eight vulcanization five cladding
LiNi0.8Co0.15Al0.05O2Tertiary cathode material.
By obtained by the present embodiment eight LiNi for vulcanizing five vanadium cladding0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to
CR2025 type button cells.Charge-discharge procedures set as follows：The voltage range of discharge and recharge is 2.7~4.3V, and charging current is
0.1C（1C=180mAh/g）, 0.1C is set to 10 times before discharge current, 1C is set to the 11st~100 time, measures electric discharge ratio first
Capacity is 195.6mAh/g, and capacity is 130.2mAh/g after the circle of circulation 100, and capability retention is 66.56%.It can be seen that, add vanadium sulphur
Lithium ion battery prepared by compound material has good cyclical stability, and capability retention is higher.
Comparative example 1
Precise 1g Ni0.8Co0.15Al0.05(OH)2Ternary anode material precursor and the hydronium(ion) lithias of 0.484g mono-（Li:
M=1.05:1）, it is lightly ground 1h and is well mixed, be put into tube type resistance furnace, in oxygen atmosphere, at 750 DEG C, calcines 15h,
After cooling, crush, obtain LiNi0.8Co0.15Al0.05O2Tertiary cathode material.
As shown in Fig. 2 being the uncoated LiNi in surface0.8Co0.15Al0.05O2Tertiary cathode material, surface is smooth complete.
By LiNi obtained by this comparative example0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to CR2025 type button cells.Fill
Discharge procedures set as follows：The voltage range of discharge and recharge is 2.7~4.3V, and charging current is 0.1C（1C=180mAh/g）, electric discharge
0.1C is set to before electric current 10 times, 1C is set to the 11st~100 time, measures first discharge specific capacity for 193.7mAh/g, circulation
Capacity is 79.8mAh/g after 100 circles, and capability retention is only 41.20%.
Claims (10)
1. a kind of ternary cathode material of lithium ion battery of vanadium sulfide cladding, it is characterised in that be made up of following methods：
（1）Vanadium sulfide is scattered in organic solvent, then carries out ultrasonic disperse, vanadium sulfide dispersion liquid is obtained；
（2）Ternary cathode material of lithium ion battery is added into step（1）In gained vanadium sulfide dispersion liquid, stir, then
Heating response is carried out in sealed reactor, then natural cooling, washed, filtered, dried, obtain mixing presoma；
（3）By step（2）Gained mixing presoma is heat-treated in reducing atmosphere, is ground after cooling, obtains vanadium sulfide cladding
Ternary cathode material of lithium ion battery.
2. the ternary cathode material of lithium ion battery that vanadium sulfide is coated according to claim 1, it is characterised in that step
（1）In, control vanadium sulfide is scattered in after organic solvent, and the concentration of vanadium ion is 0.8~100 mmol/L；The vanadium sulfide
For the one or more in vanadium disulfide, four vanadic sulfides or eight five vanadium of vulcanization；The organic solvent is methanol, ethanol, normal propyl alcohol
Or the one or more in isopropanol.
3. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 1 or claim 2, it is characterised in that step
Suddenly（1）In, the frequency of the ultrasonic disperse is 40~60kHz, and the temperature of ultrasonic disperse is 20~40 DEG C, the time of ultrasonic disperse
For 2~10h.
4. the ternary cathode material of lithium ion battery coated according to one of claims 1 to 3 vanadium sulfide, its feature exists
In step（2）In, the ternary cathode material of lithium ion battery is 1 with the mass ratio of vanadium sulfide in vanadium sulfide dispersion liquid:
8~100；The ternary cathode material of lithium ion battery is LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、
LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Or LiNi0.8Co0.15Al0.05O2In one kind
Or it is several.
5. the ternary cathode material of lithium ion battery coated according to one of Claims 1 to 4 vanadium sulfide, its feature exists
In step（2）In, the preparation method of the ternary cathode material of lithium ion battery is：By ternary cathode material of lithium ion battery
Presoma and lithium salts ground and mixed, after aerobic calcining, are cooled down, grinding,；Elemental lithium and lithium ion battery in the lithium salts
The mol ratio of metallic element total amount is 1.0~1.2 in ternary anode material precursor:1；The temperature of the calcining be 700~
1000 DEG C, the time of calcining is 5~22h.
6. the ternary cathode material of lithium ion battery that vanadium sulfide is coated according to claim 5, it is characterised in that：The lithium
Ion battery ternary anode material precursor is Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2
(OH)2、Ni0.8Co0.1Mn0.1(OH)2Or Ni0.8Co0.15Al0.05(OH)2In one or more；The lithium salts is lithium carbonate, nitre
Sour lithium or lithium hydroxide, and the one or more in the hydrate of above-mentioned lithium salts.
7. the ternary cathode material of lithium ion battery that vanadium sulfide is coated according to claim 6, it is characterised in that：When lithium from
Sub- battery ternary anode material precursor is the higher Ni of nickel content0.8Co0.1Mn0.1(OH)2And Ni0.8Co0.15Al0.05(OH)2
When, calcined at 700~750 DEG C；When ternary cathode material of lithium ion battery presoma is that nickel content is medium
Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2When, calcined at 800~850 DEG C；When lithium ion battery tertiary cathode
Material precursor is the relatively low Ni of nickel content1/3Co1/3Mn1/3(OH)2And Ni0.4Co0.2Mn0.4(OH)2When, at 900~950 DEG C
Calcining.
8. the ternary cathode material of lithium ion battery coated according to one of claim 5~7 vanadium sulfide, its feature exists
In：The atmosphere of the aerobic calcining is oxygen or air atmosphere；The time of the ground and mixed is 0.5~1.5h；The calcining
Afterwards grinding 0.5~1.0h to particle diameter be 8~12 μm.
9. the ternary cathode material of lithium ion battery coated according to one of claim 1~8 vanadium sulfide, its feature exists
In step（2）In, the time of the stirring is 1~4h；The temperature of the heating response is 120~220 DEG C, heating response
Time is 3~24h.
10. the ternary cathode material of lithium ion battery coated according to one of claim 1~9 vanadium sulfide, its feature exists
In step（3）In, the temperature of the heat treatment is 200~600 DEG C, and the time of heat treatment is 4~8h；The reducing atmosphere is
Helium, nitrogen, argon gas or argon/hydrogen gaseous mixture, wherein, the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
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