CN106960955B - The ternary cathode material of lithium ion battery and preparation method thereof of vanadium sulfide cladding - Google Patents
The ternary cathode material of lithium ion battery and preparation method thereof of vanadium sulfide cladding Download PDFInfo
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- CN106960955B CN106960955B CN201710396020.9A CN201710396020A CN106960955B CN 106960955 B CN106960955 B CN 106960955B CN 201710396020 A CN201710396020 A CN 201710396020A CN 106960955 B CN106960955 B CN 106960955B
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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
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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
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- 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
The ternary cathode material of lithium ion battery and preparation method thereof of vanadium sulfide cladding, the material is made of following methods: (1) dispersing vanadium sulfide in organic solvent, ultrasonic disperse, obtain vanadium sulfide dispersion liquid；(2) ternary cathode material of lithium ion battery is added in vanadium sulfide dispersion liquid, stirring, reaction is heated in sealing reaction kettle, it is cooling, it washs, filters, it is dry, obtain mixing presoma；(3) it is heat-treated, grinds after cooling in a reducing atmosphere, obtain the ternary cathode material of lithium ion battery of vanadium sulfide cladding.For battery made of material of the present invention in 2.7~4.3V, first 10 times are 0.1C, are set as under 1C for the 11st~100 time, first discharge specific capacity is up to 195.6mAh/g, capacity has excellent multiplying power and cycle performance up to 77.27% up to 136mAh/g, capacity retention ratio after 100 circle of circulation；The method of the present invention is simple, low in cost, easy to spread.
Description
Technical field
The present invention relates to a kind of ternary cathode material of lithium ion batteries 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 technique
Currently, anode material for lithium-ion batteries mainly has LiFePO4, cobalt acid lithium, LiMn2O4 and ternary material.But
These four materials have the defects that certain.The conductivity 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 is relatively low, and cobalt resource is very expensive and toxic；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, be environmental-friendly and the advantages that 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.The above technological deficiency is all serious to constrain the lithium ion battery
The extensive use of positive electrode, in particular, the defect of ternary material makes it be difficult to lead in electric car and hybrid-electric car
The use and popularization in domain.
The poor restriction lithium ion ternary power battery of the high rate performance and cycle performance of ternary material further develops
Critical issue.
Currently, the method for improving ternary material chemical property mainly has: the measures such as ion doping, surface cladding.Material
Surface cladding is a kind of the most frequently used, simple process, low-cost method 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 the preparation method and application thereof,
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 surface one layer of LiFePO4 of cladding
Nickle cobalt lithium manganate combination electrode with high-temperature stability, effectively inhibits reacting between electrode and electrolyte, improves material
The structural stability of material.But since its inner nuclear material selects nanoscale nickle cobalt lithium manganate, tap density is lower, and reduces nickel
The energy density of cobalt lithium manganate material.Preparation process is complicated simultaneously, higher cost, 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
Pond positive electrode surface coats one layer of barium oxide, this layer of oxide reduces the contact surface between positive electrode and electrolyte
Product, it is suppressed that the side reaction that the two occurs due to directly contacting improves the chemical property of positive electrode.The system of the material
Preparation Method is that organic solvent is added into deionized water in a heated condition, and ammonium metavanadate is precipitated 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
Tertiary cathode material surface coats one layer of VOPO4, avoid tertiary cathode material from contacting with the direct of electrolyte, inhibit 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 it should
The method of modifying of material disperses tertiary cathode material in deionized water, and moisture can seriously destroy the knot of 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, inhibits lithium ion transport, limitation
The performance of ternary material capacity.It needs to develop a kind of simple and easy use vanadium sulfide cladding commercial li-ion battery three at present
The method of first material.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of effectively drop
The residual content of low ternary material surface lithium, while electrolyte can be prevented to significantly improve ternary for the erosion of electrode surface
The ternary cathode material of lithium ion battery of the vanadium sulfide cladding of the high rate performance and cycle performance of positive electrode and its preparation side
Method.
The technical solution adopted by the present invention to solve the technical problems is as follows: the lithium ion battery ternary of vanadium sulfide cladding
Positive electrode is made of following methods:
(1) it disperses vanadium sulfide in organic solvent, then carries out ultrasonic disperse, obtain vanadium sulfide dispersion liquid；
(2) ternary cathode material of lithium ion battery is added in vanadium sulfide dispersion liquid obtained by step (1), is stirred evenly,
Heating reaction is carried out in sealing reaction kettle again, then natural cooling, washed, filtered, it is dry, obtain mixing presoma；
(3) mixing presoma obtained by step (2) is heat-treated in a reducing atmosphere, grinds after cooling, obtains vanadium sulfide
The ternary cathode material of lithium ion battery of cladding.
Preferably, in step (1), after control vanadium sulfide is scattered in organic solvent, the concentration of vanadium ion is 0.8~100
Mmol/L(more preferable 0.9~50.0 mmol/L, still more preferably 1~15 mmol/L).Vanadium ion in organic solvent is dense
Degree is relatively lower than in aqueous solution, if vanadium ion concentration is excessively high, is easy to happen agglomeration, influences covered effect, but
Being can not be too low, will cause the waste of organic solvent.
Preferably, in step (1), the vanadium sulfide is one in vanadium disulfide, four vanadic sulfides or eight five vanadium of vulcanization etc.
Kind is several.Vanadium sulfide is a kind of typical transient metal sulfide, has the two-dimensional layered structure of similar graphene.According to
The difference of sulphur and vanadium proportion, there are the materials such as vanadium disulfide, four vanadic sulfides and eight five vanadium of vulcanization, wherein leads in curing vanadium layers
It crosses S-V-S covalent bond and is connected to form sandwich structure, and interlayer is connected by weaker Van der Waals force, interlamellar spacing 5.76；Eight
Vulcanize five vanadium with three-dimensional structure, structure is in vanadium disulfide Intercalation reaction vacancy vanadium atom, and interlamellar spacing can reach
11.32 Å.Due to this special construction of vanadium sulfide, interlayer can store lesser atom, molecule and ion, can effectively improve
The chemical property of tertiary cathode material.
Preferably, in step (1), the organic solvent is one of methanol, ethyl alcohol, normal propyl alcohol or isopropanol etc. or several
Kind.Due to the especially nickelic tertiary cathode material of tertiary cathode material, such as LiNi0.8Co0.1Mn0.1O2Or
LiNi0.8Co0.15Al0.05O2Deng to moisture rdativery sensitive, the present invention uses organic solvent to replace water as dispersed phase, and avoidable three
The destruction of first cathode material structure.
Preferably, in step (1), 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 the more preferable 5~8h of 2~10h().Ultrasonic disperse may make vanadium sulfide to disperse in organic solvent
Uniformly, the ultrasonic disperse time is unsuitable too short, will lead to the uneven reunion in turn of dispersion.
Preferably, in step (2), vanadium sulfide in the ternary cathode material of lithium ion battery and vanadium sulfide dispersion liquid
Mass ratio be more preferable 1:9~30 1:8~100().If vanadium testing sulphide is too low for tertiary cathode material dosage, 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
Excessively high for tertiary cathode material dosage, then clad is blocked up, limits the rate of the insertion abjection of lithium ion, will lead to ternary
Positive electrode high rate performance is deteriorated.
Preferably, in step (2), 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 of Deng.
Preferably, in step (2), 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, cooling after aerobic calcining, 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
Molar ratio be the more preferable 1.02~1.10:1 of 1.0~1.2:1().
Preferably, the temperature of the calcining is 700~1000 DEG C, and the time of calcining is the more preferable 15~20h of 5~22h().
When calcining, if calcination temperature is too low, lithium ion cannot enter well in the lattice of ternary material；If calcination temperature is excessively high,
It will cause burn-off phenomenon, the primary particle of tertiary cathode material is become thick, and the transmission path of lithium ion is elongated, will lead to three
First positive electrode high rate performance is deteriorated, and controlling suitable calcination condition can get 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 one of lithium carbonate, lithium nitrate or lithium hydroxide etc. and 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, it is 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, it is calcined at 800~850 DEG C；Work as lithium-ion electric
Pond ternary anode material precursor is the lower Ni of nickel content1/3Co1/3Mn1/3(OH)2And Ni0.4Co0.2Mn0.4(OH)2When, 900
It is 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 partial size be 8~12 μm.
Preferably, in step (2), the time of the stirring is 1~4h.
Preferably, in step (2), the temperature of the heating reaction is 120~220 DEG C (more preferable 150~180 DEG C), is added
The time of thermal response is 3~for 24 hours (more preferable 10~20h).By heating reaction in the sealing reaction kettle, to manufacture high temperature
The atmosphere of high pressure promotes vanadium sulfide to be uniformly coated on tertiary cathode material surface.
Preferably, in step (2), the washing filter process use identical organic solvent with step (1).
Preferably, in step (3), the temperature of the heat treatment is 200~600 DEG C, and the time of heat treatment is 4~8h.Step
Suddenly in (2) after heating reaction, vanadium sulfide is to be coated on tertiary cathode material surface with more loose state, by step
Suddenly it is heat-treated under (3) described temperature and time, vanadium sulfide clad can be made more closely, it is good to obtain crystal property
Good, the close vanadium sulfide of clad coats tertiary cathode material, therefore heat treatment temperature cannot be too high.
Preferably, in step (3), the reducing atmosphere is helium, nitrogen, argon gas or argon/hydrogen gaseous mixture etc., wherein argon/
The volume fraction of hydrogen is more preferable 4~8%) 1~10%(in hydrogen gaseous mixture.
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 stable structure in the electrolytic solution can completely cut off moisture in air, carbon dioxide and electrolyte well
Corrosion prevents the generation of side reaction in electrode, inhibits the phenomenon that nickel lithium mixing in electrode, stablizes the stratiform knot of tertiary cathode material
Structure, lithium ion can steadily be embedded in, deviate from, and improve the cyclical stability of tertiary cathode material, and ensure its electrochemistry
Energy gives full play to.Vanadium sulfide has two-dimensional layered structure, itself can also be used as electrode material use, and interlayer can store lithium
Ion can improve the discharge capacity of material entirety, and China's vanadium resource is abundant, uses vanadium sulfide at low cost as covering material
It is honest and clean.
Beneficial effects of the present invention are as follows:
(1) the ternary cathode material of lithium ion battery surface of vanadium sulfide cladding of the present invention has uniform vanadium sulfide packet
Coating can prevent corrosion of the electrolyte to electrode, reduce the lithium content of electrode surface remnants；By electricity made of material of the present invention
Pond carries out charge and discharge test, the results showed that, in 2.7~4.3V, charging current is 0.1C(1C=180mAh/g), before discharge current
It is set as 0.1C 10 times, in the case that the 11st~100 time is set as 1C, first discharge specific capacity reaches as high as 195.6mAh/g,
Capacity reaches as high as 136mAh/g after 100 circle of circulation, and capacity retention ratio reaches as high as 77.27%, and it is excellent to illustrate that material of the present invention has
Different high rate performance and cycle performance；
(2) preparation process of the present invention is simple, and vanadium sulfidic materials and process costs are cheap, easy to spread.
Detailed description of the invention
Fig. 1 is the SEM figure of the ternary cathode material of lithium ion battery of 1 gained vanadium sulfide of embodiment of the present invention cladding；
Fig. 2 is the SEM figure of the uncoated ternary cathode material of lithium ion battery of 1 gained of comparative example；
Fig. 3 is the discharge cycles specific capacity of the embodiment of the present invention 1 Yu 1 gained ternary cathode material of lithium ion battery of comparative example
Curve graph；
Fig. 4 is the discharge cycles specific capacity of the embodiment of the present invention 2 Yu 1 gained ternary cathode material of lithium ion battery of comparative example
Curve graph；
Fig. 5 is the discharge cycles specific capacity of the embodiment of the present invention 3 Yu 1 gained ternary cathode material of lithium ion battery of comparative example
Curve graph；Fig. 6 is the discharge cycles specific capacity of the embodiment of the present invention 4 Yu 1 gained ternary cathode material of lithium ion battery of comparative example
Curve graph.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
The purity of the used high purity oxygen gas of the embodiment of the present invention is 99.99%；Raw material or change used in the embodiment of the present invention
Reagent is learned to obtain by routine business approach unless otherwise specified.
Li:M indicates elemental lithium and ternary cathode material of lithium ion battery forerunner in the lithium salts in the embodiment of the present invention
The molar 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)2Ternary is just
Mono- hydronium(ion) lithia (Li:M=1.05:1) of pole material precursor and 0.484g, grinding 1h are uniformly mixed, and are put into tube type resistance furnace
In, in high purity oxygen gas atmosphere, at 750 DEG C, 15h is calcined, after cooling, grinding 1h to partial size is 8~12 μm, obtains lithium ion
Battery tertiary cathode material LiNi0.8Co0.15Al0.05O2, it is put into spare in baking oven.
Reference example 2
The preparation method of ternary cathode material of lithium ion battery: precise 1g Ni0.8Co0.15Al0.05(OH)2Ternary is just
Pole material precursor and 0.426g lithium carbonate (Li:M=1.05:1), grinding 1h are uniformly mixed, are put into tube type resistance furnace, in height
In pure oxygen atmosphere, at 700 DEG C, 20h is calcined, after cooling, grinding 0.5h to partial size is 8~12 μm, obtains lithium ion battery
Tertiary cathode material LiNi0.8Co0.15Al0.05O2Tertiary cathode material is put into spare 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
Mono- hydronium(ion) lithia (Li:M=1.03:1) of material precursor and 0.469g, grinding 1h are uniformly mixed, and are put into tube type resistance furnace
In, in high purity oxygen gas atmosphere, at 800 DEG C, calcine 15h, after cooling, grinding 0.5h to partial size be 8~12 μm, obtain lithium from
Sub- battery tertiary cathode material LiNi0.6Co0.2Mn0.2O2, it is put into spare in baking oven.
Embodiment 1
(1) precise 0.05g vanadium disulfide is scattered in 80mL dehydrated alcohol, at 40kHz, 20 DEG C, ultrasound
Disperse 6h, obtains vanadium disulfide dispersion liquid；
(2) 1 gained LiNi of 0.95g reference example is taken0.8Co0.15Al0.05O2Positive tertiary cathode material is added obtained by step (1)
In vanadium disulfide dispersion liquid, after magnetic agitation 4h, mixed liquor is added in ptfe autoclave, after sealing, is placed in 180
In DEG C baking oven, 12h is reacted, is taken out after natural cooling, wash with dehydrated alcohol, after filter 23 time, is dried, obtain mixing presoma；
(3) mixing presoma obtained by step (2) is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture (volume of hydrogen point
Number obtains vanadium disulfide cladding at 400 DEG C, to calcine 6h, grinding after cooling in reducing atmosphere 5%)
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 the cladding of vanadium disulfide obtained by the present embodiment0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to CR
2025 type button cells.Charge-discharge procedures are provided that the voltage range of charge and discharge is 2.7~4.3V, charging current 0.1C
(1C=180mAh/g) is set as 0.1C 10 times before discharge current, is set as 1C the 11st~100 time, measures first discharge specific capacity
For 183.1mAh/g, capacity is 132.1mAh/g, capacity retention ratio 72.15% after circulation 100 is enclosed.As it can be seen that addition vanadium sulfide
The lithium ion battery of material preparation has good cyclical stability, and capacity retention ratio is higher.
Embodiment 2
(1) precise 0.01g vanadium disulfide is scattered in 80mL anhydrous isopropyl alcohol, at 60kHz, 40 DEG C, is surpassed
Sound disperses 8h, obtains vanadium disulfide dispersion liquid；
(2) 2 gained LiNi of 0.99g reference example is taken0.8Co0.15Al0.05O2Two sulphur obtained by step (1) are added in tertiary cathode material
Change in vanadium dispersion liquid, after magnetic agitation 2h, mixed liquor is added in ptfe autoclave, after sealing, is placed in 150 DEG C of bakings
In case, 20h is reacted, is taken out to natural cooling, is washed with anhydrous isopropyl alcohol, after filter 23 time, it is dry, obtain mixing presoma；
(3) mixing presoma obtained by step (2) is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture (volume of hydrogen point
Number obtains vanadium disulfide cladding at 200 DEG C, to calcine 6h, grinding after cooling in reducing atmosphere 8%)
LiNi0.8Co0.15Al0.05O2Tertiary cathode material.
By the LiNi of the cladding of vanadium disulfide obtained by the present embodiment0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to CR2025
Type button cell.Charge-discharge procedures be provided that charge and discharge voltage range be 2.7~4.3V, charging current be 0.1C(1C=
180mAh/g), 0.1C being set as 10 times before discharge current, being set as 1C the 11st~100 time, measuring first discharge specific capacity is
184.9mAh/g, capacity is 111mAh/g, capacity retention ratio 60% after circulation 100 is enclosed.As it can be seen that addition vanadium sulfide material system
Standby lithium ion battery has good cyclical stability, and capacity retention ratio is higher.
Embodiment 3
(1) precise 0.10g vanadium disulfide is scattered in 80mL dehydrated alcohol, at 40kHz, 20 DEG C, ultrasound
Disperse 8h, obtains vanadium disulfide dispersion liquid；
(2) 3 gained LiNi of 0.90g reference example is taken0.6Co0.2Mn0.2O2Two sulphur obtained by step (1) are added in tertiary cathode material
Change in vanadium dispersion liquid, after magnetic agitation 4h, mixed liquor is added in ptfe autoclave, after sealing, is placed in 160 DEG C of bakings
In case, 12h is reacted, is taken out to natural cooling, is washed with dehydrated alcohol, after filter 23 time, it is dry, obtain mixing presoma；
(3) mixing presoma obtained by step (2) is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture (volume of hydrogen point
Number obtains vanadium disulfide cladding at 400 DEG C, to calcine 8h, grinding after cooling in reducing atmosphere 5%)
LiNi0.6Co0.2Mn0.2O2Tertiary cathode material.
By the LiNi of the cladding of vanadium disulfide obtained by the present embodiment0.6Co0.2Mn0.2O2Tertiary cathode material is fabricated to CR2025
Type button cell.Charge-discharge procedures be provided that charge and discharge voltage range be 2.7~4.3V, charging current be 0.1C(1C=
175mAh/g), 0.1C being set as 10 times before discharge current, being set as 1C the 11st~100 time, measuring first discharge specific capacity is
176mAh/g, capacity is 136mAh/g, capacity retention ratio 77.27% after circulation 100 is enclosed.As it can be seen that addition vanadium sulfide material system
Standby lithium ion battery has good cyclical stability, and capacity retention ratio is higher.
Embodiment 4
(1) precise 0.05g eight vulcanizes five vanadium, is scattered in 80mL dehydrated alcohol, at 40kHz, 20 DEG C, surpasses
Sound disperses 6h, obtains eight vulcanizations, five vanadium dispersion liquid；
(2) 0.95g Li Ni is taken0.8Co0.15Al0.05O2Tertiary cathode material (is purchased from long-range lithium section, product type LY308)
It is added in eight five vanadium dispersion liquids of vulcanization obtained by step (1), after magnetic agitation 1h, mixed liquor is added to polytetrafluoroethyl-ne alkene reaction
It in kettle, after sealing, is placed in 180 DEG C of baking ovens, reacts 12h, take out after natural cooling, washed with dehydrated alcohol, filter 23
Afterwards, dry, obtain mixing presoma；
(3) mixing presoma obtained by step (2) is placed in tube type resistance furnace, in argon/hydrogen gaseous mixture (volume of hydrogen point
Number obtains eight vulcanizations, five vanadium cladding at 400 DEG C, to calcine 8h, grinding after cooling in reducing atmosphere 5%)
LiNi0.8Co0.15Al0.05O2Tertiary cathode material.
The LiNi for vulcanizing five vanadium cladding for obtained by the present embodiment eight0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to
CR2025 type button cell.Charge-discharge procedures are provided that the voltage range of charge and discharge is 2.7~4.3V, and charging current is
0.1C(1C=180mAh/g), 0.1C is set as 10 times before discharge current, is set as 1C the 11st~100 time, measures the ratio that discharges for the first time
Capacity is 195.6mAh/g, and capacity is 130.2mAh/g, capacity retention ratio 66.56% after 100 circle of circulation.As it can be seen that addition vanadium sulphur
The lithium ion battery of compound material preparation has good cyclical stability, and capacity retention ratio is higher.
Comparative example 1
Precise 1g Ni0.8Co0.15Al0.05(OH)2Mono- hydronium(ion) lithia of ternary anode material precursor and 0.484g
(Li:M=1.05:1) is lightly ground 1h and is uniformly mixed, be put into tube type resistance furnace, in oxygen atmosphere, at 750 DEG C, and calcining
15h is crushed after cooling, obtains LiNi0.8Co0.15Al0.05O2Tertiary cathode material.
As shown in Fig. 2, the LiNi uncoated for surface0.8Co0.15Al0.05O2Tertiary cathode material, surface are smooth complete.
By LiNi obtained by this comparative example0.8Co0.15Al0.05O2Tertiary cathode material is fabricated to CR2025 type button cell.It fills
Discharge procedures are provided that the voltage range of charge and discharge is 2.7~4.3V, and charging current is 0.1C(1C=180mAh/g), electric discharge
0.1C is set as 10 times before electric current, is set as 1C the 11st~100 time, and measuring first discharge specific capacity is 193.7mAh/g, circulation
Capacity is 79.8mAh/g after 100 circles, and capacity retention ratio is only 41.20%.
Claims (32)
1. a kind of ternary cathode material of lithium ion battery of vanadium sulfide cladding, which is characterized in that be made of following methods:
(1) it disperses vanadium sulfide in organic solvent, then carries out ultrasonic disperse, obtain vanadium sulfide dispersion liquid；The vanadium vulcanization
Object is one or more of vanadium disulfide, four vanadic sulfides or eight five vanadium of vulcanization；
(2) ternary cathode material of lithium ion battery is added in vanadium sulfide dispersion liquid obtained by step (1), is stirred evenly, then
Heating reaction is carried out in sealing reaction kettle, then natural cooling, washed, filtered, it is dry, obtain mixing presoma；The lithium ion
The mass ratio of vanadium sulfide is 1:8~100 in battery tertiary cathode material and vanadium sulfide dispersion liquid；
(3) mixing presoma obtained by step (2) is heat-treated in a reducing atmosphere, is ground after cooling, obtain vanadium sulfide cladding
Ternary cathode material of lithium ion battery.
2. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 1, which is characterized in that step
(1) in, after control vanadium sulfide is scattered in organic solvent, the concentration of vanadium ion is 0.8~100 mmol/L；The organic solvent
For one or more of methanol, ethyl alcohol, normal propyl alcohol or isopropanol.
3. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 1 or claim 2, which is characterized in that step
Suddenly in (1), 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 of vanadium sulfide cladding according to claim 1 or claim 2, which is characterized in that step
Suddenly in (2), 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 of
Or it is several.
5. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 3, which is characterized in that 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 of
Or it is several.
6. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 1 or claim 2, which is characterized in that step
Suddenly in (2), the preparation method of the ternary cathode material of lithium ion battery is: by ternary cathode material of lithium ion battery presoma
It is cooling after aerobic calcining with lithium salts ground and mixed, grinding,；Elemental lithium and lithium ion battery ternary in the lithium salts are just
The molar ratio of metallic element total amount is 1.0~1.2:1 in the material precursor of pole；The temperature of the calcining is 700~1000 DEG C, is forged
The time of burning is 5~22h.
7. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 3, which is characterized in that 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, cooling after aerobic calcining, grinding,；Elemental lithium and lithium ion battery tertiary cathode in the lithium salts
The molar ratio of metallic element total amount is 1.0~1.2:1 in material precursor；The temperature of the calcining is 700~1000 DEG C, calcining
Time be 5~22h.
8. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 4, which is characterized in that 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, cooling after aerobic calcining, grinding,；Elemental lithium and lithium ion battery tertiary cathode in the lithium salts
The molar ratio of metallic element total amount is 1.0~1.2:1 in material precursor；The temperature of the calcining is 700~1000 DEG C, calcining
Time be 5~22h.
9. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 6, 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)2One or more of；The lithium salts is lithium carbonate, nitre
One or more of sour lithium or lithium hydroxide and the hydrate of above-mentioned lithium salts.
10. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 7, it is characterised in that: described
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)2One or more of；The lithium salts is lithium carbonate, nitre
One or more of sour lithium or lithium hydroxide and the hydrate of above-mentioned lithium salts.
11. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 8, it is characterised in that: described
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)2One or more of；The lithium salts is lithium carbonate, nitre
One or more of sour lithium or lithium hydroxide and the hydrate of above-mentioned lithium salts.
12. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 9, it is characterised in that: work as lithium
Ion battery ternary anode material precursor is the higher Ni of nickel content0.8Co0.1Mn0.1(OH)2And Ni0.8Co0.15Al0.05(OH)2
When, it is 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, it is calcined at 800~850 DEG C；When lithium ion battery tertiary cathode
Material precursor is the lower Ni of nickel content1/3Co1/3Mn1/3(OH)2And Ni0.4Co0.2Mn0.4(OH)2When, at 900~950 DEG C
Calcining.
13. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 10, it is characterised in that: work as lithium
Ion battery ternary anode material precursor is the higher Ni of nickel content0.8Co0.1Mn0.1(OH)2And Ni0.8Co0.15Al0.05(OH)2
When, it is 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, it is calcined at 800~850 DEG C；When lithium ion battery tertiary cathode
Material precursor is the lower Ni of nickel content1/3Co1/3Mn1/3(OH)2And Ni0.4Co0.2Mn0.4(OH)2When, at 900~950 DEG C
Calcining.
14. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 11, it is characterised in that: work as lithium
Ion battery ternary anode material precursor is the higher Ni of nickel content0.8Co0.1Mn0.1(OH)2And Ni0.8Co0.15Al0.05(OH)2
When, it is 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, it is calcined at 800~850 DEG C；When lithium ion battery tertiary cathode
Material precursor is the lower Ni of nickel content1/3Co1/3Mn1/3(OH)2And Ni0.4Co0.2Mn0.4(OH)2When, at 900~950 DEG C
Calcining.
15. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 6, it is characterised in that: described
The atmosphere of aerobic calcining is oxygen or air atmosphere；The time of the ground and mixed is 0.5~1.5h；It is ground after the calcining
0.5~1.0h to partial size be 8~12 μm.
16. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 9, it is characterised in that: described
The atmosphere of aerobic calcining is oxygen or air atmosphere；The time of the ground and mixed is 0.5~1.5h；It is ground after the calcining
0.5~1.0h to partial size be 8~12 μm.
17. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 12, it is characterised in that: described
The atmosphere of aerobic calcining is oxygen or air atmosphere；The time of the ground and mixed is 0.5~1.5h；It is ground after the calcining
0.5~1.0h to partial size be 8~12 μm.
18. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 1 or claim 2, which is characterized in that step
Suddenly in (2), the time of the stirring is 1~4h；The temperature of the heating reaction is 120~220 DEG C, and the time for heating reaction is
3~for 24 hours.
19. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 3, which is characterized in that step
(2) in, the time of the stirring is 1~4h；The temperature of the heating reaction is 120~220 DEG C, and the time for heating reaction is 3
~for 24 hours.
20. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 4, which is characterized in that step
(2) in, the time of the stirring is 1~4h；The temperature of the heating reaction is 120~220 DEG C, and the time for heating reaction is 3
~for 24 hours.
21. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 6, which is characterized in that step
(2) in, the time of the stirring is 1~4h；The temperature of the heating reaction is 120~220 DEG C, and the time for heating reaction is 3
~for 24 hours.
22. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 9, which is characterized in that step
(2) in, the time of the stirring is 1~4h；The temperature of the heating reaction is 120~220 DEG C, and the time for heating reaction is 3
~for 24 hours.
23. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 12, which is characterized in that step
(2) in, the time of the stirring is 1~4h；The temperature of the heating reaction is 120~220 DEG C, and the time for heating reaction is 3
~for 24 hours.
24. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 15, which is characterized in that step
(2) in, the time of the stirring is 1~4h；The temperature of the heating reaction is 120~220 DEG C, and the time for heating reaction is 3
~for 24 hours.
25. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 1 or claim 2, which is characterized in that step
Suddenly in (3), the temperature of the heat treatment is 200~600 DEG C, and the time of heat treatment is 4~8h；The reducing atmosphere be helium,
Nitrogen, argon gas or argon/hydrogen gaseous mixture, wherein the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
26. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 3, which is characterized in that 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
Gas, argon gas or argon/hydrogen gaseous mixture, wherein the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
27. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 4, which is characterized in that 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
Gas, argon gas or argon/hydrogen gaseous mixture, wherein the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
28. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 6, which is characterized in that 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
Gas, argon gas or argon/hydrogen gaseous mixture, wherein the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
29. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 9, which is characterized in that 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
Gas, argon gas or argon/hydrogen gaseous mixture, wherein the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
30. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 12, which is characterized in that 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
Gas, argon gas or argon/hydrogen gaseous mixture, wherein the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
31. the ternary cathode material of lithium ion battery of vanadium sulfide cladding according to claim 15, which is characterized in that 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
Gas, argon gas or argon/hydrogen gaseous mixture, wherein the volume fraction of hydrogen is 1~10% in argon/hydrogen gaseous mixture.
32. the ternary cathode material of lithium ion battery of the 8 vanadium sulfide claddings according to claim 1, which is characterized in that 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
Gas, 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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