CN108682795A - Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) - Google Patents
Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) Download PDFInfo
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- CN108682795A CN108682795A CN201810266455.6A CN201810266455A CN108682795A CN 108682795 A CN108682795 A CN 108682795A CN 201810266455 A CN201810266455 A CN 201810266455A CN 108682795 A CN108682795 A CN 108682795A
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- cathode material
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- ternary
- lithium ion
- titanium sulfate
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 title claims abstract description 6
- 239000011248 coating agent Substances 0.000 title claims abstract description 4
- 238000005554 pickling Methods 0.000 title abstract description 9
- 239000010405 anode material Substances 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000010406 cathode material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 30
- 238000005253 cladding Methods 0.000 claims description 28
- 238000010792 warming Methods 0.000 claims description 14
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 3
- 229910001868 water Inorganic materials 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a surface pickling coating TiO of a ternary anode material of a lithium ion battery2The method relates to the technical field of lithium ion batteries, and comprises the following steps: dissolving titanyl sulfate and sulfuric acid in deionized water to prepare a saturated titanyl sulfate solution; adding a ternary positive electrode material into a saturated titanium sulfate acyl solution, carrying out ultrasonic mixing to form a suspension, continuously stirring the suspension until the color of the suspension becomes light to obtain a brown precipitate, carrying out suction filtration, washing with alcohol, and carrying out vacuum drying to obtain a dried material; placing the dried material in a muffle furnace for heat treatment, and then cooling along with the furnace to obtain TiO2A coated ternary positive electrode material. The surface modification method carries out surface modification on the ternary cathode material through the controllable pickling coating process, reduces the residual alkali on the surface of the ternary material, and simultaneously forms uniform TiO on the surface2The coating layer can effectively improve the first efficiency, the discharge capacity, the cycling stability and the water absorption characteristic in the storage process of the ternary material, and has great application value.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of ternary cathode material of lithium ion battery surface acids
Wash bags cover TiO2Method.
Background technology
Ternary layered oxide material is because of its height ratio capacity, low cost and advantages of environment protection, by as lithium ion
Cell positive material is largely used to portable equipment, electric vehicle and energy storage field.But its poor thermal stability, stable circulation
Property and storge quality significantly limit its large-scale application in practical applications there is some potential safety problems.
Thermal stability, cyclical stability and the storge quality of commercial nickel-cobalt-manganese ternary material difference are largely due to now
Batch production technique cause ternary material surface to there are largely free lithiums, be easy to and H in air2O and CO2Reaction, in material table
Face generates LiOH and Li2CO3, lead to material pH value and surface residual alkali too high levels.LiOH can be with the LiPF in electrolyte6Reaction
Generate HF, Li2CO3High-temperature storage can be caused to generate serious inflatable, seriously affect the chemical property of material, while causing to pacify
Full hidden danger.
It is a large amount of real although the residual alkali of material surface can be efficiently reduced to tertiary cathode material washing in the prior art
The material tested after showing washing resists H in air2O/CO2Ability decline.Simultaneously processed to material progress wet method cladding
Cheng Zhong, the exposed region that material surface is not wrapped by are similar to the material after washing, these regions are excessive, the cycle performance of material
It will deteriorate.In addition, existing washing or cladding process are uncontrollable due to washing and coating process, lattice defect, packet are easily caused
It covers uneven, the discharge capacity of tertiary cathode material is caused to reduce, micro-crack is more also easy to produce in storage and discharge process, material
Stability and storge quality are not improved.
Invention content
Technical problems based on background technology, the present invention propose a kind of ternary cathode material of lithium ion battery surface
Pickling coats TiO2Method, solve existing batch production technique and cause the pH value on tertiary cathode material surface excessively high, surface residual alkali
Content is high and washes caused lattice defect in cladding process, the non-uniform problem of cladding.
A kind of ternary cathode material of lithium ion battery surface acid-washing proposed by the present invention coats TiO2Method, including it is following
Step:
S1, titanium sulfate acyl and sulfuric acid are dissolved in deionized water, prepare saturation titanium sulfate acyl solution;
S2, tertiary cathode material is added in saturation titanium sulfate acyl solution, ultrasonic mixing forms suspension, by suspension
Lasting stirring filters until suspension lighter, obtains tan precipitate, and with ethanol wash, vacuum drying obtains dried material;
S3, it dried material is placed in Muffle furnace is heat-treated, then furnace cooling obtains TiO2The ternary of cladding is just
Pole material.
Preferably, in the S1,1-1.2 parts of titanium sulfate acyls and 60-100 parts of 1mol/L sulfuric acid are dissolved in 2000 parts of deionizations
The titanium sulfate acyl solution of saturation is equipped in water.
Preferably, in the S2, tertiary cathode material is added in saturation titanium sulfate acyl solution, ultrasonic mixing 25-
40min forms suspension, and suspension is continued to stir 0.5-5h, until suspension lighter, obtains tan precipitate, is filtered,
With ethanol wash, it is dried in vacuo 6-10h at 65-75 DEG C, obtains dried material.
Preferably, in the S2, tertiary cathode material is nickle cobalt lithium manganate LiNixCoyMn1-x-yO2, wherein 0.6≤x<1,0
<y≤0.2。
Preferably, in the S2, the addition of tertiary cathode material ensures the TiO that reaction generates2Quality accounting for ternary just
The 0.1-10% of pole quality of materials.
Preferably, in the S3, heat treatment operation is as follows:In air atmosphere, it is warming up to 150-200 DEG C with 2 DEG C/min,
1.5-2h is kept the temperature, then 450-500 DEG C is warming up to 5 DEG C/min, keeps the temperature 5-8h, furnace cooling obtains TiO2The ternary of cladding is just
Pole material.
Preferably, the saturation titanium sulfate acyl solution can also be saturation titanyl nitrate solution, the saturation titanyl nitrate
Titanyl nitrate and nitric acid are dissolved in deionized water by solution to be formulated.
Advantageous effect:The present invention is reacted using titanium sulfate acyl (or titanyl nitrate) reversible hydrolysis,Saturation titanium sulfate acyl (or titanyl nitrate) solution is prepared, and is led to
The amount that sulfuric acid (nitric acid) is added in control is crossed, while reducing nickel-cobalt-manganese ternary material surface residual alkali, hydrolysis is promoted to send out to the right
It is raw, in its Surface Creation metatitanic acid, then again by the processing such as being filtered, washed, drying, be sintered after, formation coated with uniform
TiO2Ternary material, avoid and side reaction and the non-uniform situation of cladding occur during wet method cladding.In addition, passing through control
Pickling time processed can achieve the purpose that regulate and control coating thickness.The present invention by controllable pickling cladding process to ternary just
Pole material carries out surface modification, and while reducing ternary material surface residual alkali, uniform TiO is formed on surface2Clad can have
Effect improves the first charge discharge efficiency, discharge capacity, cyclical stability of ternary material, promotes ternary material and resists CO in air2And H2O
Ability, in the actual production process, have huge application value.
Description of the drawings
Fig. 1 is the principle schematic that present invention saturation titanium sulfate acyl solution acid wash bags cover process;
Fig. 2 is that tertiary cathode material surface acid-washing coats TiO in the embodiment of the present invention 22Preceding and cladding TiO2SEM figures afterwards.
Specific implementation mode
Fig. 1 is the principle schematic that present invention saturation titanium sulfate acyl solution acid wash bags cover process.It can be seen from the figure that three
There is largely free lithium in first positive electrode surface, it is easy to H in air2O and CO2Reaction, material surface generate LiOH and
Li2CO3, lead to material pH value and surface residual alkali too high levels.Pickling, a side are carried out using the sulfuric acid solution of saturation titanium sulfate acyl
Sulfuric acid in the solution of face and LiOH and Li2CO3Neutralization reaction occurs, reduces material surface residual alkali content, meanwhile, promote titanium sulfate
The reaction of acyl reversible hydrolysis occurs to the right, and uniform cladding is formed in material surface in its Surface Creation metatitanic acid, then through subsequent processing
TiO2Ternary material, avoid and side reaction and the non-uniform situation of cladding occur during wet method cladding.
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of ternary cathode material of lithium ion battery surface acid-washing proposed by the present invention coats TiO2Method, including it is following
Step:
S1,1 part of titanium sulfate acyl and 60 parts of 1mol/L sulfuric acid are dissolved in the titanium sulfate that saturation is equipped in 2000 parts of deionized waters
Acyl solution;
S2, by 5 parts of tertiary cathode material LiNi0.85Co0.1Mn0.05O2It is added in saturation titanium sulfate acyl solution, ultrasonic mixing
30min is uniformly mixed, and forms suspension, and suspension is continued to stir 0.5-1h, until suspension lighter, it is heavy to obtain brown
It forms sediment, filters, with ethanol wash 3 times, be dried in vacuo 6h at 65 DEG C, obtain dried material;
S3, dried material is placed on porcelain boat, is put into Muffle furnace and is heat-treated, in air atmosphere, with 2 DEG C/min
150 DEG C are warming up to, 1.5h is kept the temperature, then 450 DEG C are warming up to 5 DEG C/min, keeps the temperature 5h, furnace cooling obtains TiO2The three of cladding
First positive electrode.
To TiO obtained in the present embodiment2The tertiary cathode material of cladding is detected.After testing, surface Ti elements
Content is few, and Ti constituent contents are about 0.2wt% or so, and ternary electrode material surface pH is greatly reduced, volume change unobvious,
But cyclical stability is improved, and 1C recycles 100 capacity and reaches 190mAh/g.This explanation, at TiO (OH)2Have under colloidal sol protection
While effect reduces surface residual alkali, avoids wet method cladding process and side reaction occurs.Since pickling time is short, final TiO2Selection
Property cladding, it can be seen that particle surface has apparent thin spot under scanning electron microscope.
Embodiment 2
A kind of ternary cathode material of lithium ion battery surface acid-washing proposed by the present invention coats TiO2Method, including it is following
Step:
S1,1 part of titanium sulfate acyl and 60 parts of 1mol/L sulfuric acid are dissolved in the titanium sulfate that saturation is equipped in 2000 parts of deionized waters
Acyl solution;
S2, by 5 parts of tertiary cathode material LiNi0.85Co0.1Mn0.05O2It is added in saturation titanium sulfate acyl solution, ultrasonic mixing
30min is uniformly mixed, and forms suspension, and suspension is continued to stir 4h, until suspension lighter, obtains tan precipitate,
It filters, with ethanol wash 3 times, is dried in vacuo 6h at 70 DEG C, obtains dried material;
S3, dried material is placed on porcelain boat, is put into Muffle furnace and is heat-treated, in air atmosphere, with 2 DEG C/min
150 DEG C are warming up to, 1.5h is kept the temperature, then 500 DEG C are warming up to 5 DEG C/min, keeps the temperature 5h, furnace cooling obtains TiO2The three of cladding
First positive electrode.
To TiO obtained in the present embodiment2The tertiary cathode material of cladding is detected.After testing, surface Ti elements
Content is about 2wt%, and ternary electrode material surface pH is greatly reduced, and capacity and cyclical stability are improved, and Fig. 2 is ternary
The front and back SEM of positive electrode cladding compares photo, it is as can be seen from the figure coated after material granule surface is more compact, surface becomes
It obtains smoothly, can detect that Ti elements are uniformly distributed from EDS Elemental redistributions.
Embodiment 3
A kind of ternary cathode material of lithium ion battery surface acid-washing proposed by the present invention coats TiO2Method, including it is following
Step:
S1,1 part of titanyl nitrate and 100 parts of 1mol/L nitric acid are dissolved in the Nitric Acid Oxidation that saturation is equipped in 2000 parts of deionized waters
Titanium solution;
S2, by 10 parts of tertiary cathode material LiNi0.85Co0.1Mn0.05O2It is added in saturation titanyl nitrate solution, ultrasonic mixing
30min is uniformly mixed, and forms suspension, and suspension is continued to stir 2h, until suspension lighter, obtains tan precipitate,
It filters, with ethanol wash 3 times, is dried in vacuo 6h at 75 DEG C, obtains dried material;
S3, dried material is placed on porcelain boat, is put into Muffle furnace and is heat-treated, in air atmosphere, with 2 DEG C/min
150 DEG C are warming up to, 1.5h is kept the temperature, then 500 DEG C are warming up to 5 DEG C/min, keeps the temperature 5h, furnace cooling obtains TiO2The three of cladding
First positive electrode.
To TiO obtained in the present embodiment2The tertiary cathode material of cladding is detected.After testing, surface Ti elements
Content is about 0.2wt%, and pH is greatly reduced, and capacity and cyclical stability are improved, 0.1C, 1C, 2C discharge capacity up to 215,
198 and 192mAh/g, 0.1C head effects recycle 100 capacity retention ratios up to 98.5% up to 92.1%.From the SEM photograph after cladding
In it can be seen that particle surface is more compact, surface is smoothened, can detect that Ti elements are uniformly distributed from EDS Elemental redistributions.
Compare Examples 1 and 2, and the pickling covered effect of the embodiment is more preferable, this oxidisability for being possible as dust technology is compared
Dilute sulfuric acid is weaker, influences smaller to ternary material particle surface.
Embodiment 4
A kind of ternary cathode material of lithium ion battery surface acid-washing proposed by the present invention coats TiO2Method, including it is following
Step:
S1,1.2 parts of titanium sulfate acyls and 100 parts of 1mol/L sulfuric acid are dissolved in the sulfuric acid that saturation is equipped in 2000 parts of deionized waters
Titanium acyl solution;
S2, by 6 parts of tertiary cathode material LiNi0.85Co0.1Mn0.05O2It is added in saturation titanium sulfate acyl solution, ultrasonic mixing
25min is uniformly mixed, and forms suspension, and suspension is continued to stir 3.5h, until suspension lighter, it is heavy to obtain brown
It forms sediment, filters, with ethanol wash 3 times, be dried in vacuo 8h at 65 DEG C, obtain dried material;
S3, dried material is placed on porcelain boat, is put into Muffle furnace and is heat-treated, in air atmosphere, with 2 DEG C/min
180 DEG C are warming up to, 1.5h is kept the temperature, then 480 DEG C are warming up to 5 DEG C/min, keeps the temperature 7h, furnace cooling obtains TiO2The three of cladding
First positive electrode.
Embodiment 5
A kind of ternary cathode material of lithium ion battery surface acid-washing proposed by the present invention coats TiO2Method, including it is following
Step:
S1,1 part of titanium sulfate acyl and 60 parts of 1mol/L sulfuric acid are dissolved in the titanium sulfate that saturation is equipped in 2000 parts of deionized waters
Acyl solution;
S2, by 5 parts of tertiary cathode material LiNi0.85Co0.1Mn0.05O2It is added in saturation titanium sulfate acyl solution, ultrasonic mixing
40min is uniformly mixed, and forms suspension, and suspension is continued to stir 5h, until suspension lighter, obtains tan precipitate,
It filters, with ethanol wash 3 times, is dried in vacuo 10h at 70 DEG C, obtains dried material;
S3, dried material is placed on porcelain boat, is put into Muffle furnace and is heat-treated, in air atmosphere, with 2 DEG C/min
200 DEG C are warming up to, 2h is kept the temperature, then 490 DEG C are warming up to 5 DEG C/min, keeps the temperature 8h, furnace cooling obtains TiO2The ternary of cladding
Positive electrode.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of ternary cathode material of lithium ion battery surface acid-washing coats TiO2Method, which is characterized in that including following step
Suddenly:
S1, titanium sulfate acyl and sulfuric acid are dissolved in deionized water, prepare saturation titanium sulfate acyl solution;
S2, tertiary cathode material is added in saturation titanium sulfate acyl solution, ultrasonic mixing forms suspension, suspension is continued
Stirring filters until suspension lighter, obtains tan precipitate, and with ethanol wash, vacuum drying obtains dried material;
S3, it dried material is placed in Muffle furnace is heat-treated, then furnace cooling obtains TiO2The tertiary cathode material of cladding
Material.
2. ternary cathode material of lithium ion battery surface acid-washing according to claim 1 coats TiO2Method, feature exists
In, in the S1, by 1-1.2 parts of titanium sulfate acyls and 60-100 parts of 1mol/L sulfuric acid be dissolved in 2000 parts of deionized waters be equipped be saturated
Titanium sulfate acyl solution.
3. ternary cathode material of lithium ion battery surface acid-washing according to claim 1 coats TiO2Method, feature exists
In, in the S2, tertiary cathode material is added in saturation titanium sulfate acyl solution, ultrasonic mixing 25-40min forms suspension,
Suspension is continued to stir 0.5-5h, until suspension lighter, tan precipitate is obtained, filters, with ethanol wash, in 65-
It is dried in vacuo 6-10h at 75 DEG C, obtains dried material.
4. ternary cathode material of lithium ion battery surface acid-washing according to claim 1 coats TiO2Method, feature exists
In in the S2, tertiary cathode material is nickle cobalt lithium manganate LiNixCoyMn1-x-yO2, wherein 0.6≤x<1,0<y≤0.2.
5. ternary cathode material of lithium ion battery surface acid-washing according to claim 1 coats TiO2Method, feature exists
In in the S2, the addition of tertiary cathode material ensures the TiO that reaction generates2Quality account for tertiary cathode material quality
0.1-10%.
6. ternary cathode material of lithium ion battery surface acid-washing according to claim 1 coats TiO2Method, feature exists
In in the S3, heat treatment operation is as follows:In air atmosphere, it is warming up to 150-200 DEG C with 2 DEG C/min, keeps the temperature 1.5-2h,
It is warming up to 450-500 DEG C with 5 DEG C/min again, keeps the temperature 5-8h, furnace cooling obtains TiO2The tertiary cathode material of cladding.
7. coating TiO according to any ternary cathode material of lithium ion battery surface acid-washings of claim 1-62Method,
It is characterized in that, the saturation titanium sulfate acyl solution can also be saturation titanyl nitrate solution, and the saturation titanyl nitrate solution is
Titanyl nitrate and nitric acid be dissolved in and is formulated in deionized water.
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