CN105375005A - Cathode material for lithium ion batteries containing nano-scale solid solution and preparation method thereof - Google Patents
Cathode material for lithium ion batteries containing nano-scale solid solution and preparation method thereof Download PDFInfo
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- CN105375005A CN105375005A CN201510694674.0A CN201510694674A CN105375005A CN 105375005 A CN105375005 A CN 105375005A CN 201510694674 A CN201510694674 A CN 201510694674A CN 105375005 A CN105375005 A CN 105375005A
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- solid solution
- lithium
- ion batteries
- lithium ion
- mixed solution
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 71
- 239000006104 solid solution Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010406 cathode material Substances 0.000 title abstract 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 24
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011787 zinc oxide Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000010405 anode material Substances 0.000 claims description 28
- 239000006183 anode active material Substances 0.000 claims description 26
- 229910018553 Ni—O Inorganic materials 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 abstract description 6
- 239000006182 cathode active material Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 2
- 238000000498 ball milling Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/624—Electric conductive 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a cathode material for lithium ion batteries containing a nano-scale solid solution. The preparation method comprises the following steps: carrying out wet-process ball-milling on zinc oxide, titanium oxide and nickel oxide, drying, sintering at the temperature of 800-1200 DEG C, and then grinding into nano-scale solid solution powder; adding the nano-scale solid solution powder in a solvent to form a first mixed solution through uniform dispersion; uniformly dispersing an active cathode material for the lithium ion batteries into the first mixed solution so that the first mixed solution is wrapped on the surface of the active cathode material for the lithium ion batteries to form a second mixed solution; and drying the second mixed solution to obtain a mixture material, calcining, cooling and smashing the mixture material, and filtering to obtain the cathode material for the lithium ion batteries. The invention also relates to the cathode material for the lithium ion batteries obtained through the method.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries containing nano-scale solid solution and preparation method thereof.
Background technology
Lithium ion battery has the advantages such as specific capacity is high, voltage is high, security performance is good, is widely used in the products such as mobile phone, camera, notebook computer, electric tool, electric bicycle and electric automobile.Along with electronic product fast development to the energy of lithium ion battery and power requirement more and more higher, and the positive electrode of lithium ion battery is the important component part of lithium ion battery, is the major influence factors of performance of lithium ion battery.
The maximum lithium ion anode material of current application mainly contains cobalt acid lithium, lithium nickelate, LiMn2O4 and cobalt nickel lithium manganate ternary material.Cobalt acid lithium is industrialization the earliest and business-like material, and the chemical property of cobalt acid lithium is comparatively stablized, conduct electricity very well, voltage platform is higher, good cycle, compacted density can reach 4.0g/cm
3but the specific capacity of cobalt acid lithium is relatively low, and only have 140mAh/g, and cobalt toxicity is comparatively large, cobalt resource is rare, expensive, and its over-charge safety performance is poor.Lithium nickelate synthesis difficulty, the poor reproducibility of material; Although layered lithium manganate has higher specific capacity, structural stability is poor, and the LiMn2O4 specific capacity of spinel-type is lower, and the structure under high temperature has to be strengthened.Although cobalt nickel lithium manganate ternary material combines the performance of cobalt acid lithium, lithium nickelate and LiMn2O4, there is Heat stability is good, the features such as under high potential the high and cost of material of specific capacity is low, but ternary material voltage platform is lower, platform discharge time is short, compacted density also lower, cycle performance is poor.
In order to improve positive electrode, conventional method carries out coating modification to positive pole material surface.At present, the Surface coating reported comprises: containing metal oxides such as magnesium, aluminium, zirconium, titaniums, containing metal fluorides etc. such as aluminium, magnesium, titanium, zirconiums.Metal oxide effectively can stop the reaction of positive electrode and electrolyte, improves the cycle performance of lithium ion battery; Metal fluoride layer can suppress the hydrofluoric acid of electrolyte and the reaction of active material, reduce the capacity attenuation of battery in charge and discharge cycles, but metallic compound does not have good conductivity, the diffusion velocity of lithium ion in this coating layer is slower, positive electrode conductive capability is caused to be deteriorated, increase the internal resistance of cell, have impact on the discharge-rate of battery, reduce the chemical property of battery.
Summary of the invention
The invention provides a kind of anode material for lithium-ion batteries containing nano-scale solid solution and preparation method thereof, can effectively solve the problem.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprising:
After zinc oxide, titanium oxide and nickel oxide are carried out wet ball grinding, drying, sinter at 800 ~ 1200 DEG C, then grind to form nanoscale solid solution powder;
Described nanoscale solid solution powder is added dispersed formation first mixed solution in solvent;
Evenly spread to by anode active material of lithium ion battery in described first mixed solution, the surface making described first mixed solution evenly be coated on described anode active material of lithium ion battery forms the second mixed solution; And
Described second mixed solution drying is obtained mixture material, by the calcining of described mixture material, cooling grinding and sieving obtains described anode material for lithium-ion batteries.
Further, the mass ratio of described zinc oxide, titanium oxide and nickel oxide is 1 ~ 5:1:1 ~ 5.
Further, the gross mass of described zinc oxide, titanium oxide and nickel oxide and the mass ratio of described anode active material of lithium ion battery are 0.001 ~ 0.1:1.
Further, the gross mass of described zinc oxide, titanium oxide and nickel oxide and the mass ratio of described anode active material of lithium ion battery are 0.01 ~ 0.05:1.
Further, described solvent is easy volatile solvent.
Further, described step nanoscale solid solution powder being added dispersed formation first mixed solution in solvent comprises: added in solvent by nanoscale solid solution powder and carry out high-speed stirred 10-60 minute; Then ultrasonic 5 ~ 30 minutes are carried out; And repeat high-speed stirred, ultrasonic circulation 3 ~ 5 times successively, thus form homodisperse first mixed solution.
Further, described the step that mixture material is calcined to be comprised: be air or oxygen atmosphere in calcination atmosphere, calcining heat is under the condition of 500 ~ 800 DEG C, calcining 3 ~ 10h.
The present invention further provides a kind of anode material for lithium-ion batteries, wherein, comprise anode active material of lithium ion battery and be coated on the nanoscale Zn-Ti-Ni-O solid solution powder on described anode active material of lithium ion battery surface.
Further, the mass ratio of described nanoscale Zn-Ti-Ni-O solid solution powder and described anode active material of lithium ion battery is 0.001 ~ 0.1:1.
Further, in described nanoscale Zn-Ti-Ni-O solid solution powder, the mass ratio of zinc oxide, titanium oxide and nickel oxide is 1 ~ 5:1:1 ~ 5.
Anode material for lithium-ion batteries provided by the invention, there is following beneficial effect: first, by at surface of positive electrode active material clad nano level Zn-Ti-Ni-O solid solution powder, coating layer can be made while isolated electrolyte and positive electrode active materials, lithium ion freely to be passed through, thus while completing discharge and recharge, avoid the decomposition of electrolyte, improve cycle performance and the stability of lithium ion battery.Secondly, Zn-Ti-Ni-O solid solution powder has good conductivity, can be greatly increased the high rate performance of positive electrode by the electronic conductivity improving material.Finally, when internal temperature of battery reaches the Curie temperature of Zn-Ti-Ni-O solid solution powder, the resistivity of Zn-Ti-Ni-O solid solution powder increases rapidly thus blocks the discharge and recharge reaction of battery, and the security performance of lithium battery is improved.In addition, the preparation method of anode material for lithium-ion batteries provided by the invention also has simple, is easy to the features such as suitability for industrialized production.
Accompanying drawing explanation
Preparation method's flow chart of the anode material for lithium-ion batteries that Fig. 1 provides for the embodiment of the present invention.
The first charge-discharge curve chart of the anode material for lithium-ion batteries that Fig. 2 provides for the embodiment of the present invention 1.
The cycle charge-discharge curve chart of the anode material for lithium-ion batteries that Fig. 3 provides for the embodiment of the present invention 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.Be understandable that, specific embodiment described herein is only for explaining the present invention, but not limitation of the invention.It also should be noted that, for convenience of description, illustrate only part related to the present invention in accompanying drawing but not entire infrastructure.
Please refer to Fig. 1, the invention provides a kind of preparation method of anode material for lithium-ion batteries, comprising:
S1, after zinc oxide, titanium oxide and nickel oxide are carried out wet ball grinding, drying, sinters, then grinds to form nanoscale solid solution powder at 800 ~ 1200 DEG C;
S2, adds dispersed formation first mixed solution in solvent by described nanoscale solid solution powder;
S3, evenly spreads to anode active material of lithium ion battery in described first mixed solution, and the surface making described first mixed solution evenly be coated on described anode active material of lithium ion battery forms the second mixed solution; And
S4, obtains mixture material by described second mixed solution drying, is calcined by described mixture material, cools and grinding and sieving obtains described anode material for lithium-ion batteries.
In step sl, experiment proves, described sintering temperature preferably 900 ~ 1000 DEG C; Preferred, described sintering temperature is 950 ~ 1000 DEG C.The time of described sintering is preferably 2-10h, preferred, and described sintering time is 3-5h.The mass ratio of described zinc oxide, titanium oxide and nickel oxide can combination in any, and can according to the concrete content ratio of the maximum operation (service) temperature determination zinc oxide of battery, titanium oxide and nickel oxide.Preferably, the mass ratio of described zinc oxide, titanium oxide and nickel oxide is 1 ~ 5:1:1 ~ 5.Preferred, the mass ratio of described zinc oxide, titanium oxide and nickel oxide is 1 ~ 2:1:1 ~ 2.
In step s 2, described solvent is selected from solvent that is volatile and that do not react with zinc oxide, titanium oxide, nickel oxide and positive active material.Described solvent is for disperseing described nanoscale solid solution powder.Described solvent can be methyl alcohol, ethanol, water, acetone, propyl alcohol etc.
Further, described step nanoscale solid solution powder being added dispersed formation first mixed solution in solvent can comprise:
S21, adds nanoscale solid solution powder in solvent and carries out high-speed stirred 10-60 minute;
S22, then carries out ultrasonic 5 ~ 30 minutes; And
S23, repeats step 21 and S22,3 ~ 5 times, thus forms homodisperse first mixed solution.Wherein, described high-speed stirred is that rotating speed is more than or equal to 60 turns/min.
In step s3, preferably, the gross mass of described zinc oxide, titanium oxide and nickel oxide and the mass ratio of described anode active material of lithium ion battery are 0.001 ~ 0.1:1.Preferred, the gross mass of described zinc oxide, titanium oxide and nickel oxide and the mass ratio of described anode active material of lithium ion battery are 0.01 ~ 0.05:1.Described anode active material of lithium ion battery can be one or more the mixture in nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, cobalt acid lithium, LiFePO4, lithium ferric manganese phosphate, lithium nickel cobalt dioxide or nickel ion doped.Described anode active material of lithium ion battery can add in described first mixed solution under the condition of high-speed stirred or ultrasonic disperse, thus described anode active material of lithium ion battery is evenly spread in described first mixed solution, and the surface making described first mixed solution evenly be coated on described anode active material of lithium ion battery forms the second mixed solution.
In step s 4 which, 4-8h is preferably described drying time.Described step of being calcined by mixture material is preferably: be air or oxygen atmosphere in calcination atmosphere, calcining heat is under the condition of 500 ~ 800 DEG C, calcining 3 ~ 10h.Preferred, described calcining heat is 500 ~ 600 DEG C.
The present invention further provides a kind of anode material for lithium-ion batteries, comprise anode active material of lithium ion battery and be coated on the nanoscale Zn-Ti-Ni-O solid solution powder on described anode active material of lithium ion battery surface.
The mass ratio of described nanoscale Zn-Ti-Ni-O solid solution powder and described anode active material of lithium ion battery is 0.001 ~ 0.1:1.Preferably, the mass ratio of described nanoscale Zn-Ti-Ni-O solid solution powder and described anode active material of lithium ion battery is 0.01 ~ 0.05:1.Further, in described nanoscale Zn-Ti-Ni-O solid solution powder, the mass ratio of zinc oxide, titanium oxide and nickel oxide is 1 ~ 5:1:1 ~ 5.Preferably, in described nanoscale Zn-Ti-Ni-O solid solution powder, the mass ratio of zinc oxide, titanium oxide and nickel oxide is 1 ~ 2:1:1 ~ 2.
Anode material for lithium-ion batteries provided by the invention, there is following beneficial effect: first, by at surface of positive electrode active material clad nano level Zn-Ti-Ni-O solid solution powder, coating layer can be made while isolated electrolyte and positive electrode active materials, lithium ion freely to be passed through, thus while completing discharge and recharge, avoid the decomposition of electrolyte, improve cycle performance and the stability of lithium ion battery.Secondly, Zn-Ti-Ni-O solid solution powder has good conductivity, can be greatly increased the high rate performance of positive electrode by the electronic conductivity improving material.Finally, when internal temperature of battery reaches the Curie temperature of Zn-Ti-Ni-O solid solution powder, the resistivity of Zn-Ti-Ni-O solid solution powder increases rapidly thus blocks the discharge and recharge reaction of battery, and the security performance of lithium battery is improved.In addition, the preparation method of anode material for lithium-ion batteries provided by the invention also has simple, is easy to the features such as suitability for industrialized production.
Embodiment 1:
Zinc oxide, titanium oxide and nickel oxide are carried out wet-mixed by the stoichiometric proportion batching of 1:1:1, mixes rear drying, sinter 3h, grinding at 1000 DEG C after, obtain nanoscale Zn-Ti-Ni-O solid solution powder; Added in absolute ethyl alcohol by nanoscale Zn-Ti-Ni-O solid solution powder and carry out high-speed stirred 30 minutes, then carry out ultrasonic 10 minutes, high-speed stirred, ultrasonic circulation 5 times, mixes formation first mixed solution successively; By positive electrode active materials LiNi
0.8co
0.15al
0.05o
2add under the condition of high-speed stirred in the first mixed solution, make clad material evenly be coated on active LiNi
0.8co
0.15al
0.05o
2surface, then by dry for mixture 6h, after dried solid material is calcined 10h at 500 DEG C, cools, pulverizes, sieving obtains positive electrode.
Please refer to Fig. 2-3, adopt blue electric battery test system to test at 25 DEG C the electrochemical property test of the positive electrode obtained, test voltage scope is 3V ~ 4.3V; High rate performance test condition: once, 0.2C charging 0.5C/1C/5C/10C respectively discharges once in 0.2C discharge and recharge; Cycle performance test condition: carry out discharge and recharge with 1C multiplying power, circulates 400 weeks, investigates capability retention.The specific discharge capacity of positive electrode under 0.2C multiplying power is 192.4mAh/g, under 0.5C multiplying power, specific discharge capacity is 189mAh/g, specific discharge capacity under 1C multiplying power is 183.5mAh/g, specific discharge capacity under 5C multiplying power is 170.2mAh/g, specific discharge capacity under 10C multiplying power is 165.7mAh/g, 10C/0.2C electric discharge ratio is 86.1%, and high rate performance is better.1C charge and discharge cycles 400 weeks capability retentions are greater than 95%, and cycle performance is better.
Embodiment 2:
Zinc oxide, titanium oxide and nickel oxide are carried out wet-mixed by the stoichiometric proportion batching of 2:1:2, mixes rear drying, after 800 DEG C of sintering 5h, grinding, obtain nanoscale Zn-Ti-Ni-O solid solution powder; Nanoscale Zn-Ti-Ni-O solid solution powder is added in deionized water and carries out high-speed stirred 30 minutes, then carry out ultrasonic 10 minutes, circulate 5 times, mix formation first mixed solution; By positive electrode active materials LiNi
0.5co
0.2mn
0.3o
2add under the condition of high-speed stirred in the first mixed solution, make clad material evenly be coated on active material LiNi
0.5co
0.2mn
0.3o
2surface, then by dry for mixture 8h, after dried solid material is calcined 8h at 600 DEG C, cools, pulverizes, sieving obtains positive electrode.
Embodiment 3:
Zinc oxide, titanium oxide and nickel oxide are carried out wet-mixed by the stoichiometric proportion batching of 3:2:5, mixes rear drying, sinter 5h, grinding at 1200 DEG C after, obtain nanoscale Zn-Ti-Ni-O solid solution powder; Nanoscale Zn-Ti-Ni-O solid solution powder is added in absolute ethyl alcohol and carries out high-speed stirred 30 minutes, then carry out ultrasonic 10 minutes, circulate 3 times, mix formation first mixed solution; By positive electrode active materials LiFePO
4add in above-mentioned mixed solution under the condition of high-speed stirred, make clad material evenly be coated on basis material LiFePO
4surface, then by dry for mixture 7h, after dried solid material is calcined 6h at 800 DEG C, cools, pulverizes, sieving obtains positive electrode.
Note, above are only preferred embodiment of the present invention and institute's application technology principle.Skilled person in the art will appreciate that and the invention is not restricted to specific embodiment described here, various obvious change can be carried out for a person skilled in the art, readjust and substitute and can not protection scope of the present invention be departed from.Therefore, although be described in further detail invention has been by above embodiment, the present invention is not limited only to above embodiment, when not departing from the present invention's design, can also comprise other Equivalent embodiments more, and scope of the present invention is determined by appended right.
Claims (10)
1., containing a preparation method for the anode material for lithium-ion batteries of nano-scale solid solution, it is characterized in that, comprising:
After zinc oxide, titanium oxide and nickel oxide are carried out wet ball grinding, drying, sinter at 800 ~ 1200 DEG C, then grind to form nanoscale solid solution powder;
Described nanoscale solid solution powder is added dispersed formation first mixed solution in solvent;
Evenly spread to by anode active material of lithium ion battery in described first mixed solution, the surface making described first mixed solution evenly be coated on described anode active material of lithium ion battery forms the second mixed solution; And
Described second mixed solution drying is obtained mixture material, by the calcining of described mixture material, cooling grinding and sieving obtains described anode material for lithium-ion batteries.
2. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 1, it is characterized in that, the mass ratio of described zinc oxide, titanium oxide and nickel oxide is 1 ~ 5:1:1 ~ 5.
3. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 1, it is characterized in that, the gross mass of described zinc oxide, titanium oxide and nickel oxide and the mass ratio of described anode active material of lithium ion battery are 0.001 ~ 0.1:1.
4. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 3, it is characterized in that, the gross mass of described zinc oxide, titanium oxide and nickel oxide and the mass ratio of described anode active material of lithium ion battery are 0.01 ~ 0.05:1.
5. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 1, it is characterized in that, described solvent is easy volatile solvent.
6. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 1, it is characterized in that, described step nanoscale solid solution powder being added dispersed formation first mixed solution in solvent comprises:
Nanoscale solid solution powder is added in solvent and carries out high-speed stirred 10-60 minute;
Then ultrasonic 5 ~ 30 minutes are carried out; And repeat high-speed stirred, ultrasonic circulation 3 ~ 5 times successively, thus form homodisperse first mixed solution.
7. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 1, is characterized in that, the described step by mixture material calcining comprises:
Be air or oxygen atmosphere in calcination atmosphere, calcining heat is under the condition of 500 ~ 800 DEG C, calcining 3 ~ 10h.
8., containing an anode material for lithium-ion batteries for nano-scale solid solution, it is characterized in that, comprise anode active material of lithium ion battery and be coated on the nanoscale Zn-Ti-Ni-O solid solution powder on described anode active material of lithium ion battery surface.
9. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 8, it is characterized in that, the mass ratio of described nanoscale Zn-Ti-Ni-O solid solution powder and described anode active material of lithium ion battery is 0.001 ~ 0.1:1.
10. the anode material for lithium-ion batteries containing nano-scale solid solution according to claim 8, it is characterized in that, in described nanoscale Zn-Ti-Ni-O solid solution powder, the mass ratio of zinc oxide, titanium oxide and nickel oxide is 1 ~ 5:1:1 ~ 5.
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