CN105006552A - Surface-coated anode material for lithium ion battery and preparation method thereof - Google Patents

Surface-coated anode material for lithium ion battery and preparation method thereof Download PDF

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Publication number
CN105006552A
CN105006552A CN201510311568.XA CN201510311568A CN105006552A CN 105006552 A CN105006552 A CN 105006552A CN 201510311568 A CN201510311568 A CN 201510311568A CN 105006552 A CN105006552 A CN 105006552A
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anode material
lithium
ion batteries
preparation
lini
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毛玉琴
韩珽
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Haining Mei Darui New Material Science And Technology Ltd
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Haining Mei Darui New Material Science And Technology Ltd
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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
    • H01M4/52—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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a surface-coated anode material for a lithium ion battery and a preparation method thereof. The general chemical formula of the anode material is LiNi1-a-bCoaAlbO2/M, wherein 0.1<a<0.3 and 0.01<b<0.2, M is a coating layer, the coating layer is AlxZn1-xO, and 0<x<=0.1. In the LiNi1-a-bCoaAlbO2, a=0.15, and b=0.05. The weight ratio of the coating layer to the LiNi1-a-bCoaAlbO2 is 0.001-0.1:1. The preparation method of the anode material comprises the following steps of mixing, coating, spray drying, calcining and the like. The surface-coated anode material for the lithium ion battery and the preparation method thereof have the advantages of being simple and practical in synthetic process, low in equipment requirement, free from pollution and good in industrial application prospect; the large-current discharging characteristic and high-temperature characteristic of the material are good, the powder size distribution is uniform, and good dispersity and mobility are achieved.

Description

Anode material for lithium-ion batteries of a kind of surface coating modification and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery, particularly relate to anode material for lithium-ion batteries of a kind of surface coating modification and preparation method thereof.
Background technology
Lithium ion battery is owing to having higher energy density, long cycle life, the plurality of advantages such as lower self-discharge rate and environmental friendliness, it has been current mobile phone, digital camera, the reference power supply of the mobile communication equipments such as notebook computer, simultaneously, at new-energy automobile, also placed high hopes by people in the energy storage aspect of wind power generation and solar power generation.But if will successfully apply in these areas, lithium ion battery just must in battery price, fail safe, and further lifting is done in the aspects such as useful life.
Nickel cobalt lithium aluminate material and the LiCoO used at present 2, LiMn 2o 4, LiFePO 4and LiNi 1/3mn 1/3co 1/3o 2etc. comparing, there is higher specific capacity, larger energy density and lower cost, being thus subject to paying close attention to of researcher.But the shortcomings such as the moisture absorption of this material is high, cycle performance is stable not make it be subject to a definite limitation in application aspect.In order to solve these problems above-mentioned, researcher proposes the method for various modification, as Surface coating, doping vario-property, acid treatment and circulation preliminary treatment etc.Wherein, coatedly the most effective modified method is considered to.Namely coating modification is adopt liquid phase or solid phase method, other materials of coated one deck outside nickel cobalt lithium aluminate material, improves the cycle performance of positive electrode, high rate performance, overcharging resisting performance and thermal stability etc. by the surface state changing electrode.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.
Summary of the invention
Object of the present invention aims to provide positive pole material of secondary lithium battery of a kind of surface coating modification and preparation method thereof.By to LiNi 1-a-bco aal bo 2it is coated that positive electrode carries out finishing, and the cycle performance of lithium battery and security performance are improved.
The object of the invention is to be achieved through the following technical solutions:
First aspect, a kind of anode material for lithium-ion batteries of surface coating modification, chemical general formula is LiNi 1-a-bco aal bo 2/ M, wherein 0.1<a<0.3,0.01<b<0.2, M are coating layer, it is characterized in that, described coating layer is Al xzn 1-xo, wherein 0 < x≤0.1.
As preferably, described LiNi 1-a-bco aal bo 2in a=0.15, b=0.05.
As preferably, described coating layer and LiNi 1-a-bco aal bo 2mass ratio be 0.001 ~ 0.1:1.
As further preferred, described coating layer and LiNi 1-a-bco aal bo 2mass ratio be 0.001 ~ 0.05:1.
Second aspect, a kind of preparation method of anode material for lithium-ion batteries of a kind of surface coating modification as described in relation to the first aspect, is characterized in that, comprise the following steps:
(1) insoluble aluminum contained compound of Nano grade and zinc compound are added to the water and carry out Homogeneous phase mixing and form mixed liquor;
by positive electrode LiNi 1-a-bco aal bo 2step is joined under the condition stirred in mixed liquor in, make clad material evenly be coated on active material LiNi 1-a-bco aal bo 2particle surface;
by step the mixture of gained, by spraying dry, after then dried solid material being calcined a period of time at a certain temperature, cools, pulverizes, sieving obtains positive electrode.
As preferably, the aluminum contained compound of described Nano grade is one or more in alundum (Al2O3), aluminium hydroxide and aluminium nitride.
As preferably, the zinc compound of described Nano grade is zinc oxide.
As preferably, described LiNi 1-a-bco aal bo 2in a=0.15, b=0.05.
As preferably, described LiNi 1-a-bco aal bo 2d50 be 5 ~ 25 μm, D10>=5 μm, D90≤30 μm.
As preferably, described calcining heat is 500 ~ 800 DEG C, and calcination time is 3 ~ 10h, and calcination atmosphere is oxygen atmosphere.
Compared with prior art, great advantage of the present invention and beneficial effect as follows:
(1) the present invention adopts cheapness, the Al element doping ZnO of environmental protection comes LiNi 1-a-bco aal bo 2material carries out finishing, improves the heavy-current discharge characteristic of material on the one hand by improving electron conductivity, and the existence of this coating layer also can prevent electrolyte at active material LiNi on the other hand 1-a-bco aal bo 2the decomposition on surface, and then improve its hot properties.
the present invention adopts spraying dry, and drying efficiency is high, and diameter of particle is evenly distributed, and has good dispersiveness and mobility.
synthesis technique of the present invention is simple, and equipment requirement is low, pollution-free, has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the anode material for lithium-ion batteries first charge-discharge curve chart of the surface coating modification of embodiment 1.
Fig. 2 is the anode material for lithium-ion batteries cycle charge-discharge curve chart of the surface coating modification of embodiment 1.
Embodiment
In order to have darker understanding to the present invention; below in conjunction with embodiment, technical scheme is clearly and completely described; but embodiments of the invention are only used to explain the present invention; and unrestricted the present invention; the every other case study on implementation that those skilled in the art obtain under the prerequisite not making creative work, all belongs to protection scope of the present invention.
Embodiment 1:
The alundum (Al2O3) of Nano grade and the zinc oxide of Nano grade are joined in deionized water and carries out high-speed stirred, mix and form Homogeneous phase mixing liquid; By positive electrode LiNi 0.8co 0.15al 0.05o 2join in above-mentioned mixed liquor under the condition stirred, make clad material evenly be coated on active material LiNi 0.8co 0.15al 0.05o 2particle surface; By mixture by spraying dry, after then dried solid material being calcined 6h at 500 DEG C, cool, pulverize, sieving obtains the positive electrode of modification.Wherein active material LiNi 0.8co 0.15al 0.05o 2d10=6.28 μm, D50=18.75 μm, D90=28.40 μm.
The electrochemical property test of material adopts blue electric battery test system to test at 25 DEG C, high rate performance test condition: test voltage scope be 3V ~ 4.3V, 0.1C discharge and recharge once; Cycle performance test condition: test voltage scope is 3V ~ 4.3V, carries out discharge and recharge with 1C multiplying power, circulates 500 weeks, investigates capability retention.The specific discharge capacity of material under 0.1C multiplying power is that 195.6mAh/g, 1C charge and discharge cycles 500 weeks capability retentions are greater than 93%, and cycle performance is better.
Embodiment 2:
The aluminium hydroxide of Nano grade and the zinc oxide of Nano grade are joined in deionized water and carries out high-speed stirred, mix and form Homogeneous phase mixing liquid; By positive electrode LiNi 0.8co 0.15al 0.05o 2join in above-mentioned mixed liquor under the condition stirred, make clad material evenly be coated on active material LiNi 0.8co 0.15al 0.05o 2particle surface; By mixture by spraying dry, after then dried solid material being calcined 8h at 600 DEG C, cool, pulverize, sieving obtains the positive electrode of modification.Wherein active material LiNi 0.8co 0.15al 0.05o 2d10=5.43 μm, D50=20.76 μm, D90=27.35 μm.
Embodiment 3:
The aluminium hydroxide of Nano grade and the zinc oxide of Nano grade are joined in deionized water and carries out high-speed stirred, mix and form Homogeneous phase mixing liquid; By positive electrode LiNi 0.8co 0.15al 0.05o 2join in above-mentioned mixed liquor under the condition stirred, make clad material evenly be coated on active material LiNi 0.8co 0.15al 0.05o 2particle surface; By mixture by spraying dry, after then dried solid material being calcined 5h at 800 DEG C, cool, pulverize, sieving obtains the positive electrode of modification.Wherein active material LiNi 0.8co 0.15al 0.05o 2d10=7.33 μm, D50=15.87 μm, D90=21.64 μm.

Claims (10)

1. an anode material for lithium-ion batteries for surface coating modification, chemical general formula is LiNi 1-a-bco aal bo 2/ M, wherein 0.1<a<0.3,0.01<b<0.2, M are coating layer, it is characterized in that, described coating layer is Al xzn 1-xo, wherein 0 < x≤0.1.
2. the anode material for lithium-ion batteries of surface coating modification according to claim 1, is characterized in that, described LiNi 1-a-bco aal bo 2in a=0.15, b=0.05.
3. the anode material for lithium-ion batteries of surface coating modification according to claim 1, is characterized in that, described coating layer and LiNi 1-a-bco aal bo 2mass ratio be 0.001 ~ 0.1:1.
4. the anode material for lithium-ion batteries of surface coating modification according to claim 1, is characterized in that, described coating layer and LiNi 1-a-bco aal bo 2mass ratio be 0.001 ~ 0.05:1.
5. a preparation method for the anode material for lithium-ion batteries of surface coating modification as claimed in claim 1, is characterized in that, comprises the following steps:
(1) insoluble aluminum contained compound of Nano grade and zinc compound are added to the water and carry out Homogeneous phase mixing and form mixed liquor;
by positive electrode LiNi 1-a-bco aal bo 2step is joined under the condition stirred in mixed liquor in, make clad material evenly be coated on active material particle surface;
by step the mixture of gained, by spraying dry, after then dried solid material being calcined a period of time at a certain temperature, cools, pulverizes, sieving obtains positive electrode.
6. the preparation method of the anode material for lithium-ion batteries of surface coating modification according to claim 5, is characterized in that, the aluminum contained compound of described Nano grade is one or more in alundum (Al2O3), aluminium hydroxide and aluminium nitride.
7. the preparation method of the anode material for lithium-ion batteries of surface coating modification according to claim 5, is characterized in that, the zinc compound of described Nano grade is zinc oxide.
8. the preparation method of the anode material for lithium-ion batteries of surface coating modification according to claim 5, is characterized in that, described LiNi 1-a-bco aal bo 2in a=0.15, b=0.05.
9. the preparation method of the anode material for lithium-ion batteries of surface coating modification according to claim 5, is characterized in that, described LiNi 1-a-bco aal bo 2d50 be 5 ~ 25 μm, D10>=5 μm, D90≤30 μm.
10. the preparation method of the anode material for lithium-ion batteries of surface coating modification according to claim 5, is characterized in that, described calcining heat is 500 ~ 800 DEG C, and calcination time is 3 ~ 10h, and calcination atmosphere is oxygen atmosphere.
CN201510311568.XA 2015-06-09 2015-06-09 Surface-coated anode material for lithium ion battery and preparation method thereof Pending CN105006552A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105355878A (en) * 2015-11-09 2016-02-24 浙江美达瑞新材料科技有限公司 Material used as positive electrode of lithium ion battery and preparation method therefor
CN108448094A (en) * 2018-03-21 2018-08-24 深圳新恒业电池科技有限公司 A kind of surface modification device of positive electrode and a kind of preparation method of positive electrode
CN108807913A (en) * 2018-06-13 2018-11-13 中科廊坊过程工程研究院 One kind anode material for lithium-ion batteries containing zirconium and preparation method thereof and lithium ion battery
CN109494370A (en) * 2018-12-12 2019-03-19 北方奥钛纳米技术有限公司 A kind of method for coating of electrode material of lithium battery and electrode material containing clad
WO2019080237A1 (en) * 2017-10-24 2019-05-02 中航锂电（洛阳）有限公司 High safety coated high nickel ternary positive electrode material, positive electrode, and lithium ion battery
CN112805847A (en) * 2018-10-02 2021-05-14 巴斯夫欧洲公司 Method for producing an at least partially coated electrode active material
CN113039663A (en) * 2018-10-02 2021-06-25 巴斯夫欧洲公司 Method for preparing partially coated electrode active material

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CN102394290A (en) * 2011-11-18 2012-03-28 青岛华冠恒远锂电科技有限公司 Anode material of lithium ion battery and preparation method thereof
CN103151528A (en) * 2013-02-28 2013-06-12 天津工业大学 Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material
WO2014051089A1 (en) * 2012-09-28 2014-04-03 住友金属鉱山株式会社 Nickel-cobalt compound hydroxide and method and device for producing same, positive electrode active substance for nonaqueous electrolyte secondary cell and method for producing same, and nonaqueous electrolyte secondary cell
CN104617303A (en) * 2015-01-13 2015-05-13 海宁美达瑞新材料科技有限公司 Composite modified lithium ion battery cathode material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102394290A (en) * 2011-11-18 2012-03-28 青岛华冠恒远锂电科技有限公司 Anode material of lithium ion battery and preparation method thereof
WO2014051089A1 (en) * 2012-09-28 2014-04-03 住友金属鉱山株式会社 Nickel-cobalt compound hydroxide and method and device for producing same, positive electrode active substance for nonaqueous electrolyte secondary cell and method for producing same, and nonaqueous electrolyte secondary cell
CN103151528A (en) * 2013-02-28 2013-06-12 天津工业大学 Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material
CN104617303A (en) * 2015-01-13 2015-05-13 海宁美达瑞新材料科技有限公司 Composite modified lithium ion battery cathode material and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105355878A (en) * 2015-11-09 2016-02-24 浙江美达瑞新材料科技有限公司 Material used as positive electrode of lithium ion battery and preparation method therefor
WO2019080237A1 (en) * 2017-10-24 2019-05-02 中航锂电（洛阳）有限公司 High safety coated high nickel ternary positive electrode material, positive electrode, and lithium ion battery
CN108448094A (en) * 2018-03-21 2018-08-24 深圳新恒业电池科技有限公司 A kind of surface modification device of positive electrode and a kind of preparation method of positive electrode
CN108807913A (en) * 2018-06-13 2018-11-13 中科廊坊过程工程研究院 One kind anode material for lithium-ion batteries containing zirconium and preparation method thereof and lithium ion battery
CN112805847A (en) * 2018-10-02 2021-05-14 巴斯夫欧洲公司 Method for producing an at least partially coated electrode active material
CN113039663A (en) * 2018-10-02 2021-06-25 巴斯夫欧洲公司 Method for preparing partially coated electrode active material
CN109494370A (en) * 2018-12-12 2019-03-19 北方奥钛纳米技术有限公司 A kind of method for coating of electrode material of lithium battery and electrode material containing clad

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Application publication date: 20151028