CN107644997A - A kind of positive electrode surface coating modification method based on sodium carboxymethylcellulose - Google Patents

A kind of positive electrode surface coating modification method based on sodium carboxymethylcellulose Download PDF

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Publication number
CN107644997A
CN107644997A CN201610575022.XA CN201610575022A CN107644997A CN 107644997 A CN107644997 A CN 107644997A CN 201610575022 A CN201610575022 A CN 201610575022A CN 107644997 A CN107644997 A CN 107644997A
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positive electrode
lini
sodium carboxymethylcellulose
slurry
zno
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李斯蓉
陈春华
翁朵
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Samsung Huanxin Xian Power Battery Co Ltd
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Samsung Huanxin Xian Power Battery Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of positive electrode surface coating modification method of the new lithium ion battery based on sodium carboxymethylcellulose, the composite is by the use of sodium carboxymethylcellulose as binding agent, by ZnO and Al2O3It is wrapped in positive electrode (LiNi0.5Mn1.5O4) surface formation advanced composite material (ACM).Surface parcel composite construction effectively suppresses oxidation of the electrolyte in electrode material surface, improves LiNi0.5Mn1.5O4The cyclical stability of/Li half-cells, coulombic efficiency is improved, and reduce the sliding of charging and discharging curve, shown more excellent chemical property, can be widely used in commercialized energy-storage battery electrolysis material.

Description

A kind of positive electrode surface coating modification method based on sodium carboxymethylcellulose
Technical field
The present invention relates to electrode modification technical field in energy-storage battery, more particularly to it is a kind of based on sodium carboxymethylcellulose The surface coated method of modifying of novel anode material.
Background technology
With the development of electric automobile and hybrid-electric car in recent years, people propose to lithium ion battery energy density Higher and higher requirement.And the key that lithium ion battery energy density improves at present is the energy density of positive electrode.Due to The energy density of positive electrode is the integration of specific discharge capacity and discharge voltage, therefore selects the lithium-ion electric of high charge-discharge voltage Pond electrode material (such as LiNi0.5Mn1.5O4、LiCoPO4Deng) the integral energy density of battery can be effectively improved.But business at present Oxidation Decomposition can occur under high potential for lithium-ion battery electrolytes.Oxidation Decomposition of the electrolyte under hyperbaric environment is not only The consumption of Reversible Cycle lithium in battery can be caused, and so as to cause the reduction of energy density, its oxidative degradation products also can be to battery Security performance causes significant impact.
At present in literature research, it is proved to be a kind of to active material surface by inert materials such as oxide, fluorides Electrolyte surface reaction can effectively be suppressed, the method for guard electrode material, be widely used in LiCoO2、LiMn2O4、 LiNi0.5Mn1.5O4And the equal material of rich lithium.Sun et al. is prepared for the LiNi of ZnO claddings0.5Mn1.5O4Material, propose that ZnO can With caused HF in Electolyte-absorptive and improve LiNi0.5Mn1.5O4The stability of structure, material can be effectively improved at high temperature Cyclical stability.This monoxide seizure HF mechanism has also obtained Fan et al. accreditation and use, for explaining how empty nothing Sizing Nano-meter SiO_22Layer is to LiNi0.5Mn1.5O4The raising of cyclical stability.Manthiram seminar is respectively with Mo (M=Al, Zn Or Bi) and MPO4(M=Al or Co) is to LiNi0.42Mn1.5Zn0.08O4And Li1.2Ni0.13Co0.13Mn0.54O2Coated, found These Surface coatings can improve the surface stability of electrode material, and circulation and high rate performance also all improve obvious.In addition, Wu etc. People uses ZrO2And ZrP2O7To LiNi0.5Mn1.5O4Surface modification is carried out, finds LiNi0.5Mn1.5O4Heat endurance and capacity keep Rate is obtained for good improvement.
The content of the invention
In view of this, the technical problems to be solved by the invention are to provide a kind of new based on sodium carboxymethylcellulose Electrode material surface cladding method of modifying, ZnO-LiNi provided by the invention0.5Mn1.5O4And Al2O3-LiNi0.5Mn1.5O4 Composite shows the excellent properties such as charging and discharging curve sliding reduces, cyclical stability improves in half-cell test.
To achieve these goals, the present invention provides following technical scheme.
The present invention relates to a kind of new positive electrode surface coating modification method based on sodium carboxymethylcellulose, and it is special Sign is:By sodium carboxymethylcellulose as zinc oxide (ZnO) and alundum (Al2O3) (Al2O3) surface coated binding agent.
Described positive electrode is mainly LiNi0.5Mn1.5O4、LiMn2O4、LiCoO2Or one kind in rich lithium phase material.
Described Surface coating material ZnO and Al2O3, it is characterised in that:The dosage of the material is the positive pole material being wrapped by Expect the 1%-5% of quality.Zn sources and Al sources are respectively zinc acetate and aluminium isopropoxide.
The method of modifying of described novel surface cladding, it is characterised in that:The system of described surface coated positive electrode Standby process is as follows:
A) zinc acetate/aluminium isopropoxide and sodium carboxymethylcellulose of mass ratio, all it is dissolved in aqueous phase under agitation In, stir to homogeneous phase;
B) it is slowly added to LiNi into above-mentioned solution0.5Mn1.5O4Powder prepares thick slurry, continues to stir slurry Form uniform slurry.
C) slurry of preparation is directly sintered into 1h at 200 DEG C -350 DEG C in air atmosphere, then at 400 DEG C -600 DEG C Continue to be cooled to the uniform sample of room temperature acquisition surface parcel after sintering 1h.
Brief description of the drawings
Fig. 1 is LiNi0.5Mn1.5O4, 2wt%ZnO-LiNi0.5Mn1.5O4And 2wt%Al2O3-LiNi0.5Mn1.5O4The X of sample X ray diffraction (XRD) spectrogram, bottom collection of illustrative plates are LiNi0.5Mn1.5O4The standard spectrogram of (JCPDS 80-2162).
Fig. 2 is 2wt%ZnO-LiNi0.5Mn1.5O4And 2wt%Al2O3-LiNi0.5Mn1.5O4With LiNi0.5Mn1.5O4Sample Scanning electron Electronic Speculum (SEM) spectrogram.
Fig. 3 is LiNi0.5Mn1.5O4| | Li half-cells are in 3.5-5.0V, the charging and discharging curve of C/20 and 30 DEG C of circulation.
Fig. 4 is sample ZnO-LiNi0.5Mn1.5O4And Al2O3-LiNi0.5Mn1.5O4In half-cell, under 3.5-5.0V, C/ The electric discharge end (a) of 20 and 30 DEG C of circulations and charging end (b) cut off are to cycle-index graph of a relation.
Fig. 5 is ZnO-LiNi0.5Mn1.5O4Half-cell and Al2O3-LiNi0.5Mn1.5O4Half-cell, 3.5-5.0V, C/20 and The discharge capacity circulated under the conditions of 30 DEG C is to cycle-index graph of a relation, with 1M LiPF6EC/DMC is electrolyte.
Embodiment
Embodiment 1
For surface coated LiNi0.5Mn1.5O4Electrode powder obtains from the purchase of battery material producer.2wt%ZnO is coated LiNi0.5Mn1.5O4Prepared by procedure below:0.54g zinc acetates and 0.11g sodium carboxymethylcelluloses (CMC, D.S.=0.7) are first It is first dissolved in 7ml water, stirring is slowly added to LiNi after 30 minutes0.5Mn1.5O4Powder obtains thick slurry, continues to stir Slurry 2h.Then by slurry directly in air atmosphere 240 DEG C of sintering 1h, and 400 DEG C of sintering 1h, it is cooled to room temperature.2wt% Al2O3The LiNi of cladding0.5Mn1.5O4Preparation method is similar with the above method:With 0.4g aluminum isopropylates and 0.11g Methyl celluloses Plain sodium is dissolved in 7ml water, and stirring is slowly added to LiNi after 30 minutes0.5Mn1.5O4Powder obtains thick slurry, continues to stir Mix slurry 2h.Then in atmosphere 140 DEG C sintering 1h, then 400 DEG C sinter 1h be cooled to room temperature.In order to simply distinguish sample, By 2wt%ZnO or 2wt%Al2O3The LiNi of cladding0.5Mn1.5O4ZnO-LiNi is denoted as respectively0.5Mn1.5O4And Al2O3- LiNi0.5Mn1.5O4

Claims (4)

  1. A kind of 1. positive electrode surface coating modification method based on sodium carboxymethylcellulose, it is characterised in that:It is fine by carboxymethyl Plain sodium is tieed up as zinc oxide (ZnO) and alundum (Al2O3) (Al2O3) surface coated binding agent.
  2. 2. positive electrode as claimed in claim 1 is mainly LiNi0.5Mn1.5O4、LiMn2O4、LiCoO2Or in rich lithium phase material One kind.
  3. 3. Surface coating material ZnO and Al as claimed in claim 12O3, it is characterised in that:The dosage of the material is to be wrapped The 1%-5% for the positive electrode quality covered, Zn sources and Al sources are respectively zinc acetate and aluminium isopropoxide.
  4. 4. surface coated method of modifying as claimed in claim 1, it is characterised in that:Described surface coated positive electrode Preparation process it is as follows:
    A) zinc acetate/aluminium isopropoxide and sodium carboxymethylcellulose of mass ratio, all it is dissolved in aqueous phase, stirs under agitation Mix to homogeneous phase;
    B) it is slowly added to LiNi into above-mentioned solution0.5Mn1.5O4Powder prepares thick slurry, continues stirring slurry and is formed Uniform slurry;
    C) slurry of preparation is directly sintered into 1h at 200 DEG C -350 DEG C in air atmosphere, then continued at 400 DEG C -600 DEG C Room temperature is cooled to after sintering 1h and obtains the uniform sample of surface parcel.
CN201610575022.XA 2016-07-20 2016-07-20 A kind of positive electrode surface coating modification method based on sodium carboxymethylcellulose Pending CN107644997A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108232176A (en) * 2018-02-07 2018-06-29 中南大学 A kind of lithium-sulfur cell cathode material and preparation method thereof
CN109037639A (en) * 2018-08-05 2018-12-18 南京理工大学 A kind of preparation method coating nickel element adulterated lithium manganate composite material
CN112072092A (en) * 2020-09-17 2020-12-11 杭州肄康新材料有限公司 Electrode material, preparation method thereof and lithium battery adopting electrode material
CN112670463A (en) * 2020-04-16 2021-04-16 宁波杉杉新材料科技有限公司 Graphite negative electrode material and preparation method and application thereof

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CN105449191A (en) * 2015-12-26 2016-03-30 长春瑛隆材料科技有限公司 Preparation method of lithium ion battery cathode material
CN105633384A (en) * 2016-03-24 2016-06-01 江门市科恒实业股份有限公司 Surface modification process for cathode material for power lithium-ion battery

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CN101834289A (en) * 2010-04-28 2010-09-15 东莞新能源科技有限公司 Preparation method of lithium-ion battery anode material with oxide coated on surface
CN103811743A (en) * 2012-11-15 2014-05-21 华为技术有限公司 Lithium-rich anode material, lithium battery anode and lithium battery
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Publication number Priority date Publication date Assignee Title
CN108232176A (en) * 2018-02-07 2018-06-29 中南大学 A kind of lithium-sulfur cell cathode material and preparation method thereof
CN108232176B (en) * 2018-02-07 2020-11-13 中南大学 Lithium-sulfur battery cathode material and preparation method thereof
CN109037639A (en) * 2018-08-05 2018-12-18 南京理工大学 A kind of preparation method coating nickel element adulterated lithium manganate composite material
CN112670463A (en) * 2020-04-16 2021-04-16 宁波杉杉新材料科技有限公司 Graphite negative electrode material and preparation method and application thereof
CN112072092A (en) * 2020-09-17 2020-12-11 杭州肄康新材料有限公司 Electrode material, preparation method thereof and lithium battery adopting electrode material

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