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 PDFInfo
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- 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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- 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
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
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)
- 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. positive electrode as claimed in claim 1 is mainly LiNi0.5Mn1.5O4、LiMn2O4、LiCoO2Or in rich lithium phase material One kind.
- 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. 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.
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Cited By (4)
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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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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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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