CN108539168A - A method of improving anode material of lithium battery ageing resistance - Google Patents
A method of improving anode material of lithium battery ageing resistance Download PDFInfo
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- CN108539168A CN108539168A CN201810334094.4A CN201810334094A CN108539168A CN 108539168 A CN108539168 A CN 108539168A CN 201810334094 A CN201810334094 A CN 201810334094A CN 108539168 A CN108539168 A CN 108539168A
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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
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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
- 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
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 present invention relates to anode material of lithium battery and its surface chemical modifications, belong to electrode material of lithium battery process for modifying surface field.The method for improving anode material of lithium battery ageing resistance includes the following steps：A. under room temperature environment air conditions, positive electrode powder is transferred in container；B. it by coating material, is added in the container described in step a, container is sealed；C. by mixing in coating material and container of the positive electrode powder described in step b, curing obtains the positive electrode powder of surface chemical modification；The positive electrode powder for the surface chemical modification that step c is obtained is as anode material of lithium battery.Polymer-modified layer can be formed in situ in positive electrode particle surface under the conditions of normal pressure, room temperature environment in the present invention, this is conducive to inhibit being in direct contact for surrounding air, electrolyte and active material, improves the high rate performance and cyclical stability of positive electrode.
Description
Technical field
The present invention relates to lithium ion batteries（Abbreviation lithium battery）Positive electrode and its surface chemical modification, belong to lithium battery
Pole material surface modifying technology field.
Background technology
Positive electrode（Also known as cathode material）It is the important component of lithium battery, it decides that the energy of lithium battery is close
Degree, cyclical stability, safety and cost（Electrochimica Acta, 2016, 222, 685-692）.Common lithium
Cell positive material has：Cobalt acid lithium (LiCoO2, be abbreviated as LCO), LiMn2O4 (LiMn2O4, be abbreviated as LMO), LiFePO4
(LiFePO4, it is abbreviated as LFP) and manganese, nickel doping cobalt acid lithium ternary electrode material (LiNi x Mn y Co z O2, x + y + z = 1)。
Above-mentioned positive electrode there is a problem that in actual application two kinds it is important：First, positive electrode electronic conductivity and ion
The low problem of conductivity；Second is that positive electrode is exposed to the problem of performance degradation in surrounding air, i.e. problem of aging.
So far, researcher has developed a variety of methods, preferably solves positive electrode electronic conductivity, ion
The low problem of conductivity.The method taken has, and reduces particle size, control particle composition and pattern, doping metals and/or non-gold
Belong to element and by the compound method of positive electrode and carbon, polymer, organic compound, inorganic compound（Nature
materials, 2008, 7, 741-747; Advanced Energy Materials, 2012, 2, 1028-1032;
Nature materials, 2002, 1, 123-128; Nano letters, 2014, 14, 6828-6835;
Chemistry of Materials, 2012, 24, 3212-3218; Nature, 2009, 458, 190-193;
Journal of Power Sources, 2016, 318, 93-112; Chemistry of Materials, 2015,
27, 4057-4065; Journal of the Electrochemical Society, 2012, 159, A305-A309;
Angewandte Chemie, 2011, 50, 6884-6887; ACS applied materials & interfaces,
2015, 7, 18519-18529.）.
About the problem of aging of positive electrode, just there are researcher discovery, positive electrode early in 2008（Such as LFP, carbon
Coat LFP (LFP/C)）It is exposed in air or is contacted with water, since the hydrophily of Li can cause positive electrode to take off lithium, to
Its chemical property is caused to be decayed（Electrochemical and Solid-State Letters, 2008, 11, A4-
A8; Journal of Power Sources, 2008, 185, 698-710; Electrochemical and Solid-
State Letters, 2008, 11, A12-A16.）.Positive electrode in weighing, dispense, take and meeting during electrode fabrication
It is contacted with surrounding air, positive electrode after contacting with the air undergoes long-time storage（January or several months）Afterwards, electrochemistry
It can be substantially reduced（See embodiment）.Chen groups propose it is a kind of addition pyrroles, high temperature thermal reduction method, can make always
The LFP/C changed restores preferable chemical property（Electrochemistry Communications, 2008, 10,
1442-1444.）.Compared to the traditional method of this " first decay and restore afterwards ", providing one kind makes positive electrode from by environment sky
The method of gas aging, it is clear that there is even more important scientific meaning and actual application value.However up to the present, there has been no needles
For solving the relevant report of positive electrode problem of aging.
CN102544514A discloses a kind of surface-carbon-modified cathode anode material for lithium-ion batteries and preparation method thereof, the preparation
Method is that anode material for lithium-ion batteries LiMn is made first0.5Ni1.5O4, then with LiMn obtained0.5Ni1.5O4It is molten with organic matter
The concurrent biochemical reaction of liquid uniform stirring under 80~100 °C of heating condition 15~60 minutes, obtains to surface and is coated with high score
Then the anode material for lithium-ion batteries of son is carbonized in 550 ~ 750 °C in an inert atmosphere by being filtered, washed and drying,
To obtain the anode material for lithium-ion batteries of surface-carbon-modified cathode.
CN104600282A discloses a kind of surface modifying and decorating anode material for lithium-ion batteries（Such as cobalt acid lithium, lithium nickelate
Deng）And preparation method thereof.Wherein preparation method includes the following steps：（1）By anode material for lithium-ion batteries and a kind of or one kind
Above metal acetate salt is sufficiently mixed；（2）Said mixture is increased into temperature to 80 ~ 450 °C, makes low melting point in mixture
Acetate reach melting or congruent melting state, and realize complete wetting and completely cladding on positive electrode surface；（3）Further rise
High-temperature makes the metal acetate salt clad on positive electrode surface be decomposed into metal oxide clad and gold to 300 ~ 800 °C
Belong to ion and diffuse to form doping vario-property layer to material internal, obtains surface modified anode material for lithium-ion batteries.
As previously mentioned, positive electrode and carbon or inorganic matter is compound, be conducive to the electronics and/or ion that improve positive electrode
Conductivity.Meanwhile such carbon or inorganic matter clad can prevent the hydrone in air and active material to a certain extent
（I.e. the above LiMn0.5Ni1.5O4, cobalt acid lithium, lithium nickelate etc.）It is in direct contact, this is conducive to improve positive electrode in environment
Ageing resistance in air.But positive electrode surface modification as described in CN102544514A and CN104600282A or
The way of cladding, since during surface modification or cladding, positive electrode experienced high-temperature burning process, this can cause surface
Decorative layer shrinks, divides, being unevenly distributed, coating incomplete phenomenon.In other words, disposable surface is carried out to positive electrode to repair
Decorations or cladding, are evenly distributed on positive electrode surface it is difficult to obtain, coat complete decorative layer（Journal of Materials
Chemistry, 2011, 21, 14680;Journal of The Electrochemical Society, 2015, 162,
A2201-A2207;Journal of Alloys and Compounds, 2017, 706, 24-40.）, this can undoubtedly be caused
The phenomenon that positive electrode partial denudation.Hydrone in surrounding air can be contacted by diffusion with exposed position, cause positive material
Material takes off lithium, aging, reduces its chemical property.
CN1652376A discloses a kind of anode material for lithium-ion batteries, preparation method and its lithium ion battery.It is described
Lithium ion anode material refer to functional polymer moditied processing LiMn2O4, the functional polymer be by contain CN,
The vinyl monomer of CON, CO or COO functional group is in the solution through a kind of polymer obtained from Raolical polymerizable.
The LiMn for the functional polymer modification that CN1652376A is provided2O4It has as a drawback that, is as coating material first
Functional polymer is not easy to obtain and non-conductive, is grafted to active material（That is LiMn2O4）Electrode material can be reduced behind surface
Electronic conductivity；Secondly, either by LiMn2O4It is mixed LiMn with functional polymer solution still2O4It polymerize with functionality
Object monomer, initiator mix in the solution, in-situ polymerization, obtains functional polymer and is grafted LiMn2O4Process be necessarily accompanied with
The volatilization of the organic matters such as solvent, unreacted monomer, environment are unfriendly.
CN107437617A discloses a kind of improvement richness lithium material electrification driven based on metal-organic framework material
The surface modification method of performance is learned, includes mainly following steps：（1）By suitable rich lithium material and suitable organic ligand
Mixing；（2）Said mixture is positioned over heated under vacuum reaction；（3）By product obtained in the previous step in inert atmosphere
Under be thermally treated resulting in carbon ＆ nickel cobalt (alloy) quantum dot heterostructures structures cladding rich lithium material.The carbon ＆ nickel that CN107437617A is provided
The rich lithium material of cobalt alloy quantum dot heterostructures structure cladding, the advantage is that, what organic ligand was formed under vacuum, heating condition
Organic ligand steam can be combined in a manner of vapor deposition with richness lithium material particle surface, this is conducive in rich lithium material
Grain surface forms uniform decorative layer；The disadvantage is that, selected organic ligand（Methylimidazole or 2-methylimidazole）Boiling point is high,
Vapor deposition processes needs carry out under vacuum, heating condition, and technological requirement is high；It is deposited on active material（Rich lithium material）Particle
The organic ligand on surface is non-conductive, needs further high-temperature heat treatment（450~480 °C）It is converted into carbon, complex steps, energy consumption
It is high；Moreover, the carbon-coating complete cladding difficult to realize to rich lithium material particle surface obtained through high-temperature heat treatment.
Aging after being contacted with surrounding air in view of positive electrode is attributed to exposed position and environment not by surface modification
Lithium is taken off caused by after hydrone contact in air, it is clear that it is to improve it to surrounding air to carry out secondary cladding to positive electrode
The effective way of ageing resistance.Secondary surface modification/cladding is carried out to positive electrode, to meet following requirement as far as possible：（1）
It is complete to the cladding of positive electrode particle, to cut off contact path of the hydrone with active material；（2）Cladding layer component will use up
May be conductive, the high rate performance of material cannot be reduced；（3）The thickness of clad wants moderate, coats layer component institute in the composite
Accounting for mass percent cannot be excessive, i.e., cannot be to sacrifice the specific energy of positive electrode as cost；（4）Technique is simple, nothing
Waste, it is environmental-friendly.Secondary surface modification is carried out to carbon coating positive electrode, existing literature there are a large amount of records, such as uses machine
Tool mixing method（Such as ball-milling method）, mixing method, the in-situ modification method completed in the solution in solvent（Advanced Materials,
2007, 19, 848-851; J. Mater. Chem. A, 2014, 2, 19315-19323; Journal of Power
Sources, 2010, 195, 5351-5359; Angewandte Chemie, 2011, 50, 6884-6887.）.Machinery
Mixing method is unfavorable for realizing active material particle cladding, and the modification method process route based on solvent/solution is long, can generate waste liquid,
It easily leads to active material in modification and takes off lithium.In short, the above method cannot meet carries out secondary surface to positive electrode
The requirement of modification/cladding.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of simple sides improving anode material of lithium battery ageing resistance
Method.
In order to solve the problems, such as positive electrode performance degradation after contacting with the air during transport, storage and use, carry
It is high its to tolerance in surrounding air, the present invention provides a kind of straightforward procedure that positive electrode is surface modified/is coated.It should
Method use aumospheric pressure cvd technology, make coating material molecular vapor deposition in positive electrode particle surface, and
Grain surface in situ growth forms the polymer film of isolated environment air water molecule and active substances in cathode materials contact channel.It adopts
The positive electrode modified with the technology of the present invention has good tolerance to surrounding air, and can be obviously improved the positive material of starting
The chemical property of material.Present invention process flow is short, without waste, environmental-friendly, at low cost, is suitble to large-scale industrial application.
Term is explained：
LCO：Cobalt acid lithium (LiCoO2)。
LCO/C：Carbon coating cobalt acid lithium (LiCoO2/C)。
LMO:LiMn2O4 (LiMn2O4)。
LMO/C:Carbon coating LiMn2O4 (LiMn2O4/C)。
LFP：LiFePO4 (LiFePO4)。
LFP/C：Carbon-coated LiFePO 4 for lithium ion batteries (LiFePO4/C)。
LNMCO:Manganese, nickel doping cobalt acid lithium ternary electrode material (LiNi x Mn y Co z O2, x + y + z = 1)。
LNMCO/C：Carbon coating manganese, nickel adulterate cobalt acid lithium ternary electrode material.
Carbon coating cobalt acid lithium (LiCoO2/ C), carbon coating LiMn2O4 (LiMn2O4/ C), carbon-coated LiFePO 4 for lithium ion batteries (LiFePO4/
C), carbon coating manganese, nickel doping cobalt acid lithium ternary electrode material are referred to as carbon coating positive electrode.
" carbon " described in above-mentioned " carbon coating " is synthesis carbon, i.e., with organic compound, organic polymer, organic polymer
For precursor, the part graphitized carbon obtained by high-temperature heat treatment.
Aging：Positive electrode is exposed to certain time in surrounding air, compared with the starting positive electrode, electrochemistry
The phenomenon that performance degradation.
Ageing resistance：The positive electrode of surface chemical modification is exposed to certain time in surrounding air, and without table
The starting positive electrode of face modification is compared, the unattenuated phenomenon of chemical property；Alternatively, with it is in identical environment,
The phenomenon that positive electrode of non-surface modification is compared, and chemical property attenuation degree is substantially reduced.
Curing：After coating material is mixed with positive electrode powder to be finished in closed container, coating material
Molecule evaporation is deposited on positive electrode powder surface, then nucleation in situ, growth, the process for forming polymer.
Specific discharge capacity：The electricity that unit mass active material or battery can release, unit：MAh/g（mA h
g-1）.
Capacity retention ratio：The electricity that active material is released under certain current density and the electric discharge under a certain current density
The ratio between amount, alternatively, active material recycles the electricity and discharge capacity for the first time that can be released after a fixing turn under certain current density
The ratio between.
A method of improving anode material of lithium battery ageing resistance, it is characterised in that：Positive electrode, which uses, to come to the surface
Learn the positive electrode powder of modification.
Preferably, a method of improving anode material of lithium battery ageing resistance, include the following steps：
A. under room temperature environment air conditions, positive electrode powder is transferred in container；
B. it by coating material, is added in the container described in step a, container is sealed；
C. by mixing in coating material and container of the positive electrode powder described in step b, curing obtains surface chemical modification
Positive electrode powder；
The positive electrode powder for the surface chemical modification that step c is obtained is as anode material of lithium battery.
Room temperature environment air conditions described in step a, range of temperature therein are 0 40 °C, surrounding air
Relative humidity is 20 80%.
Positive electrode described in step a is LiCoO2、LiCoO2/C、LiMn2O4、LiMn2O4/C、LiFePO4、
LiFePO4/C、LiNi x Mn y Co z O2 (x + y + z=1) or LiNi x Mn y Co z O2/C (x + y + z=1), wherein carbon
The mass percentage of carbon is less than 5% in clad anode material.Positive electrode powder described in step a, particle size >=
800 mesh.Preferably, the positive electrode powder described in step a, particle size are 0.1 ~ 18 μm.
Container described in step a is salable, with stirring, the container with charge door.
Container described in step a, material are stainless steel, enamel, enamel, ceramics, glass or plastics.
Material powder described in step a and container, wherein the volume of powder is no more than the 60% of vessel volume.
Coating material described in step b refers to that the volume mass ratio of coating material and positive electrode powder is
0.5‒30 mL/kg。
Coating material described in step b is aniline, thiophene, pyrroles, 2-aminotoluene, 3- methylanilines, 2- ethyls
Aniline, 3- ethyl aniline, 2- vinyl aniline, 3- vinyl aniline, 3,4- ethene dioxythiophenes, 3 methyl thiophene, 3- ethyls
Thiophene, 3- vinyl thiophenes, 3,4- ethylene dioxies pyrroles, 1- benzyl -3,4- ethylene dioxies pyrroles, 3- methylpyrroles, 3- ethyls
Pyrroles or 3- vinyl pyrroles.
Mixing described in step c, mode are stirring, shake or vibrate.
Curing described in step c, curing time are 7 30 days, stir material during curing daily 24 times, stir every time
It is 1 30 min to mix the time.
Preferably, the positive electrode powder of the surface chemical modification described in step c is that the surface of positive electrode covers one layer
Finishing coat.
It is furthermore preferred that finishing coat is conducting polymer oligomer.The conducting polymer oligomer, to contain 8 ~ 14
The oligomer of a monomer, weight average molecular weight distribution are 522 ~ 1276；Molecular weight distribution index is 1.1 ~ 1.3.Preferably, institute
It is aniline, thiophene, pyrroles, 2-aminotoluene, 3- methylanilines, 2- ethyl aniline, 3- ethyl aniline, 2- vinyl benzenes to state monomer
Amine, 3- vinyl aniline, 3,4- ethene dioxythiophenes, 3 methyl thiophene, 3- ethylthiophenes, 3- vinyl thiophenes, 3,4- ethylene
Dioxypyrrole, 1- benzyl -3,4- ethylene dioxies pyrroles, 3- methylpyrroles or 3- N-ethyl pyrrole Ns or 3- vinyl pyrroles.
It is furthermore preferred that the conducting polymer oligomer, monomer is pyrroles, and N 1s high-resolution XPS spectrum figures, which are shown, to be located at
400, the peak of 400.7,402 eV.
It is furthermore preferred that the conducting polymer oligomer, monomer is aniline, and N 1s high-resolution XPS spectrum figures, which are shown, to be located at
399.2, the peak of 400.0,401.0 eV.
It is furthermore preferred that the conducting polymer oligomer, monomer is thiophene, and S 2p high-resolution XPS spectrum figures, which are shown, to be located at
The peak of 163.8 and 164.8 eV.
Preferably, the method for improving anode material of lithium battery ageing resistance, which is characterized in that recycled at 1 C
The specific discharge capacity of 100 circles reaches 70 ~ 140 mA h g‒1, capacity retention ratio is 85 ~ 92%.
Advantageous effect
1, currently invention addresses anode material of lithium battery is solved, performance declines after contacting with the air during transport, storage and use
The problem of subtracting, i.e. problem of aging make coating material molecular vapor deposition in positive material using aumospheric pressure cvd technology
Expect particle surface, growth in situ, the polymer film for forming isolation hydrone and active contacts channel.Relative to positive material
Material only needs micro coating material, can significantly improve ageing resistance of the positive electrode in surrounding air.
2, the polymer film being formed in situ in positive electrode particle surface can mitigate the direct of electrolyte and active material
Contact, this is conducive to the high rate performance and cyclical stability that improve positive electrode.
3, the technology of the present invention method is simple, technological process is short, without waste, environmental-friendly, at low cost, suitable scale chemical industry
Industry application.
Description of the drawings
Fig. 1 is the XRD diagram of sample：(a) LFP/C; (b) cLFP-2; (c) cLFPM-2; (d) cLFP-4; (e)
cLFPM-4。
Fig. 2 is the graph of molecular weight distribution of the surfaces sample cLFPM-2 pyrroles's oligomer.
Fig. 3 is the N 1s spectrograms of sample：(a) LFP/C; (b) cLFP-2; (c) cLFPM-2.
The SEM that Fig. 4 is sample LFP/C schemes.
The SEM that Fig. 5 is sample cLFPM-4 schemes.
The high rate performance figure of Fig. 6 samples cLFPM-2, LFP/C and cLFP-2.
Fig. 7 is the stable circulation linearity curve that sample cLFPM-2, LFP/C and cLFP-2 recycle 100 circles at 1 C.
Fig. 8 is the high rate performance figure of sample cLFPM-4, LFP/C and cLFP-4.
Fig. 9 is the stable circulation linearity curve that sample cLFPM-4, LFP/C and cLFP-4 recycle 100 circles at 1 C.
Figure 10 is the XRD diagram of sample：(a) LMO; (b) LMO-2; (c) LMOM-2.
The SEM that Figure 11 is sample LMO schemes.
The SEM that Figure 12 is sample LMOM-2 schemes.
Figure 13 is the S 2p figures of sample：(a) LMO; (b) LMOM-2.
Figure 14 is the TOF LC-MS figures of the surfaces sample LMOM-2 thiophene oligomer.
Figure 15 is the graph of molecular weight distribution of the surfaces sample LMOM-2 thiophene oligomer.
Figure 16 is the high rate performance figure of sample LMOM-2, LMO and LMO-2.
Figure 17 is the discharge curve of sample LMOM-2, LMO and LMO-2 at 1 C.
Figure 18 is the XRD diagram of sample：(a) LNMCO/C; (b) cLNMCOM-2; (c) cLNMCO-2.
The SEM that Figure 19 is sample LNMCO/C schemes.
The EDS that Figure 20 is sample LNMCO/C schemes.
Figure 21 is the N 1s figures of sample：(a) cLNMCOM-2; (b) LNMCO/C; (c) cLNMCO-2.
Figure 22 is that the GPC of the surfaces sample cLNMCOM-2 Oligoanilines schemes.
Figure 23 is the high rate performance figure of sample LNMCOM-2, LNMCO/C and cLNMCO-2.
Figure 24 is the discharge curve at 1 C of sample LNMCOM-2, LNMCO/C and cLNMCO-2.
Table 1 is the unit cell volume and pore volume tables of data of sample.
Specific implementation mode
It is further elaborated below by specific embodiment and in conjunction with attached drawing to technical scheme of the present invention, these embodiments
It is intended merely to illustrate technical scheme of the present invention, and the limitation to the claims in the present invention content cannot be considered as.
In embodiment
LFP, LMO, LNMCO, LCO, LFP/C, LMO/C, LNMCO/C and LCO/C win electrochemical material net purchased from match；
Pyrroles is purchased from Shanghai Tong Yuan Chemical Co., Ltd.s；
Aniline is purchased from Tianjin great Mao chemical reagents corporations；
Thiophene is purchased from Tianjin Long Yu Chemical Co., Ltd.s；
2- ethyl aniline, 3,4- ethene dioxythiophenes, 3- N-ethyl pyrrole Ns, 3- vinyl thiophenes, 3- ethyl aniline are purchased from Mike woods
Biochemical technology Co., Ltd.
X-ray powder diffraction (XRD) figure of sample is through German Bruker companies Advance D8 in description of the invention
The detection of X-ray powder diffraction instrument obtains；The molecular weight distribution of sample surfaces oligomer is through U.S.'s Waters E2695 gel infiltrations
Chromatograph (GPC) detection obtains；Level four bars flight time liquid phase-mass spectrogram (TOF LC-MS) is through 6520 level four bars of Agilent
Flight time liquid phase-mass spectrometer detection obtains；Scanning electron microscope (SEM) figure, X-ray energy dispersive spectrum (EDS) and element point
Butut is detected through Hitachi S-4800 field emission scanning electron microscopes and is obtained；The transmission electron microscope photo (TEM) of sample is through Japanese JEOL
Company's JEM-2100 transmission electron microscopes detection obtains；X-ray photoelectron spectroscopy (XPS) is through Thermo Fisher
The detection of 250 x-ray photoelectron spectroscopies of Scientific Escalab obtains；The chemical property of sample is through CHI 660E
Electrochemical analyser and the detection of LANHE CT2001A cell testers obtain.
Unless otherwise instructed, the size of positive electrode powder of the present invention is 0.1 ~ 18 μm.In above-mentioned size range
The purpose of the present invention is inside can reach, those skilled in the art can select the size range of powder as needed.
Embodiment 1
A method of anode material of lithium battery ageing resistance being improved, by taking positive electrode is LFP/C powders as an example, step is such as
Under：
(1) preparation of the LFP/C powders of surface modification
5 μ L pyrroles are added to and fill 10 g LFP/C powders（The size of powder granule is 0.1 ~ 1.5 μm）50 mL containers
In, container is sealed, shaking container makes LFP/C powders be uniformly mixed with pyrroles, cures 7 days at room temperature.During curing, shake daily
Visibly moved device 2 times, each shake time are no less than 1 min, the LFP/C powder samples of surface modification are obtained after the maturation period, by this
Sample is referred to as cLFPM.
(2) senile experiment
The container stopper for filling cLFPM samples is opened, so that cLFPM samples is exposed in surrounding air, to make sample and surrounding air
It comes into full contact with, daily shakes container occlusion 3 times, each shake time is no less than 1 min, opens plug after shaking every time, makes sample
Again it exposes in surrounding air.Ageing time is continuously 2 months, ranging from 15 38 °C of variation of ambient temperature, and humidity changes model
Enclose is 20 75%.Sample after senile experiment is known as cLFPM-2, wherein 2 be ageing time（Month）.
Compare senile experiment
CLFPM samples described in above-mentioned senile experiment are replaced with starting LFP/C samples, remaining experimental implementation and condition are constant.
Sample after senile experiment is known as cLFP-2, wherein 2 be ageing time（Month）.
(3) electrochemical property test of sample
Using sample obtained by embodiment, as positive active material, lithium piece is cathode, the LiPF of 1 mol/L6It is dissolved in ethylene carbonate：
Dimethyl carbonate：Diethyl carbonate（Volume ratio is 1:1:1）For electrolyte, microporous polypropylene membrane is diaphragm, assembles CR2032 knobs
Detain battery（Int. J. Electrochem. Sci., 2018, 13,1376-1389.）.
Using CHI 660E electrochemical analysers and LANHE CT2001A cell testers to the button cell that is assembled into
Row test, the chemical property of evaluation starting LFP/C, cLFPM-2 and cLFP-2 sample.
Embodiment 2
A method of anode material of lithium battery ageing resistance being improved, by taking positive electrode is LFP/C powders as an example, step is such as
Under：
(1) preparation of the LFP/C powders of surface modification
20 μ L pyrroles are added to and fill 10 g LFP/C powders（The size of powder granule is 0.1 ~ 1.5 μm）50 mL hold
In device, container is sealed, shaking container makes LFP/C powders be uniformly mixed with pyrroles, cures 30 days at room temperature.During curing, often
Its shake container 2 times, each shake time are no less than 1 min, the LFP/C powder samples of surface modification are obtained after the maturation period,
The sample is referred to as cLFPM.
(2) senile experiment
The container stopper for filling cLFPM samples is opened, so that cLFPM samples is exposed in surrounding air, to make sample and surrounding air
It comes into full contact with, daily shakes container occlusion 3 times, each shake time is no less than 1 min, opens plug after shaking every time, makes sample
Again it exposes in surrounding air.Ageing time is continuously 4 months, ranging from 15 40 °C of variation of ambient temperature, and humidity changes model
Enclose is 20 80%.Sample after senile experiment is known as cLFPM-4, wherein 4 be ageing time（Month）.
Compare senile experiment
CLFPM samples described in above-mentioned senile experiment are replaced with starting LFP/C samples, remaining experimental implementation and condition are constant.
Sample after senile experiment is known as cLFP-4, wherein 4 be ageing time（Month）.
(3) electrochemical property test of sample
Electrochemical property test is carried out to sample according to method described in embodiment 1 (3).
Interpretation of result
Fig. 1 is the XRD diagram of sample cLFPM-2, LFP/C and cLFP-2.It will be seen from figure 1 that each diffraction maximum in Fig. 1 a, b, c
LFP in position and document（JCPDS 83-2092）The position of each diffraction maximum is very identical, this explanation is old by surface modification, air
After change, the object of LFP components is mutually without substantially changeing in cLFPM-2 with cLFP-2 samples.But from the change of sample unit cell volume
Change is seen（Table 1）, compared with LFP/C, the unit cell volume of cLFP-2 slightly reduces, and the unit cell volume of cLFPM-2 is almost unchanged；
The reduction of cLFP-2 unit cell volumes is caused by taking off lithium due to LFP.The result shows the sample of non-surface modification can be by ring
Border air aging, and the sample Jing Guo surface modification will not be by surrounding air aging.
The pyrroles added in experimentation can be in LFP/C after being adsorbed by LFP/C particle surfaces by vapor deposition
The synergistic effect of micro-air is lower in the metal ion and system of surface exposure aoxidizes, polymerize, in exposed particle surface shape
At one layer of pyrroles's oligomer protective film.Pyrroles's oligomer weight average molecular weight (M w) it is 780, molecular weight distribution index is
1.27, the oligomer that corresponding pyrrole ring average number is 12（Fig. 2）.
Fig. 3 is the N 1s high-resolution XPS spectrum figures of sample.From figure 3, it can be seen that with sample LFP/C（Fig. 3 a）And cLFP-2
（Fig. 3 b）It compares, the cLFPM-2 samples modified by pyrroles's oligomer（Fig. 3 c）Middle N 1s peak-to-peak signals are remarkably reinforced.Position in Fig. 3 c
N H, C N are corresponded to respectively in the peak of 400,400.7,402 eV+With C=N+Component, N 1s of these three components in traditional polypyrrole
It is frequently seen in spectrogram（Synthetic Metals, 2004, 145, 15-22; Polymer Degradation and Stability, 2015, 120, 392-401.）.XPS the result shows that, can be at LFP/C using patented technology of the present invention
Grain surface forms pyrroles's oligomer.
Fig. 4 and Fig. 5 is sample LFP/C（Fig. 4）、cLFPM-4（Fig. 5）SEM figure.Compared with originating LFP/C samples, pass through
Variation of the sample in particle size and pattern after surface modification is difficult to differentiate between, this is because formed in LFP/C particle surfaces
Azole polymer is the result of atomic size thickness.
Molecular dynamics simulation result of calculation shows pyrroles's vapour molecule preferentially at LFP/C carbon layer on surface hole position（I.e.
LFP exposed positions combine）, then nucleation in situ, growth, form the atomic layer level thickness for inhibiting surrounding air to be in direct contact with LFP
Azole polymer protective film.The nitrogen adsorption desorption test result of sample shows with pyrroles and LFP/C volume mass ratios（μL/
g）Increase, the pore volume of sample is gradually reduced（Table 1）.This explanation, the calculated results and experimental result are identical.
Fig. 6 is the high rate performance figure of sample cLFPM-2, LFP/C and cLFP-2.Although compared with low range（< 0.5 C）Under,
The specific discharge capacity of cLFPM-2 and LFP/C is closer to, but compared with high magnification（≥ 0.5 C）Under, the electric discharge specific volume of cLFPM-2
Amount is apparently higher than the specific discharge capacity of LFP/C.And compared to LFP/C, in the case where multiplying power is higher than 0.2 C, cLFP-2's puts
Electric specific capacity is substantially reduced.
Fig. 7 is the stable circulation linearity curve that sample cLFPM-2, LFP/C and cLFP-2 recycle 100 circles at 1 C.From figure
As can be seen that the initial discharge specific capacity of cLFPM-2, LFP/C and cLFP-2 are respectively 147,137 and 132 mA h g‒1, cycle
After 100 circles, the specific discharge capacity of cLFPM-2, LFP/C and cLFP-2 are respectively 137,116 and 97 mA h g‒1, capacity retention ratio
Respectively 88.4%, 84.7% and 73.5%.
Fig. 8 is the high rate performance figure of sample cLFPM-4, LFP/C and cLFP-4.In multiplying power≤2 C, cLFPM-4 with
The specific discharge capacity of LFP/C is closer to, but when multiplying power increases to 5 C, specific discharge capacity the putting higher than LFP/C of cLFPM-4
Electric specific capacity.And compared to LFP/C, it is within the scope of 0.1 5 C in multiplying power, the specific discharge capacity of cLFP-4 is substantially reduced.
Fig. 9 is the stable circulation linearity curve that sample cLFPM-4, LFP/C and cLFP-4 recycle 100 circles at 1 C.cLFPM-
4, the initial discharge specific capacity of LFP/C and cLFP-4 is respectively 140,137 and 121 mA h g‒1, after cycle 100 is enclosed, discharge ratio
Capacity remains 127,116 and 94 mA h g respectively‒1, capacity retention ratio is respectively 90.7%, 84.7% and 77.7%.
The above results show that even if mass percentage of pyrroles's oligomer in cLFPM compounds be about 5/10000ths
In the case of, the sample of surface modification after aging 2 months, recycles the specific discharge capacity ratios of 100 circles in surrounding air under 1 C
The specific discharge capacity of starting LFP/C samples improves 18.1%；And the sample of non-surface modification, aging 2 in surrounding air
The specific discharge capacity of 100 circles is recycled after month, under 1 C reduces 16.4% compared with the specific discharge capacity of beginning LFP/C sample.
When mass percentage of pyrroles's oligomer in cLFPM compounds is about 2/1000ths, the sample of surface modification
Product recycle electric discharge ratio of the specific discharge capacity compared with beginning LFP/C sample of 100 circles in surrounding air after aging 4 months, under 1 C
Capacity improves 9.5%；And the sample of non-surface modification, 100 circles are recycled in surrounding air after aging 4 months, under 1 C
Specific discharge capacity reduce 20.0% compared with the specific discharge capacity of beginning LFP/C sample.
To sum up, patented technology of the present invention can improve LFP/C anodes in the case where conducting polymer monomer dosage is few
Ageing resistance of the material in surrounding air, and its chemical property can be improved.
Table 1
Embodiment 3
A method of anode material of lithium battery ageing resistance being improved, by taking positive electrode is LMO powders as an example, steps are as follows：
(1) preparation of the LMO powders of surface modification
100 μ L thiophene are added to and fill 10 g LMO powders（The size of powder granule is 0.2 ~ 1 μm）50 mL containers
In, container is sealed, shaking container makes LMO powders be uniformly mixed with thiophene, cures 30 days at room temperature.During curing, shake daily
Visibly moved device 2 times, each shake time are no less than 1 min, the LMO powder samples of surface modification are obtained after the maturation period, by the sample
Product are referred to as LMOM.
(2) senile experiment
The container stopper for filling LMOM samples is opened, so that LMOM samples is exposed in surrounding air, to make sample be filled with surrounding air
It taps and touches, daily shake container occlusion 3 times, each shake time is no less than 1 min, opens plug after shaking every time, makes sample weight
It is new to expose in surrounding air.Ageing time is continuously 2 months, ranging from 5 38 °C of variation of ambient temperature, and range of humidity variation is
20‒75%.Sample after senile experiment is known as LMOM-2, wherein 2 be ageing time（Month）.
Compare senile experiment
LMOM samples described in above-mentioned senile experiment are replaced with starting LMO samples, remaining experimental implementation and condition are constant.It will be old
Change the sample after testing and be known as LMO-2, wherein 2 be ageing time（Month）.
(3) electrochemical property test of sample
Using CHI 660E electrochemical analysers and LANHE CT2001A cell testers to originating LMO, LMOM-2 and LMO-2
The chemical property of sample is compared test.
Interpretation of result
Figure 10 is the XRD diagram of sample LMO, LMOM-2 and LMO-2.LMO in the position of each diffraction maximum and document in Figure 10（JCPDS
88-1026）The position of each diffraction maximum is very identical, illustrates the object for not changing LMO by surface modification, environmental air aging
Phase.But in terms of the unit cell volume of sample, compared to LMO, the unit cell volume of LMO-2 slightly reduces, and the structure cell body of LMOM-2
Product does not change（Table 1）.The result shows the sample of non-surface modification, being placed 2 months in surrounding air partly to take off
Lithium, aging, and the sample of surface modification has good tolerance in surrounding air.
Figure 11 and Figure 12 is that the SEM of sample LMO and LMOM-2 scheme.Compared with LMO（Figure 11）, LMOM-2 samples（Figure 12）
Variation on granule-morphology and size is difficult to differentiate, this is because thiophen polymer is that atomic size thickness is made in LMOM-2 samples
At.
Figure 13 is the S 2p figures of sample LMO and LMOM-2.Compared with sample LMO（Figure 13 a）, the S 2p signal peaks of LMOM-2
It is remarkably reinforced（Figure 13 b）.Wherein, the peak for being located at 163.8 and 164.8 eV corresponds to S 2p respectively3/2With S 2p1/2Component, this and text
It offers（J. Mater. Chem. A, 2016, 4, 19060–19069）The S 2p of middle polythiophene3/2With S 2p1/2Component peaks connect very much
Closely.This result shows that, there is thiophen polymer on the surfaces LMOM-2.
Through TOF LC-MS（Figure 14）Show with GPC detections（Figure 15）, the thiophen polymer of LMOM-2 sample surfaces is thiophene
It is low to correspond to the thiophene containing 12 thiphene rings in polymer chain for oligomer, weight average molecular weight 977, breadth coefficient 1.06
Aggressiveness.
Figure 16 is the high rate performance figure of sample LMO, LMOM-2 and LMO-2.Although in 0.1 C, the starting of three kinds of samples
Specific capacity is closer to, but only LMOM-2 samples have higher cyclical stability after 0.1 C cycles, 10 circle.It is just forthright again
For energy, the high rate performance of three kinds of samples is followed successively by LMOM-2> LMO > LMO-2.
Figure 17 is the discharge curve of sample LMO, LMOM-2 and LMO-2 at 1 C.LMOM-2, LMO and LMO-2 are in 1 C
Under specific discharge capacity be respectively 85.8,68.0 and 40.1 mA h g‒1, and discharge platform is along LMOM-2, LMO, LMO-2 sequence
It continuously decreases.Compared to LMO, specific discharge capacities of the LMOM-2 at 1 C improves 26.2%, and electric discharges of the LMO-2 at 1 C
Specific capacity reduces 41.0%
When the above results show that the quality when thiophene oligomer accounts for about the 1% of LMOM compound quality, LMOM can be made to be exposed to ring
Border air remains to keep the specific capacity and high rate performance better than starting LMO samples after 2 months, and the LMO of non-surface modification is passed through
After surrounding air aging 2 months, the chemical property relatively starting LMO of gained LMO-2 samples is decreased obviously.This explanation, particle table
Ageing resistances of the LMO in surrounding air can be improved in the micro thiophene oligomer modification in face, and improves its chemical property.
Embodiment 4
A method of anode material of lithium battery ageing resistance being improved, by taking positive electrode is LNMCO/C powders as an example, step is such as
Under：
(1) preparation of the LNMCO/C powders of surface modification
50 μ L aniline are added to and fill 10 g LNMCO/C powders（The size of powder granule is 2 ~ 18 μm）50 mL containers
In, container is sealed, shaking container makes LNMCO/C powders be uniformly mixed with aniline, cures 14 days at room temperature.During curing, often
Its shake container 2 times, each shake time are no less than 1 min, the LNMCO/C powder samples of surface modification are obtained after the maturation period
The sample is referred to as cLNMCOM by product.
(2) senile experiment
The container stopper for filling cLNMCOM samples is opened, so that cLNMCOM samples is exposed in surrounding air, to make sample and environment
Air comes into full contact with, and daily shakes container occlusion 3 times, and each shake time is no less than 1 min, opens plug after shaking every time, makes
Sample exposes in surrounding air again.Ageing time is continuously 2 months, ranging from 0 26 °C of variation of ambient temperature, humidity variation
Ranging from 20 70%.Sample after senile experiment is known as cLNMCOM-2, wherein 2 be ageing time（Month）.
Compare senile experiment
CLNMCOM samples described in above-mentioned senile experiment are replaced with starting LNMCO/C samples, remaining experimental implementation and condition are not
Become.Sample after senile experiment is known as cLNMCO-2, wherein 2 be ageing time（Month）.
(3) electrochemical property test of sample
Using CHI 660E electrochemical analysers and LANHE CT2001A cell testers to originating cLNMCOM-2, LNMCO/C
It is compared test with the chemical property of cLNMCO-2 samples.
Interpretation of result
Figure 18 is the XRD diagram of sample LNMCO/C, cLNMCOM-2 and cLNMCO-2.In Figure 18 a, b, c the position of each diffraction maximum and
LNMCO in document（Chem. Mater. 2005, 17, 3695-3704）The position of each diffraction maximum is very identical, this illustrates process
After surface modification, air aging, the object of LNMCO components is mutually without substantially changeing in cLNMCOM-2 with cLNMCO-2 samples.
The R factors of sample can be calculated according to Figure 18（(I 006 + I 012)/I 101）, the R of LNMCO/C, cLNMCOM-2 and cLNMCO-2 because
Son is respectively 0.43,0.41 and 0.50.From the point of view of the R factors, by the sample of burin-in process again after surface modification, R because
Son is closer to initial sample；And non-surface modification is placed in the sample of aging in surrounding air, R factor variations are larger.
This explanation, places 2 months in surrounding air, can make LNMCO/C agings.
The SEM and EDS that Figure 19 and Figure 20 is LNMCO/C scheme.The class ball that sample LNMCO/C is mainly 9 13 μm by size
Shape particle forms, and the particle of these large-sizes is made of smaller 0.8 0.9 μm of the submicron particles accumulation of size
（Figure 19）.EDS analysis results（Figure 20）Show that the atomic ratio of tri- kinds of elements of Ni, Mn, Co in LNMCO/C samples is 5:3:2, this
Illustrate that the LNMCO/C samples in embodiment are LiNi0.5Mn0.3Co0.2O2/C。
Figure 21 is the N 1s spectrograms of sample cLNMCOM-2, LNMCO/C and cLNMCO-2.With LNMCO/C and cLNMCO-2 phases
Than the N 1s peak-to-peak signals of cLNMCOM-2 samples are remarkably reinforced, this cLNMCOM-2 sample surfaces of explanation Jing Guo surface modification has N
Element.Wherein, positioned at the peak of 399.2,400.0,401.0 eV be attributed to respectively the N of quinone ring=, the NH of phenyl ring and polaron N+
=.It is very close in the N 1s spectrograms of these polyanilines of N components synthesized by conventional solution method（Colloid Polym. Sci.
2017, 295, 1527-1534）, this illustrates the aniline for being adsorbed on the surfaces LNMCO/C, aniline polymerization is formd by oxidation polymerization
Object.
Show through GPC detections（Figure 22）, the aniline polymer of cLNMCOM-2 sample surfaces is Oligoanilines, heavy
Molecular weight is 1126, breadth coefficient 1.1, the Oligoanilines containing 12 aniline units in corresponding polymer chain.
Figure 23 is the high rate performance figure of cLNMCOM-2, LNMCO/C and cLNMCO-2 sample.Under each multiplying power,
The specific discharge capacity of cLNMCO-2 is below LNMCO/C, this illustrates LNMCO/C after aging in 2 months, and chemical property is apparent
Decline.On the contrary, cLNMCOM-2 is under the multiplying power more than 0.2 C, specific discharge capacity is above LNMCO/C.
Although at 0.1 C, the starting specific capacity of cLNMCOM-2 and the starting specific capacity of LNMCO/C are closer to, and are followed
After ring 10 encloses, the former specific capacity is apparently higher than the latter.For cLNMCOM-2 samples, after 10 circles are recycled at 2 C, discharge ratio
Capacity is 88.9 mA h g‒1, compared to the starting specific capacity at 0.1 C, capacity retention ratio 51.5%.And for
LNMCO/C samples, after 10 circles are recycled at 2 C, specific discharge capacity is 52.8 mA h g‒1, compared to the starting at 0.1 C
Specific capacity, capacity retention ratio 30.8%.
Figure 24 is discharge curve of cLNMCOM-2, LNMCO/C and cLNMCO-2 sample at 1 C.It can from Figure 24
Go out, the specific discharge capacity of cLNMCOM-2, LNMCO/C and cLNMCO-2 at 1 C is respectively 130.7,107.2 and 93.5 mA h
g‒1.Compared to LNMCO/C, specific discharge capacities of the cLNMCOM-2 at 1 C improves 21.9%, and cLNMCO-2 is at 1 C
Specific discharge capacity reduces 12.8%.
When the above results show that the quality when Oligoanilines accounts for about 5/1000ths of cLNMCOM compound quality, it can make
After cLNMCOM is exposed to surrounding air 2 months, remain to keep the specific capacity and high rate performance better than starting LNMCO/C samples.Phase
Instead, the LNMCO/C of non-surface modification is after surrounding air aging 2 months, the chemical property of gained cLNMCO-2 samples（Than
Capacity, high rate performance and cyclical stability）It is decreased obviously compared with starting LNMCO/C.
Embodiment 5
Other with embodiment 4, the difference is that, 300 μ L 2- ethyl aniline are added to and fill 10 g LNMCO powders（Powder
The size of body particle is 2 ~ 18 μm）50 mL containers in, container is sealed, shake container make LNMCO powders and 2- ethylo benzenes
Amine is uniformly mixed, and is cured 10 days at room temperature.During curing, it being shaken every day container 4 times, each shake time is no less than 10 min,
The LNMCO positive electrode samples of surface modification are obtained after maturation period.
Compared to starting LNMCO samples, the LNMCO of surface modification is after surrounding air aging 2 months, and sample is at 1 C
Specific discharge capacity can be improved 27.3%.
Embodiment 6
Other with embodiment 3, the difference is that, 200 μ L 3,4-rthylene dioxythiophenes are added to and fill 10 g LCO powder
Body（The size of powder granule is 2 ~ 10 μm）50 mL containers in, container is sealed, shake container make LCO powders and 3,4- second
Alkene dioxy thiophene is uniformly mixed, and is cured 14 days at room temperature.During curing, it is shaken every day container 3 times, each shake time is no less than
5 min obtain the LCO positive electrode samples of surface modification after the maturation period.
Compared to starting LCO samples, the LCO of surface modification is after surrounding air aging 2 months, sample putting at 1 C
Electric specific capacity can be improved 24.8%.
Embodiment 7
Other with embodiment 1, the difference is that, 300 μ L 3- N-ethyl pyrrole Ns are added to and fill 10 g LFP powders（Powder
The size of particle is 0.5 ~ 5 μm）50 mL containers in, container is sealed, shaking container keeps LFP powders and 3- N-ethyl pyrrole Ns mixed
It closes uniformly, cures 7 days at room temperature.During curing, it is shaken every day container 3 times, each shake time is no less than 2 min, maturation period
After surface modification LFP positive electrode samples.
Compared to starting LFP samples, the LFP of surface modification is after surrounding air aging 2 months, sample putting at 1 C
Electric specific capacity can be improved 26.7%.
Embodiment 8
Other with embodiment 1, the difference is that, 100 μ L 3- vinyl thiophenes are added to and fill 10 g LCO/C powders
（The size of powder granule is 0.1 ~ 2 μm）50 mL containers in, container is sealed, shake container make LCO/C powders and 3- second
Alkenyl thiophene is uniformly mixed, and is cured 14 days at room temperature.During curing, it is shaken every day container 4 times, each shake time is no less than 5
Min obtains the LCO/C positive electrode samples of surface modification after the maturation period.
Compared to starting LCO/C samples, the LCO/C of surface modification is after surrounding air aging 2 months, and sample is at 1 C
Specific discharge capacity can be improved 17.5%.
Embodiment 9
Other with embodiment 3, the difference is that, 300 μ L 3- ethyl aniline are added to and fill 10 g LMO/C powders（Powder
The size of body particle is 1 ~ 10 μm）50 mL containers in, container is sealed, shake container make LMO/C powders and 3- ethylo benzenes
Amine is uniformly mixed, and is cured 10 days at room temperature.During curing, it being shaken every day container 4 times, each shake time is no less than 10 min,
The LMO/C positive electrode samples of surface modification are obtained after maturation period.
Compared to starting LMO/C samples, the LMO/C of surface modification is after surrounding air aging 2 months, and sample is at 1 C
Specific discharge capacity can be improved 19.1%.
Claims (10)
1. a kind of method improving anode material of lithium battery ageing resistance, it is characterised in that：Positive electrode uses surface chemistry
The positive electrode powder of modification.
2. the method for improving anode material of lithium battery ageing resistance as described in claim 1, which is characterized in that including following
Step：
A. under room temperature environment air conditions, positive electrode powder is transferred in container；
B. it by coating material, is added in the container described in step a, container is sealed；
C. by mixing in coating material and container of the positive electrode powder described in step b, curing obtains surface chemical modification
Positive electrode powder；
The positive electrode powder for the surface chemical modification that step c is obtained is as anode material of lithium battery.
3. the method for improving anode material of lithium battery ageing resistance as claimed in claim 2, which is characterized in that in step a
The room temperature environment air conditions, range of temperature therein are 0 40 °C, and the relative humidity of surrounding air is 20
80%。
4. the method for improving anode material of lithium battery ageing resistance as claimed in claim 2, which is characterized in that in step a
The positive electrode is LiCoO2、LiCoO2/C、LiMn2O4、LiMn2O4/C、LiFePO4、LiFePO4/C、
LiNi x Mn y Co z O2 (x + y + z=1) or LiNi x Mn y Co z O2/C (x + y + z=1), wherein carbon coating anode material
The mass percentage of carbon is less than 5% in material；Positive electrode powder described in step a, the mesh of particle size >=800；It is preferred that
, the positive electrode powder described in step a, particle size is 0.1 ~ 18 μm.
5. the method for improving anode material of lithium battery ageing resistance as claimed in claim 2, which is characterized in that in step a
The material powder and container, wherein the volume of powder is no more than the 60% of vessel volume.
6. the method for improving anode material of lithium battery ageing resistance such as claim 2-5 any one of them, which is characterized in that
It is 0.5 30 mL/ that coating material described in step b, which refers to coating material, with the volume mass ratio of positive electrode powder
kg；
Coating material described in step b is aniline, thiophene, pyrroles, 2-aminotoluene, 3- methylanilines, 2- ethylo benzenes
Amine, 3- ethyl aniline, 2- vinyl aniline, 3- vinyl aniline, 3,4- ethene dioxythiophenes, 3 methyl thiophene, 3- ethyl thiophenes
Pheno, 3- vinyl thiophenes, 3,4- ethylene dioxies pyrroles, 1- benzyl -3,4- ethylene dioxies pyrroles, 3- methylpyrroles, 3- ethyl pyrroles
It coughs up or 3- vinyl pyrroles.
7. the method for improving anode material of lithium battery ageing resistance such as claim 2-6 any one of them, which is characterized in that
Mixing described in step c, mode are stirring, shake or vibrate.
8. the method for improving anode material of lithium battery ageing resistance such as claim 2-7 any one of them, which is characterized in that
Curing described in step c, curing time are 7 30 days, stir material during curing daily 24 times, each mixing time is
1‒30 min。
9. the method for improving anode material of lithium battery ageing resistance such as claim 2-8 any one of them, which is characterized in that
The positive electrode powder of surface chemical modification described in step c is that the surface of positive electrode covers layer of surface decorative layer；
It is furthermore preferred that finishing coat is conducting polymer oligomer；
The conducting polymer oligomer, to contain the oligomer of 8 ~ 14 monomers, weight average molecular weight distribution is 522 ~
1276；Molecular weight distribution index is 1.1 ~ 1.3；
Preferably, the monomer is aniline, thiophene, pyrroles, 2-aminotoluene, 3- methylanilines, 2- ethyl aniline, 3- ethylo benzenes
Amine, 2- vinyl aniline, 3- vinyl aniline, 3,4- ethene dioxythiophenes, 3 methyl thiophene, 3- ethylthiophenes, 3- vinyl
Thiophene, 3,4- ethylene dioxies pyrroles, 1- benzyl -3,4- ethylene dioxies pyrroles, 3- methylpyrroles or 3- N-ethyl pyrrole Ns or 3- ethylene
Base pyrroles；
It is furthermore preferred that the conducting polymer oligomer, monomer is pyrroles, N 1s high-resolution XPS spectrum figures show positioned at 400,
400.7, the peak of 402 eV；
It is furthermore preferred that the conducting polymer oligomer, monomer is aniline, N 1s high-resolution XPS spectrum figures show positioned at 399.2,
400.0, the peak of 401.0 eV；
It is furthermore preferred that the conducting polymer oligomer, monomer is thiophene, and S 2p high-resolution XPS spectrum figures are shown positioned at 163.8 Hes
164.8 the peak of eV.
10. such as the method that claim 2-9 any one of them improves anode material of lithium battery ageing resistance, feature exists
In the specific discharge capacity for recycling 100 circles at 1 C reaches 70 ~ 140 mA h g‒1, capacity retention ratio is 85 ~ 92%.
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