CN106299299A - A kind of anode material for lithium-ion batteries with surface hydrophobic and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries with surface hydrophobic and preparation method thereof Download PDFInfo
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- CN106299299A CN106299299A CN201610839291.2A CN201610839291A CN106299299A CN 106299299 A CN106299299 A CN 106299299A CN 201610839291 A CN201610839291 A CN 201610839291A CN 106299299 A CN106299299 A CN 106299299A
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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
- H01M4/36—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/48—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
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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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- 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
A kind of anode material for lithium-ion batteries with surface hydrophobic and preparation method thereof, the present invention relates to anode material for lithium-ion batteries that a kind of process for modifying surface obtains and preparation method thereof.The invention aims to solve tradition positive electrode cycle performance, storge quality and the problem poor with compatibility of electrolyte thereof.There is one layer of Organic substance hydrophobic layer on the surface of the anode material for lithium-ion batteries with surface hydrophobic of the present invention, and the thickness of this hydrophobic layer is 0.5nm～20nm, and the mass content of hydrophobic layer is 0.1%～10%；The preparation method of the anode material for lithium-ion batteries with surface hydrophobic of the present invention is the Organic substance and organic solvent mix homogeneously with hydrophobic performance to be stirred with positive electrode and reacted again obtain mixture at 30～80 DEG C, mixture is filtrated to get solid filter cake, and the process that then solid filter cake carries out two thermogrades obtains the positive electrode of the present invention.Material prepared by the present invention is for lithium ion battery.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries that a kind of process for modifying surface obtains and preparation method thereof.
Background technology
Positive electrode is the key factor determining performance of lithium ion battery, the energy density of lithium ion battery, safety, one-tenth
The performances such as basis and cycle life are all closely related with positive electrode.Along with the development of lithium ion battery technology, to positive electrode
Performance it is also proposed tightened up requirement, such as safety, cost and cycle performance etc..The eighties in 20th century, American scholar
J.B.Goodenough et al. is found that cobalt acid lithium (LiCoO first2) as the positive electrode of deintercalate lithium ions, and can apply for
Patents.Hereafter, cobalt acid lithium relies on excellent chemical property and good electrode machining performance in the nineties in 20th century
The positive electrode of business-like small-sized electronic product lithium ion battery just it is successfully applied to by Sony corporation of Japan.But, closely
Over Nian, the application of lithium ion battery is constantly expanded, and obtains the most widely in fields such as electric motor car and scale energy storage
Application.Lithium ion battery is had higher requirement by these new applications.In the process, cobalt acid lithium material is due to it
The shortcoming such as high cost and poor heat stability, has been not suitable as the positive pole of lithium ion battery particularly power-type lithium ion battery
Material, therefore develops new anode material for lithium-ion batteries extremely urgent.
At present, the positive electrode master used it is hopeful in large-scale lithium ion battery particularly power-type lithium ion battery most
Spinel lithium manganate (LiMn to be included2O4), LiFePO4 (LiFePO4) and nickel cobalt manganese (LiNixCoyMnzO2) and nickel cobalt aluminum
(LiNixCoyAlzO2) ternary system material.Lithium manganate material has abundant raw material source, low cost, running voltage advantages of higher,
But its specific capacity is relatively low, and the cyclical stability under long-term cyclical stability particularly high temperature is bad.LiFePO4 has
Low cost, have extended cycle life, structural stability and heat stability advantages of higher, but its electronics and ionic conductivity are the lowest, make
Obtain this material high-rate charge-discharge capability and cryogenic property is poor.Additionally, this material there is also, specific capacity is low, product stability and
The shortcomings such as concordance is bad and tap density is low, electrode machining poor performance.Ternary system material (includes nickel cobalt manganese and nickel cobalt aluminum
Deng) initially utilized hydroxide co-precipitation presoma at high temperature sintering by Japanese scholars T.Ohzuku and Canada scholar J.Dahn
Lower preparation.Such material has higher specific capacity and preferable structural stability and a heat stability, but there is also relatively costly,
Electrode machining poor performance and processing environment is required the shortcomings such as strict.
Many disadvantages in order to overcome existing positive electrode to exist improves its performance simultaneously, and people have carried out substantial amounts of research
Work and achieve good effect.After 2000, along with anode material for lithium-ion batteries research is goed deep into by scholars,
The surface nature of the discovery positive electrode shadow to its processing characteristics and chemical property, particularly cycle performance and high-temperature stability
Ringing very big, therefore the coating modification on positive electrode surface becomes the hot fields of research.Researcher many employings nothing the most both at home and abroad
Positive electrode is coated with and surface modification by machine oxide or phosphate, such as aluminium oxide, magnesium oxide, titanium oxide and phosphoric acid
Aluminum etc..Although using inorganic oxide or phosphate positive electrode to be carried out coating modification and can improve its cycle performance and safety
Performance, but be typically passed through high-temperature heat treatment process, in the process metal-oxide or Phosphate coating material can with just
Pole material reacts, and after often leading to cladding, the capacity of material reduces and the problem such as concordance variation.And, positive pole material
Material, the ternary system anode material that particularly nickel comparision contents is high, owing to its own face pH value is too high, configure process at anode sizing agent
In the easily moisture absorption, make slurry present jelly state, cause slurry to be coated with and battery with two side terminals is deteriorated and disqualification rate
Rising, and the follow-up pole piece moisture absorption also results in the drastically decline of battery performance, this leverages positive electrode particularly
The industrialization process of ternary system anode material.Although inorganic oxide or phosphatic coating modification can reduce ternary system positive pole
The surface pH value of material, but its effect inconspicuous.Therefore, the water resistance improving positive electrode has become as lithium ion battery
Technology and the important need of industry development.
Summary of the invention
The invention aims to solve tradition positive electrode cycle performance, storge quality and compatible with electrolyte thereof
Property difference problem, and provide a kind of anode material for lithium-ion batteries with surface hydrophobic and preparation method thereof.
There is one layer of Organic substance hydrophobic layer on the surface of the anode material for lithium-ion batteries with surface hydrophobic of the present invention, should
The thickness of hydrophobic layer is 0.5nm～20nm, and the mass content of hydrophobic layer is 0.1%～10%；This positive electrode is layer structure
Or the combination of one or more in the anode material for lithium-ion batteries of spinel structure.
Described Organic substance hydrophobic layer is RSiX3, wherein R is epoxide, sulfydryl, amino, vinyl, ethyoxyl, epoxy radicals, acyl
One or more in amido, methacryloxy, aminopropyl, urea groups, NCO organo-functional group, X is can water
One or more in the halogen of solution, alkoxyl, acyloxy.
The positive electrode of layered structure is LiNixCoyMnzM1‐x‐y‐zO2, wherein 0≤x≤1,0≤y≤1,0≤z≤
1, M is in Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi
One or more.
The preparation method of the anode material for lithium-ion batteries with surface hydrophobic of the present invention sequentially includes the following steps:
One, will there is the Organic substance a and organic solvent b of hydrophobic performance according to 1:(1～40) volume ratio dissolve, stir 30
～60min obtains organic solution c；
Two, by positive electrode and organic solution c according to 1:(0.2～20) mass ratio mixing, stir at 30～80 DEG C
30～180min obtain solidliquid mixture d；
Three, solidliquid mixture d being filtrated to get solid filter cake, in the solid filter cake obtained, the mass content of Organic substance a is not
More than 10%；
Four, by the solid filter cake that obtains in dry atmosphere, temperature is to process 0.5～5h at 50～200 DEG C, Jin Er
Temperature is heat treatment 0.5～10h under the vacuum of 100～300 DEG C or inert atmosphere conditions, i.e. obtain surface modified one layer organic
The anode material for lithium-ion batteries of thing hydrophobic layer.
Organic substance a described in step one is RSiX3, wherein R is epoxide, sulfydryl, amino, vinyl, ethyoxyl, epoxy
One or more in base, amide groups, methacryloxy, aminopropyl, urea groups, NCO organo-functional group, X is energy
One or more in the halogen of enough hydrolysis, alkoxyl, acyloxy.
Described organic solvent b is in ethanol, methanol, isopropanol, acetone, ether, ethyl acetate, benzene, toluene, normal hexane
One or both and above mixture；
Described alr mode is the one in mechanical agitation, magnetic agitation or ultrasonic agitation.
Positive electrode described in step 2 includes the cobalt acid lithium of stratiform or spinel-type, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt
One or both and above mixture in lithium aluminate, stratiform rich lithium manganese base solid solution.
Described inert atmosphere is nitrogen or argon.
The present invention is relative to the advantage of prior art:
1. anode material for lithium-ion batteries surface is during coated by hydrophobic Organic substance, and Organic substance first can be with lithium-ion electric
Positive electrode surface, pond reacts, and forms SiO M (M is the metal in positive electrode) covalent bond.Meanwhile, hydrophobic organic
Thing molecule the most mutually associate formation cancellated thin film cover on positive electrode surface, make anode material for lithium-ion batteries surface
Realize organic hydrophobization of uniformity.
2. the surface water-repellent layer of material can protect anode material for lithium-ion batteries surface not corroded by water, prevent lithium from
Sub-cell positive material go lithiumation.Meanwhile, during anode sizing agent configures, it is possible to prevent the slurry moisture absorption, improves positive pole and be coated with
The concordance of cloth and reliability, hence it is evident that improve the processing characteristics of positive electrode.
3. the Organic substance on anode material for lithium-ion batteries surface can improve the compatibility of itself and organic electrolyte, accelerates electricity
The impregnation process of electrolyte in the preparation process of pond, also helps the generation of interfacial electrochemistry reaction.
4. in electrochemistry cyclic process, the anode material for lithium-ion batteries surface organic matter prepared by the inventive method
The side reaction that can effectively stop positive electrode and electrolyte occurs, and slows down in electrolyte HF to anode material for lithium-ion batteries
Corrode, improve the cyclical stability of anode material for lithium-ion batteries.
5. the preparation technology of the present invention is simple, and low cost, is easily achieved industrialization.
Accompanying drawing explanation
Fig. 1 is the Li (Ni of the original material used in embodiment 10.73Co0.12Mn0.15)O2Anode material for lithium-ion batteries
Scanning electron microscope (SEM) photograph；
Fig. 2 is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane@Li of embodiment 1 preparation
(Ni0.73Co0.12Mn0.15)O2Anode material for lithium-ion batteries scanning electron microscope (SEM) photograph；
Fig. 3 is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane@Li of embodiment 1 preparation
(Ni0.73Co0.12Mn0.15)O2Anode material for lithium-ion batteries X ray diffracting spectrum；
Fig. 4 is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane@Li of embodiment 1 preparation
(Ni0.73Co0.12Mn0.15)O2The infrared Absorption spectrogram of anode material for lithium-ion batteries；
Fig. 5 is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane@Li of embodiment 1 preparation
(Ni0.73Co0.12Mn0.15)O2Anode material for lithium-ion batteries and the electrochemistry cyclic curve comparison diagram of original material；Wherein 1 is
Placing aerial original material, 2 is to place lithium ion cell positive material prepared by aerial employing the technology of the present invention
Material.
Fig. 6 is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane@Li of embodiment 1 preparation
(Ni0.73Co0.12Mn0.15)O2Anode material for lithium-ion batteries and the electrochemistry high rate performance comparison diagram of original material.Wherein 1 is
Placing aerial original material, 2 is to place lithium ion cell positive material prepared by aerial employing the technology of the present invention
Material.
Fig. 7 is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane@Li of embodiment 1 preparation
(Ni0.73Co0.12Mn0.15)O2After anode material for lithium-ion batteries and original material seal preservation respectively and place in atmosphere
Electrochemistry cycle performance comparison diagram.Wherein 1 is to seal the original material preserved, and 2 is to seal the employing the technology of the present invention system preserved
Standby anode material for lithium-ion batteries, 3 for placing aerial original material, and 4 for placing the aerial employing present invention
Anode material for lithium-ion batteries prepared by technology.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes between each detailed description of the invention
Combination in any.
Detailed description of the invention one: the surface of the anode material for lithium-ion batteries with surface hydrophobic of present embodiment has
One layer of Organic substance hydrophobic layer, the thickness of this hydrophobic layer is 0.5nm～20nm, and the mass content of hydrophobic layer is 0.1%～10%；Should
Positive electrode is the combination of one or more in the anode material for lithium-ion batteries of layer structure or spinel structure.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one, and described Organic substance hydrophobic layer is
RSiX3, wherein R is epoxide, sulfydryl, amino, vinyl, ethyoxyl, epoxy radicals, amide groups, methacryloxy, ammonia third
One or more in base, urea groups, NCO organo-functional group, X be can hydrolyze halogen, alkoxyl, in acyloxy
One or more.Other steps are identical with detailed description of the invention one with parameter.
Detailed description of the invention three: present embodiment unlike detailed description of the invention one, the positive pole of layered structure
Material is LiNixCoyMnzM1‐x‐y‐zO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1, M is Zr, Fe, Sm, Pr, Nb, Ga, Zn,
One or more in Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi.Other steps and parameter
Identical with detailed description of the invention one.
Detailed description of the invention four: the lithium ion cell positive material with surface hydrophobic as described in detailed description of the invention one
The preparation method of material sequentially includes the following steps:
One, will there is the Organic substance a and organic solvent b of hydrophobic performance according to 1:(1～40) volume ratio dissolve, stir 30
～60min obtains organic solution c；
Two, by positive electrode and organic solution c according to 1:(0.2～20) mass ratio mixing, stir at 30～80 DEG C
30～180min obtain solidliquid mixture d；
Three, solidliquid mixture d being filtrated to get solid filter cake, in the solid filter cake obtained, the mass content of Organic substance a is not
More than 10%；
Four, by the solid filter cake that obtains in dry atmosphere, temperature is to process 0.5～5h at 50～200 DEG C, Jin Er
Temperature is heat treatment 0.5～10h under the vacuum of 100～300 DEG C or inert atmosphere conditions, i.e. obtain surface modified one layer organic
The anode material for lithium-ion batteries of thing hydrophobic layer.
Detailed description of the invention five: present embodiment Organic substance a unlike detailed description of the invention four, described in step one
For RSiX3, wherein R is epoxide, sulfydryl, amino, vinyl, ethyoxyl, epoxy radicals, amide groups, methacryloxy, ammonia third
One or more in base, urea groups, NCO organo-functional group, X be can hydrolyze halogen, alkoxyl, in acyloxy
One or more.Other steps are identical with detailed description of the invention four with parameter.
Detailed description of the invention six: present embodiment is unlike detailed description of the invention four, and described organic solvent b is second
One or both and above mixture in alcohol, methanol, isopropanol, acetone, ether, ethyl acetate, benzene, toluene, normal hexane.
Other steps are identical with detailed description of the invention four with parameter.
Detailed description of the invention seven: present embodiment is unlike detailed description of the invention four, and described alr mode is machine
One in tool stirring, magnetic agitation or ultrasonic agitation.Other steps are identical with detailed description of the invention four with parameter.
Detailed description of the invention eight: present embodiment unlike detailed description of the invention four, positive pole material described in step 2
Material includes the cobalt acid lithium of stratiform or spinel-type, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, stratiform rich lithium manganese base solid solution
In one or more mixture.Other steps are identical with detailed description of the invention four with parameter.
Detailed description of the invention nine: present embodiment is unlike detailed description of the invention four, and described inert atmosphere is nitrogen
Or argon.Other steps are identical with detailed description of the invention four with parameter.
Embodiment 1
The preparation method of the anode material for lithium-ion batteries with surface hydrophobic of the present embodiment sequentially includes the following steps:
(1) γ-glycidyl ether oxygen propyl trimethoxy silicane is dissolved in ethanol according to volume ratio 1:6, stirring
20min；
(2) nickle cobalt lithium manganate is joined γ-glycidyl ether oxygen propyl trimethoxy silicane according to the mass ratio of 1:10
Solution stirs 30min；
(3) solidliquid mixture is filtrated to get the solid filter cake that organic solvent content is 5%；
(4) filter cake is carried out under the conditions of 300 DEG C heat treatment, after processing 4h, obtain required product.
Embodiment 2
The preparation method of the anode material for lithium-ion batteries with surface hydrophobic of the present embodiment sequentially includes the following steps:
(1) by γ-glycidyl ether oxygen propyl trimethoxy silicane and the mixture of APTES
It is dissolved in ethanol according to volume ratio 1:5, stirs 30min；
(2) by nickel cobalt lithium aluminate according to the mass ratio of 1:8 join γ-glycidyl ether oxygen propyl trimethoxy silicane and
The mixture solution of APTES stirs 45min；
(3) solidliquid mixture is filtered to obtaining the solid filter cake that organic solvent content is 4%；
(4) filter cake is carried out under the conditions of 250 DEG C heat treatment, after processing 4h, obtain required product.
Embodiment 3
The preparation method of the anode material for lithium-ion batteries with surface hydrophobic of the present embodiment sequentially includes the following steps:
(1) by the mixture of γ-mercaptopropyl trimethoxysilane KH580 and γ-mercaptopropyl trimethoxysilane according to body
Amass and be dissolved in acetone than 1:5, stir 20min；
(2) cobalt acid lithium is joined γ-mercaptopropyl trimethoxysilane KH580 and γ-mercapto propyl group according to the mass ratio of 1:5
The mixture solution of trimethoxy silane stirs 60min；
(3) solidliquid mixture is filtered to obtaining the solid filter cake that organic solvent content is 5%；
(4) filter cake is carried out under the conditions of 200 DEG C heat treatment, after processing 5h, obtain required product.
In order to measure the chemical property of the nickel-cobalt lithium manganate cathode material using process for modifying surface of the present invention to prepare, will
The nickel-cobalt lithium manganate cathode material of the surface modification of above-mentioned synthesis, acetylene black and PVDF (Kynoar) are according to 8:1:1's
Ratio is mixed to form slurry at normal temperatures and pressures, and even application is in aluminum foil substrate.By the anode pole piece that obtains 120 DEG C of conditions
After lower drying, compress under a certain pressure, continue to dry 10 hours at 120 DEG C, then anode pole piece is cut out punching and become area
For 1cm2Thin rounded flakes as positive pole, the LiPF with lithium sheet as negative pole, with concentration as 1mol/L6EC+DMC (volume ratio 1:1)
Solution is electrolyte, is assembled into experimental cell in the glove box of full argon.
Experimental cell uses new prestige electro-chemical test passage to carry out charge and discharge cycles test.Charging and discharging currents is 100mA/g,
Charge cutoff voltage is 4.30V, and discharge cut-off voltage is 3.0V.From accompanying drawing 5 charging and discharging curve it is found that after modification
Nickel-cobalt lithium manganate cathode material is higher than unmodified material capacity；And after being exposed in air ambient, modified lithium
Ion battery positive electrode wants height more than unmodified positive electrode capacity, compares after original material processed by the inventive method
Material the most cruelly leak after do not occur substantially to decay in performance.
Anode material for lithium-ion batteries from the high rate performance curve of accompanying drawing 6 it is found that after modification is with unmodified
Material high rate performance basically identical；But it is an exposure in air ambient the anode material for lithium-ion batteries after post-modification the most not
Decay, and after unmodified material exposes in atmosphere, high rate performance there occurs substantially decay.
The anode material for lithium-ion batteries with surface hydrophobic that process for modifying surface of the present invention prepares is existed
Granular size and morphology observation is carried out on HitachiS-4000 electronic scanner microscope.From accompanying drawing 1 and accompanying drawing 2 it is found that adopt
The nickel-cobalt lithium manganate material prepared with the process for modifying surface of the present invention is not clearly distinguished from original material, all presents complete
Spheroidal particle, particle size, in 5-15 microns, even particle size, smooth surface, illustrates the surface modification of the present invention
Technology can well maintain original pattern and the structure of positive electrode.
The crystal structure of the nickel-cobalt lithium manganate cathode material prepared by process for modifying surface of the present invention uses RigakuB/
Max-2400X x ray diffractometer x is analyzed.It appeared that surface modifying material has the layer structure of standard from accompanying drawing 3,
Free from admixture exists mutually, shows that the process for modifying surface of the present invention is technology as mild as a dove, will not produce the body construction of material
Raw impact.
The nickel-cobalt lithium manganate cathode material prepared by process for modifying surface of the present invention uses Thermo Scientific infrared
Spectrogrph is analyzed.It appeared that synthetic surfaces has the organic characteristic peak of corresponding surface hydrophobicity from accompanying drawing 4
Exist.
Claims (9)
1. an anode material for lithium-ion batteries with surface hydrophobic, it is characterised in that the surface of this positive electrode has
Layer Organic substance hydrophobic layer, the thickness of this hydrophobic layer is 0.5nm～20nm, and the mass content of hydrophobic layer is 0.1%～10%；This is just
Pole material is the combination of one or more in the anode material for lithium-ion batteries of layer structure or spinel structure.
A kind of anode material for lithium-ion batteries with surface hydrophobic the most according to claim 1, it is characterised in that institute
Stating Organic substance hydrophobic layer is RSiX3, wherein R is epoxide, sulfydryl, amino, vinyl, ethyoxyl, epoxy radicals, amide groups, methyl
One or more in acryloxy, aminopropyl, urea groups, NCO organo-functional group, X be can hydrolyze halogen,
One or more in alkoxyl, acyloxy.
A kind of anode material for lithium-ion batteries with surface hydrophobic the most according to claim 1, it is characterised in that institute
The positive electrode stating layer structure is LiNixCoyMnzM1-x-y-zO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1, M is Zr, Fe,
One or several in Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi
Kind.
The preparation method of a kind of anode material for lithium-ion batteries with surface hydrophobic, it is special
Levying and be, the method sequentially includes the following steps:
One, will there is the Organic substance a and organic solvent b of hydrophobic performance according to 1:(1～40) volume ratio dissolve, stirring 30～
60min obtains organic solution c；
Two, by positive electrode and organic solution c according to 1:(0.2～20) mass ratio mixing, stir at 30～80 DEG C 30～
180min obtains solidliquid mixture d；
Three, solidliquid mixture d being filtrated to get solid filter cake, in the solid filter cake obtained, the mass content of Organic substance a is not more than
10%；
Four, by the solid filter cake that obtains in dry atmosphere, temperature is to process 0.5～5h at 50～200 DEG C, and then in temperature
It is heat treatment 0.5～10h under the vacuum of 100～300 DEG C or inert atmosphere conditions, i.e. obtains surface and modified one layer of Organic substance and dredge
The anode material for lithium-ion batteries of water layer.
The preparation method of a kind of anode material for lithium-ion batteries with surface hydrophobic the most according to claim 4, its
Being characterised by, the Organic substance a described in step one is RSiX3, wherein R is epoxide, sulfydryl, amino, vinyl, ethyoxyl, epoxy
One kind of multiple in base, amide groups, methacryloxy, aminopropyl, urea groups, NCO organo-functional group, X is can
One or more in the halogen of hydrolysis, alkoxyl, acyloxy.
The preparation method of a kind of anode material for lithium-ion batteries with surface hydrophobic the most according to claim 4, its
Being characterised by, described organic solvent b is in ethanol, methanol, isopropanol, acetone, ether, ethyl acetate, benzene, toluene, normal hexane
One or both and above mixture.
The preparation method of a kind of anode material for lithium-ion batteries with surface hydrophobic the most according to claim 4, its
Being characterised by, described alr mode is the one in mechanical agitation, magnetic agitation or ultrasonic agitation.
The preparation method of a kind of anode material for lithium-ion batteries with surface hydrophobic the most according to claim 4, its
Being characterised by, positive electrode described in step 2 includes the cobalt acid lithium of stratiform or spinel-type, LiMn2O4, nickle cobalt lithium manganate, nickel
One or both and above mixture in cobalt lithium aluminate, stratiform rich lithium manganese base solid solution.
The preparation method of a kind of anode material for lithium-ion batteries with surface hydrophobic the most according to claim 4, its
Being characterised by, described inert atmosphere is nitrogen or argon.
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| CN109778301A (en) * | 2019-01-03 | 2019-05-21 | 北京工业大学 | The preparation of one type monocrystalline lithium-rich oxide material and application |
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| CN112216821A (en) * | 2019-07-09 | 2021-01-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Battery material and preparation method and application thereof |
| CN110364719A (en) * | 2019-07-25 | 2019-10-22 | 苏州大学 | The nickelic metal oxide materials and preparation method thereof of silicon oxygen modification |
| WO2021012708A1 (en) * | 2019-07-25 | 2021-01-28 | 苏州大学 | Siloxane modified high nickel metal oxide material and preparation method therefor |
| CN111600002A (en) * | 2020-05-30 | 2020-08-28 | 海宏(唐河)新能源科技有限公司 | Preparation method of aluminum triethoxide coated nickel cobalt lithium manganate modified material |
| CN112397719A (en) * | 2020-11-16 | 2021-02-23 | 华鼎国联动力电池有限公司 | Hydrophobic lithium battery positive electrode material, positive electrode and preparation method thereof |
| CN114551789A (en) * | 2020-11-26 | 2022-05-27 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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| CN114864887B (en) * | 2022-04-07 | 2023-09-22 | 湖南金硅科技有限公司 | Modification method for fluidity of silicon oxide |
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