CN108565452A - A method of handling anode material for lithium-ion batteries using acid high polymer - Google Patents
A method of handling anode material for lithium-ion batteries using acid high polymer Download PDFInfo
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- CN108565452A CN108565452A CN201810084074.6A CN201810084074A CN108565452A CN 108565452 A CN108565452 A CN 108565452A CN 201810084074 A CN201810084074 A CN 201810084074A CN 108565452 A CN108565452 A CN 108565452A
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- acid
- lithium
- high polymer
- anode material
- 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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- 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 method handling anode material for lithium-ion batteries using acid high polymer, the method includes the following steps：Preparing has hydrophobic acid high polymer；To have hydrophobic acid high polymer and organic solvent to be uniformly mixed, and obtain organic solution；Organic solution and positive electrode are stirred at normal temperatures and mixture is obtained by the reaction；By the further heating evaporation of obtained mixture, forming alkalinity reduces and has hydrophobic positive electrode, further promotes the cycle performance of material.The method for preparing anode material of the present invention is handled positive electrode using with certain acidity and hydrophobic solvent, the solvent can leniently have an effect with positive electrode, and keep positive electrode crystal structure complete, positive electrode any surface finish that treated, alkalinity reduces, and has surface hydrophobic.
Description
Technical field
The present invention relates to the processing methods of anode material for lithium-ion batteries, more specifically, being related to a kind of using acid high
The method that polymers handles anode material for lithium-ion batteries.
Background technology
In the 1980s, American scholar J.B.Goodenough et al. is found that cobalt acid lithium (LiCoO for the first time2) can be with
As the positive electrode of deintercalate lithium ions, hereafter, cobalt acid lithium relies on excellent chemical property and good electrode machining performance
Commercialized small-sized electronic product lithium ion battery is being successfully applied to just by Sony Corporation of Japan in early 1990s
Pole material.Now, lithium ion battery has been widely used in all kinds of small-sized portable electronic products and electric tool, and by
Gradually largely apply to new-energy automobile market.Positive electrode is the key that manufacture lithium ion battery in lithium battery industry, due to just
Pole material specific capacity is significantly lower than general negative material, often so that the performance of negative material is unable to give full play so that just
Pole material property directly affects the indices of final battery.
Currently, the shortcomings of cobalt acid lithium material is due to its high cost and poor thermal stability, has been not suitable as lithium-ion electric
The positive electrode of pond especially power-type lithium ion battery.Also, for lithium ion battery material, since preparation process needs add
Add excessive lithium to obtain the positive electrode of good crystallinity, when dispensing can slightly improve Li/M ratios (i.e. lithium salts is suitably excessive) and come more
It mends and is lost caused by sintering process, therefore how much can all have a small amount of Li residues (at high temperature with Li2The form presence of O),
Temperature is reduced to Li after room temperature2O can adsorb the CO in air2And H2O and form LiOH and Li2CO3Deng making positive electrode exist
The excessive problem of surface lithium residue.
In addition, in storage, if exposure is in air, in the active oxygen anion meeting on positive electrode surface and air
CO2With reaction of moisture and generate carbonate, while lithium ion from ontology move to surface and material surface formed Li2CO3.By
It is excessively high in own face pH value, the easy to absorb moisture in anode sizing agent configuration process, make slurry present jelly state, cause slurry without
Method is coated with and battery with two side terminals is deteriorated and disqualification rate rises, and subsequent pole piece can also the moisture absorption in air, these
Lithium residue can deteriorate the electrochemical environment of battery, promote electrolyte decomposition, reduce battery performance, also result in electrode machining
The problem of energy difference.This leverages the industrialization process of positive electrode especially ternary system anode material.
For the above problem, existing solution is to carry out double sintering in lower temperature by the way of washing
Technique, reduce the remaining content of anode material for lithium-ion batteries surface alkalinty lithium.This method can be by the alkaline, lithium on surface
Residual clean ratio more thoroughly, but processing after positive electrode times volumetric properties be decreased obviously.And it is carried out using inorganic acid
Processing, acidity are easy that cathode material structure is made to change, and influence the integrality of anode material for lithium-ion batteries crystal structure.
Therefore it provides a kind of easy method reduces the alkalinity of anode material for lithium-ion batteries, and make it have hydrophobic
Property, and the problem of do not influence the chemical property of positive electrode, be those skilled in the art's urgent need to resolve.
Invention content
In view of this, the present invention is more in order to solve positive electrode surface lithium residue, electrode machining caused by alkalinity is excessively high
The problem of contact with moisture in difficult, positive electrode and air causes chemical property to reduce provides a kind of using acid high
The method that polymers handles anode material for lithium-ion batteries.
To achieve the goals above, the present invention adopts the following technical scheme that：
A method of anode material for lithium-ion batteries being handled using acid high polymer, this approach includes the following steps：
Step 1：It is 1 by volume by dense inorganic acid and water：1.5~100 ratio is diluted as bottom liquid；It will
The dopant and polymer monomer of low-surface-energy are 1 in mass ratio：20~1000 ratio is added in the liquid of bottom；It is 5 in temperature
In~8 DEG C of whipping process, oxidant was added every 1~3 minute, obtains having wash with distilled water hydrophobic acid high poly-
Object；
Step 2：It is 1 in mass ratio by acid high polymer and organic solvent：50~1000 ratio is dissolved, stirring
It is made into organic solution；
Step 3：The organic solution that positive electrode and step 2 are obtained is 1 in mass ratio：0.1~50 ratio mixing,
Solidliquid mixture is obtained after stirring；
Step 4：By solidliquid mixture at 100~200 DEG C heating evaporation, be in temperature by obtained solid powder
Drying is evaporated in vacuo at 50~200 DEG C to get being reduced to alkalinity and having hydrophobic anode material for lithium-ion batteries；
The total dosage of oxidant in the step 1 is 1.5~5 times of polymer monomer quality, the reaction time 120~
360min；
The stir process time in the step 2 is 30~60min；
30~180min of stir process time in the step 3；
Vacuum evaporation drying time in the step 4 is 0.5~12h, high poly- in the anode material for lithium-ion batteries
The mass content of object is 0.1%~6%.
By using above-mentioned technical proposal, beneficial effects of the present invention are as follows：
Preferably, the inorganic acid in the step 1 is the mixture of one or both of hydrochloric acid and phosphoric acid.
Preferably, the dopant of the low-surface-energy in the step 1 be acetic acid, it is lauric acid/dodecanoic acid, perfluoro caprylic acid (PFOA), complete
Fluorine decanedioic acid (PFSEA), perfluorooctane sulfonate (PFOS), threonine, proline, arginine, valine, trifluoromethanesulfonic acid lithium, ten
Dialkyl benzene sulfonic acids sodium (SDBS), dinonyl how one or more mixtures in sulfonic acid, dioctyl succinate sulfonic acid.
By using above-mentioned preferred embodiment, beneficial effects of the present invention are as follows：
The high polymer of preparation can be made to have acidity using the mixture of one or both of inorganic acid hydrochloric acid and phosphoric acid,
Prepare acidic polymer.
Using the dopant of low-surface-energy, the surface nature of prepared high polymer can be improved, make it have hydrophobicity.
Preferably, the polymer monomer in the step 1 is aniline, lactic acid, glycolic, one kind in ethylene glycol or more
Kind mixture.
Preferably, the oxidant in the step 1 is (NH4)2S2O8、K2Cr2O7、KIO3、FeCl3、H2O2、 MnO2In
One or more mixtures.
Preferably, the hydrophobic acid high polymer that has prepared in the step 1 is polyaniline (PANI), polylactic acid
(PLA), polyglycolic acid (PGA), polylactide polyglycolic acid copolymer (PLGA), polyaniline ethylene glycol copolymer (PANI-PEG)
And one or more mixtures in the above polymer monomer and other monomer copolymers.
By using above-mentioned preferred embodiment, beneficial effects of the present invention are as follows：
By using these oxidants, polymer monomer used can be efficiently oxidized to stablize, had excellent performance
High polymer.And the high polymer of the preparation made due to the use of the dopant of inorganic acid and low-surface-energy while there is hydrophobicity
And acidity.
Preferably, the organic solvent in the step 2 is N-Methyl pyrrolidone (NMP), n,N-Dimethylformamide
(DMF), dichloromethane, one kind in chloroform, benzene, toluene, ether, isopropanol, hexafluoroisopropyl alcohol, acetone, n-hexane
Or in which several mixture.
By using above-mentioned preferred embodiment, beneficial effects of the present invention are as follows：
Prepared high polymer is diluted using organic solvent, the dosage of high polymer can be reduced, it is cost-effective.
Preferably, the positive electrode of layered structure is LiNixCoyMnzM1-x-y-zO2, wherein 0≤x≤1,0≤y≤
1,0≤z≤1, M Mg, Al, Fe, Zr, Sm, Pr, Nb, Ga, Zn, Y, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn,
One or more of Sb, La, Bi.
Preferably, the agitating mode in the step 1 is one kind in mechanical agitation, magnetic agitation or ultrasonic agitation.
Preferably, the positive electrode in the step 3 includes but not limited to the cobalt acid lithium of stratiform or spinel-type, mangaic acid
The mixture of one or both of lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, stratiform rich lithium manganese base solid solution or more.
By using above-mentioned preferred embodiment, beneficial effects of the present invention are as follows：
There is hydrophobic acid high polymer by prepared by doping vario-property, use scope is wide, can act on it is a variety of just
Pole material cleans up the residue on positive electrode surface, and further obtains the positive electrode with surface hydrophobic, has
Effect avoids the contact with moisture in air, the effective performance for improving positive electrode.
In conclusion compared with prior art, lithium ion is handled using acid high polymer the present disclosure provides a kind of
The method of cell positive material, main effect are as follows：
1, anode material for lithium-ion batteries surface is in the processing procedure of acid high polymer, acid high polymer first can and table
The alkaline, lithium residue such as Li in face2O、Li2CO3And LiOH, react, the excessive alkaline, lithium remnants in surface dissolved, make lithium from
Sub- cell positive material surface is brighter and cleaner, and alkalinity reduces；
2, treated through having hydrophobic acid high polymer positive electrode, has surface hydrophobic, can effectively avoid
With the contact with moisture in air；
3, washing methods of the present invention, reaction process is mild, compared with traditional washing and acid solution are washed, Bu Huigai
Become the crystal structure of anode material for lithium-ion batteries, keeps perfection of crystal, it is without side-effects to lithium ion battery；
4, preparation process of the invention is simple, lower cost for material, is suitable for industrialized production.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the original material Li (Ni used in the embodiment of the present invention 10.8Co0.1Mn0.1)O2Lithium ion cell positive material
Expect scanning electron microscope (SEM) photograph；
Fig. 2 is the original material Li (Ni used in the embodiment of the present invention 10.8Co0.1Mn0.1)O2Lithium ion cell positive material
Expect scanning electron microscope (SEM) photograph；
Fig. 3 is the Li (Ni of hydrophobic polyaniline washing prepared by the embodiment of the present invention 10.8Co0.1Mn0.1)O2Lithium ion battery
Positive electrode scanning electron microscope (SEM) photograph；
Fig. 4 is the Li (Ni of hydrophobic polyaniline washing prepared by the embodiment of the present invention 10.8Co0.1Mn0.1)O2Lithium ion battery
Positive electrode scanning electron microscope (SEM) photograph；
Fig. 5 is the Li (Ni of hydrophobic polyaniline washing prepared by the embodiment of the present invention 10.8Co0.1Mn0.1)O2Lithium ion battery
Positive electrode X-ray diffraction refine collection of illustrative plates；
Fig. 6 is the Li (Ni of hydrophobic polyaniline processing prepared by embodiment 10.8Co0.1Mn0.1)O2Lithium ion cell positive material
Material and the common positive electrode of washing process and the electrochemistry cyclic curve comparison diagram of original material；
Fig. 7 is the Li (Ni of hydrophobic polyaniline washing prepared by embodiment 10.8Co0.1Mn0.1)O2Lithium ion cell positive material
The curve of double curvature comparison diagram of material and the positive electrode and original material that further coat.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The invention discloses a kind of methods handling anode material for lithium-ion batteries using acid high polymer, and key step is such as
Under：
Step 1: dense inorganic acid is pressed 1：1.5~100 volume ratio dilution is used as bottom liquid, by the dopant of low-surface-energy
With polymer monomer with 1：20~1000 mass ratio is added in the liquid of bottom, under conditions of 5~8 DEG C, stirring, every 1~3 minute
Oxidant is added, the total dosage of oxidant is 1.5~5 times, 120~360min of reaction time of polymer monomer quality, with distillation
Water cleans three times, obtains having hydrophobic acid high polymer；
Step 2: by acid high polymer and organic matter solvent according to 1：50~1000 mass ratio dissolving, stir process 30
~60min is made into organic solution；
Step 3: by positive electrode and organic solution with 1：0.1~50 mass ratio mixing, stir process 30~
180min obtains solidliquid mixture；
Step 4: by solidliquid mixture at 100~200 DEG C heating evaporation, be in temperature by obtained solid powder
Dry 0.5~12h is evaporated in vacuo at 50~200 DEG C to get being reduced to alkalinity and having hydrophobic lithium ion cell positive material
Material, wherein the mass content of high polymer is 0.1%~6% in obtained positive electrode.
In order to further state technical scheme of the present invention, below will by specific embodiment to the present invention into advance one
The discussion of step：
Embodiment 1
Present embodiment discloses a kind of method handling anode material for lithium-ion batteries using acid high polymer, it is specific by with
Lower step carries out：
(1) concentrated hydrochloric acid is pressed 1:3 volume ratio dilution is used as bottom liquid, by perfluoro caprylic acid (PFOA) and aniline with 1：50
Mass ratio is added in the liquid of bottom, and under conditions of 5~8 DEG C, stirring, (NH is added at intervals of two minutes4)2S2O8, (NH4)2S2O8Total dosage
It is 2.5 times of aniline quality used, reaction time 240min, wash with distilled water three times, obtains having hydrophobic acid poly-
Aniline；
(2) have hydrophobic polyaniline according to 1 by what is obtained in (1):200 mass ratio is dissolved into N- crassitudes
In ketone, ultrasonic agitation processing 60min is made into the organic solution containing polyaniline；
(3) by nickel cobalt manganese lithium anode material and polyaniline detergent with 1：20 mass ratio mixing, ultrasonic agitation processing
60min obtains solidliquid mixture；
(4) by solidliquid mixture be 120 DEG C in temperature at be evaporated in vacuo dry 8h to get the lithium-ion electric reduced to alkalinity
Pond positive electrode.
Embodiment 2
Present embodiment discloses a kind of method handling anode material for lithium-ion batteries using acid high polymer, it is specific by with
Lower step carries out：
(1) concentrated hydrochloric acid is pressed 1：5 volume ratio dilution is used as bottom liquid, by neopelex (SDBS) and lactic acid
With 1：50 mass ratio is added in the liquid of bottom, and under conditions of 5~8 DEG C, stirring, K is added at intervals of two minutes2Cr2O7, K2Cr2O7It is total to use
Amount is 2 times, reaction time 300min of lactic acid quality used, three times wash with distilled water, obtains having hydrophobic polylactic acid；
(2) by the polylactic acid obtained in (1) according to 1:150 mass ratio is dissolved into N,N-dimethylformamide (DMF)
In, ultrasonic agitation processing 50min is made into organic solution containing polylactic acid；
(3) by nickel cobalt manganese lithium anode material and polylactic acid detergent with 1：15 mass ratio mixing, ultrasonic agitation processing
45min obtains solidliquid mixture；
(4) by solidliquid mixture be 100 DEG C in temperature at be evaporated in vacuo dry 12h to get the lithium ion reduced to alkalinity
Cell positive material.
Embodiment 3
Present embodiment discloses a kind of method handling anode material for lithium-ion batteries using acid high polymer, it is specific by with
Lower step carries out：
(1) concentrated phosphoric acid is pressed 1：8 volume ratio dilution is used as bottom liquid, by valine, aniline and lactic acid with 1：25：25 matter
Under conditions of 5~8 DEG C, stirring, FeCl was added every 2.5 minutes than being added in the liquid of bottom in amount3, FeCl3Total dosage is benzene used
2.5 times of amine and lactic acid quality, reaction time 360min, three times wash with distilled water, obtain having hydrophobic polyaniline with
The mixture of polylactic acid；
(2) by the mixture of the polyaniline and polylactic acid that are obtained in (1) according to 1:1 mass ratio is dissolved into acetone, is surpassed
Sound stir process 45min is made into the mixture organic solution containing polyaniline and polylactic acid；
(3) by nickel cobalt manganese lithium anode material and polyaniline and the mixture detergent solution of polylactic acid with 1：15 quality
Than mixing, ultrasonic agitation processing 45min obtains solidliquid mixture；
(4) it is that dry 10h is evaporated in vacuo at 120 DEG C to get the lithium-ion electric reduced to alkalinity by solidliquid mixture temperature
Pond positive electrode.
Embodiment 4
Present embodiment discloses a kind of method handling anode material for lithium-ion batteries using acid high polymer, it is specific by with
Lower step carries out：
(1) concentrated hydrochloric acid is pressed 1:20 volume ratio dilution is used as bottom liquid, by perfluorooctane sulfonate (PFOS) and glycolic with 1：
100 mass ratio is added in the liquid of bottom, and under conditions of 5~8 DEG C, stirring, KIO was added every 1 minute3, KIO3Total dosage is institute
With 2 times of aniline quality, reaction time 300min, wash with distilled water three times, obtain that there is hydrophobic acid polyglycolic acid；
(2) have hydrophobic polyglycolic acid according to 1 by what is obtained in (1):100 mass ratio is dissolved into N- methyl pyrroles
In pyrrolidone, ultrasonic agitation processing 60min is made into the organic solution containing polyglycolic acid；
(3) by nickel cobalt manganese lithium anode material and polyglycolic acid detergent with 1：15 mass ratio mixing, ultrasonic agitation processing
60min obtains solidliquid mixture；
(4) by solidliquid mixture be 100 DEG C in temperature at be evaporated in vacuo dry 10h to get the lithium ion reduced to alkalinity
Cell positive material.
Embodiment 5
Present embodiment discloses a kind of method handling anode material for lithium-ion batteries using acid high polymer, it is specific by with
Lower step carries out：
(1) concentrated phosphoric acid is pressed 1：10 volume ratio dilution is used as bottom liquid, and by dinonyl, how sulfonic acid and ethylene glycol are with 1：100
Mass ratio is added in the liquid of bottom, and under conditions of 5~8 DEG C, stirring, MnO is added at intervals of two minutes2, MnO2Total dosage is lactic acid used
2.5 times of quality, reaction time 270min three times wash with distilled water, obtain having hydrophobic polyethylene glycol；
(2) by the polyethylene glycol obtained in (1) according to 1:150 mass ratio is dissolved into isopropanol, ultrasonic agitation processing
60min is made into the organic solution containing polyethylene glycol；
(3) by nickel cobalt manganese lithium anode material and polyethylene glycol detergent with 1：10 mass ratio mixing, ultrasonic agitation processing
45min obtains solidliquid mixture；
(4) by solidliquid mixture be 120 DEG C in temperature at be evaporated in vacuo dry 12h to get the lithium ion reduced to alkalinity
Cell positive material.
In order to measure the chemical property using nickel-cobalt lithium manganate cathode material made from process for modifying surface of the present invention, hair
A person of good sense has carried out further test experiments：
Nickel-cobalt lithium manganate cathode material, acetylene black and PVDF (Kynoar) that the surface of above-mentioned synthesis is modified are pressed
According to 8:1:1 ratio is mixed to form slurry at normal temperatures and pressures, and even application is in aluminum foil substrate.
It after obtained anode pole piece is dried under the conditions of 120 DEG C, compresses under a certain pressure, continuation is dried at 120 DEG C
10 hours dry, it is 1cm that anode pole piece, which is then cut out punching into area,2Thin rounded flakes as anode, using lithium piece as cathode, with dense
Degree is the LiPF of 1mol/L6EC+DMC (volume ratios 1：1) solution is electrolyte, and reality is assembled into the glove box full of argon gas
Electrical verification pond.
Experimental cell carries out charge and discharge cycles test using new prestige electro-chemical test channel.Charging and discharging currents are 200mA/
G, charge cutoff voltage 4.30V, discharge cut-off voltage 3.0V.
From in 6 charging and discharging curve of attached drawing it can be found that washing after nickel-cobalt lithium manganate cathode material than original material
Material capacity wants high；And under hot conditions, the anode material for lithium-ion batteries of carrying out washing treatment is recycled than unmodified positive electrode
Performance is obviously improved.
From in the high rate performance curve of attached drawing 7 it can be found that processing after anode material for lithium-ion batteries with it is unmodified
Material under low range performance it is almost the same；But under the conditions of high magnification, capacity boost is apparent.
Anode material for lithium-ion batteries with surface hydrophobic made from process for modifying surface of the present invention is existed
Granular size and morphology observation are carried out on HitachiS-4000 electronic scanner microscopes.
From attached drawing 1-4 it can be found that nickel-cobalt lithium manganate material made from process for modifying surface using the present invention with it is original
There is no significant differences on the whole for material, complete spheric granules are all presented, for particle size in 5-15 microns, particle is big
Small uniformly surface is smooth, illustrates that the process for modifying surface of the present invention can be very good to maintain the original pattern and knot of positive electrode
Structure, and under the conditions of high-resolution, it can be seen that the material after washing, surface are cleaner.
The crystal structure that the present invention is handled to nickel-cobalt lithium manganate cathode material obtained through acid high polymer uses
RigakuB/Max-2400X x ray diffractometer xs are analyzed.It can be found that surface modifying material has the layer of standard from attached drawing 5
Shape structure, free from admixture mutually exist, and show that the process for modifying surface of the present invention is technology as mild as a dove, will not be to the ontology of material
Structure has an impact.
In order to further realize technical scheme of the present invention, the inorganic acid in step 1 of the present invention is in hydrochloric acid and phosphoric acid
One or both mixture.
In order to further realize technical scheme of the present invention, the dopant of the low-surface-energy in the step 1 is second
Acid, lauric acid/dodecanoic acid, perfluoro caprylic acid (PFOA), perfluor decanedioic acid (PFSEA), perfluorooctane sulfonate (PFOS), threonine, proline, essence
Propylhomoserin, valine, trifluoromethanesulfonic acid lithium, neopelex (SDBS), dinonyl how sulfonic acid, dioctyl succinate sulfonic acid
In one or more mixtures.
In order to further realize technical scheme of the present invention, polymer monomer in the step 1 be aniline, lactic acid,
One or more mixtures in glycolic, ethylene glycol.
In order to further realize technical scheme of the present invention, the oxidant in the step 1 is (NH4)2S2O8、
K2Cr2O7、KIO3、FeCl3、H2O2、MnO2In one or more mixtures.
In order to further realize technical scheme of the present invention, having for being prepared in the step 1 is hydrophobic acid high
Polymers is polyaniline (PANI), polylactic acid (PLA), polyglycolic acid (PGA), polylactide polyglycolic acid copolymer (PLGA), polyphenyl
Amine ethylene glycol copolymer (PANI-PEG) and the above polymer monomer are mixed with one or more in other monomer copolymers
Object.
In order to further realize that technical scheme of the present invention, the positive electrode of layered structure be
LiNixCoyMnzM1-x-y-zO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1, M Mg, Al, Fe, Zr, Sm, Pr, Nb, Ga, Zn,
Y, one or more of Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi.
In order to further realize technical scheme of the present invention, the organic solvent in the step 2 is N- crassitudes
Ketone (NMP), n,N-Dimethylformamide (DMF), dichloromethane, chloroform, benzene, toluene, ether, isopropanol, hexafluoro are different
One kind in propyl alcohol, acetone, n-hexane or in which several mixtures.
In order to further realize technical scheme of the present invention, the agitating mode in the step 1 is mechanical agitation, magnetic
One kind in power stirring or ultrasonic agitation.
In order to further realize that technical scheme of the present invention, the positive electrode in the step 3 include but not limited to layer
One kind in the cobalt acid lithium of shape or spinel-type, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, stratiform rich lithium manganese base solid solution
Or two kinds or more of mixture.
Each embodiment is described by the way of progressive in this specification, the highlights of each of the examples are with other
The difference of embodiment, just to refer each other for identical similar portion between each embodiment.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest range caused.
Claims (10)
1. a kind of method handling anode material for lithium-ion batteries using acid high polymer, which is characterized in that this method include with
Lower step：
Step 1：It is 1 by volume by dense inorganic acid and water：1.5~100 ratio is diluted as bottom liquid；By low surface
The dopant and polymer monomer of energy are 1 in mass ratio：20~1000 ratio is added in the liquid of bottom；It it is 5~8 DEG C in temperature
In whipping process, oxidant was added every 1~3 minute, obtains that there is hydrophobic acid high polymer wash with distilled water；
Step 2：It is 1 in mass ratio by acid high polymer and organic solvent：50~1000 ratio is dissolved, and stirring is made into
Organic solution；
Step 3：The organic solution that positive electrode and step 2 are obtained is 1 in mass ratio：0.1~50 ratio mixing, stirring
After obtain solidliquid mixture；
Step 4：By solidliquid mixture at 100~200 DEG C heating evaporation, by obtained solid powder temperature be 50~200
Drying is evaporated in vacuo at DEG C to get being reduced to alkalinity and having hydrophobic anode material for lithium-ion batteries；
The total dosage of oxidant in the step 1 is 1.5~5 times of polymer monomer quality, 120~360min of reaction time；
The stir process time in the step 2 is 30~60min；
30~180min of stir process time in the step 3；
Vacuum evaporation drying time in the step 4 is 0.5~12h, high polymer in the anode material for lithium-ion batteries
Mass content is 0.1%~6%.
2. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is that the inorganic acid in the step 1 is the mixture of one or both of hydrochloric acid and phosphoric acid.
3. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is, the dopant of the low-surface-energy in the step 1 is that acetic acid, lauric acid/dodecanoic acid, perfluoro caprylic acid, perfluor decanedioic acid, perfluor are pungent
Sulfonic acid, threonine, proline, arginine, valine, trifluoromethanesulfonic acid lithium, neopelex, dinonyl how sulfonic acid,
One or more mixtures in dioctyl succinate sulfonic acid.
4. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is that the polymer monomer in the step 1 is one or more mixtures in aniline, lactic acid, glycolic, ethylene glycol.
5. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is that the oxidant in the step 1 is (NH4)2S2O8、K2Cr2O7、KIO3、FeCl3、H2O2、MnO2In one kind or more
Kind mixture.
6. the method according to claim 1 for handling anode material for lithium-ion batteries using acid high polymer, feature exist
In the hydrophobic acid high polymer that has prepared in the step 1 is polyaniline, polylactic acid, polyglycolic acid, polylactic acid poly
Ethanol copolymer, polyaniline ethylene glycol copolymer and the above polymer monomer and one kind or more in other monomer copolymers
Kind mixture.
7. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is that the positive electrode of layered structure is LiNixCoyMnzM1-x-y-zO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1,
M is in Mg, Al, Fe, Zr, Sm, Pr, Nb, Ga, Zn, Y, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi
It is one or more of.
8. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is that the organic solvent in the step 2 is N-Methyl pyrrolidone, n,N-Dimethylformamide, dichloromethane, trichlorine
One kind in methane, benzene, toluene, ether, isopropanol, hexafluoroisopropyl alcohol, acetone, n-hexane or in which several mixtures.
9. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is that the agitating mode in the step 1 is one kind in mechanical agitation, magnetic agitation or ultrasonic agitation.
10. a kind of method handling anode material for lithium-ion batteries using acid high polymer according to claim 1, special
Sign is that the positive electrode in the step 3 includes but not limited to cobalt acid lithium, LiMn2O4, the nickel cobalt manganese of stratiform or spinel-type
The mixture of one or both of sour lithium, nickel cobalt lithium aluminate, stratiform rich lithium manganese base solid solution or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786735A (en) * | 2018-12-17 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Washing liquid for reducing surface alkalinity of high-nickel cathode material for lithium ion battery |
| CN111834629A (en) * | 2019-04-17 | 2020-10-27 | 北京新能源汽车股份有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN112803011A (en) * | 2021-03-23 | 2021-05-14 | 上海电气集团股份有限公司 | Surface modified positive electrode material, battery and preparation method and application thereof |
| CN113690411A (en) * | 2020-05-19 | 2021-11-23 | 溧阳中科海钠科技有限责任公司 | Method for reducing pH value of positive electrode material of sodium-ion battery and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474663A (en) * | 2013-09-15 | 2013-12-25 | 东莞新能源科技有限公司 | Lithium ion battery, anode material and preparation method of anode material |
| CN106299299A (en) * | 2016-09-21 | 2017-01-04 | 哈尔滨工业大学 | A kind of anode material for lithium-ion batteries with surface hydrophobic and preparation method thereof |
| CN107331857A (en) * | 2017-07-03 | 2017-11-07 | 宁波富理电池材料科技有限公司 | A kind of positive electrode of surface treatment, surface treatment method and lithium ion battery |
-
2018
- 2018-01-29 CN CN201810084074.6A patent/CN108565452B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474663A (en) * | 2013-09-15 | 2013-12-25 | 东莞新能源科技有限公司 | Lithium ion battery, anode material and preparation method of anode material |
| CN106299299A (en) * | 2016-09-21 | 2017-01-04 | 哈尔滨工业大学 | A kind of anode material for lithium-ion batteries with surface hydrophobic and preparation method thereof |
| CN107331857A (en) * | 2017-07-03 | 2017-11-07 | 宁波富理电池材料科技有限公司 | A kind of positive electrode of surface treatment, surface treatment method and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| SHENG XU，CHUNYU DU等: "A Mild Surface Washing Method Using Protonated Polyaniline for Ni-rich LiNi0.8Co0.1Mn0.1O2 Material of Lithium Ion Batteries", 《ELECTROCHIMICA ACTA》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786735A (en) * | 2018-12-17 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Washing liquid for reducing surface alkalinity of high-nickel cathode material for lithium ion battery |
| CN111834629A (en) * | 2019-04-17 | 2020-10-27 | 北京新能源汽车股份有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN113690411A (en) * | 2020-05-19 | 2021-11-23 | 溧阳中科海钠科技有限责任公司 | Method for reducing pH value of positive electrode material of sodium-ion battery and application |
| CN112803011A (en) * | 2021-03-23 | 2021-05-14 | 上海电气集团股份有限公司 | Surface modified positive electrode material, battery and preparation method and application thereof |
| CN112803011B (en) * | 2021-03-23 | 2023-03-07 | 上海电气集团股份有限公司 | Surface modified positive electrode material, battery and preparation method and application thereof |
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