CN105514344A - Method for realizing surface modification of negative electrode of lithium ion battery through electrophoretic deposition of graphene - Google Patents

Method for realizing surface modification of negative electrode of lithium ion battery through electrophoretic deposition of graphene Download PDF

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CN105514344A
CN105514344A CN201510854496.3A CN201510854496A CN105514344A CN 105514344 A CN105514344 A CN 105514344A CN 201510854496 A CN201510854496 A CN 201510854496A CN 105514344 A CN105514344 A CN 105514344A
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graphene
lithium ion
ion battery
negative electrode
battery cathode
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CN105514344B (en
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方海涛
李霏
王亚杰
洪达
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • 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
    • 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
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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 provides a method for realizing surface modification of the negative electrode of a lithium ion battery through electrophoretic deposition of graphene. The method comprises the following steps: adding a stable graphene dispersion liquid into an electrophoresis cell; with a coated negative electrode of the lithium ion battery as an electrophoresis negative electrode and inert sheet metal as an electrophoresis positive electrode, allowing the electrodes to maintain a certain distance; and depositing graphene onto the surface of the negative electrode of the lithium ion battery under the condition of proper deposition voltage and deposition time so as to obtain the negative electrode surface-modified by graphene. The method provided by the invention can effectively improve initial specific capacity and cycle performance of the negative electrode and is simple in process and low in production cost.

Description

The method of lithium ion battery cathode surface modification is realized by electrophoretic deposition Graphene
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of method being realized lithium ion battery cathode surface modification by electrophoretic deposition Graphene.
Background technology
Lithium ion battery, owing to having that monomer voltage is high, specific energy is large, self discharge is little and the advantage such as memory-less effect, is widely used in fields such as notebook computer, mobile phone, wearable device, electric motor cars.But lithium ion battery capacity in charge and discharge cycles process can be decayed gradually, shortens its useful life.For reducing use cost, cycle performance of lithium ion battery also needs to improve constantly.
In order to improve the cycle performance of lithium ion battery, the means often taked for negative electrode researcher have the bulk phase-doped xenogenesis element of surface modification, cathode material.Wherein surface modification utilizes the methods such as solwution method (as sol-gal process and solvent steam seasoning) or ald at cathode material surface deposition out-phase material, utilizes ald can also realize at negative electrode overall pole piece uniform deposition out-phase material.The out-phase material deposited has the side reaction suppressed in charging process between negative electrode and electrolyte, slow down the decomposition of electrolyte and form stable interfacial reaction film (i.e. solid-electrolyteinterphaselayer in electrode/electrolyte interface, SEI film) function, also have simultaneously suppress cathode material by the function of the HF impurity stripping in electrolyte.Therefore surface modification improves the stability of negative electrode, and then can improve the cycle performance of full battery.Graphene is a kind of material with carbon element with two-dimension plane structure, has the advantage of high conductivity and high chemical stability, is suitable as the coating modification layer material of the various cathode material of lithium ion battery.Existing research report is all from cathode material powder, utilizes graphene dispersing solution or graphite oxide dispersion, finally realizes coated at cathode powder material surface of Graphene.Such as, cathode material powder is joined in graphite oxide solution, after graphite oxide is coated on cathode material particle surface, then through solution reduction agent reduction or heating deoxidation and reduction, graphite oxide is converted into Graphene, the composite material of obtained graphene coated cathode material particle.Being mixed with binding agent and conductive additive by this composite material is coated in aluminum foil current collector, finally obtains the negative electrode of Graphene modification.But the gap structure of surface deposition Graphene can reduce the tap density of composite material, this will cause the reduction of lithium ion battery volumetric specific energy.
Summary of the invention
The object of the invention is to the defect solving above-mentioned prior art, utilize the electrophoretic deposition technique of graphene solution, at coated cathode surface deposited graphite alkene, realize the Graphene modification of the overall pole piece of target, add the conductivity of negative electrode, can effectively improve the initial specific capacities of electrode and improve cycle performance.The method technical process is simple, and production cost is low.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A kind of method being realized lithium ion battery cathode surface modification by electrophoretic deposition Graphene, described method of modifying adds in tiselius apparatus by Graphene stable dispersions, using coated lithium ion battery cathode as electrophoresis negative pole, inert metal sheet or graphite flake are as electrophoresis positive pole, electrode keeps certain spacing, under suitable deposition voltage and sedimentation time, Graphene is deposited on lithium ion battery cathode surface, namely obtains the lithium ion battery cathode of graphenic surface modification.
Further, realize the method for lithium ion battery cathode surface modification as described above by electrophoretic deposition Graphene, electrode spacing is 1-20cm, and deposition voltage is 2-1000V, and sedimentation time is 1-600min.
Further, realize the method for lithium ion battery cathode surface modification as described above by electrophoretic deposition Graphene, for the preparation of lithium ion battery cathode or active material be one or more of llowing group of materials:
LiFePO 4, LiCoPO 4, Li 3v 2(PO 4) 3, LiFe xmn 1-xpO 4(0<x<1), Li 2mnSiO 4, Li 2feSiO 4, LiCoO 2, LiNiO 2, LiMnO 2, LiMn 2o 4, LiNi 1-xco xo 2(0<x<1), LiNi 1-xmn xo 2(0<x<1), LiCo 1-xmn xo 2(0<x<1), LiM xmn 2-xo 4(M=Ni, Co, Fe, Cr, Cu, Al, Ti, Zr, Ge and Sn, 0<x<2), LiNi 1-xal xo 2one or more combination in one or more combination in one or more combination in (0<x≤0.6), above-mentioned active material various heterogeneous ion doping material separately, above-mentioned active material non-graphite alkene surface coating modification material, Li ani xco ym zo 2wherein, one or more combination in M=Mn, Al, Fe, Mg, Cu, Sr, Ga, In, Ge, Zr, Cr, La, Ce, Ti, Ca, V, B, Be, Y, Mo, Tb, Ho, Tm, Nb, Sn, Zn, Pr, Si, 0.95≤a≤1.25,0<x<1.0,0<y<1.0,0<z<1.0, x+y+z=1, Li ani xco ym zo 2one or more combination in non-graphite alkene coating modification material.
Further, realize the method for lithium ion battery cathode surface modification as described above by electrophoretic deposition Graphene, described inert metal sheet is the one in Ti sheet, Pd sheet, Au sheet, Pt sheet, Pb sheet, stainless steel substrates.
Further, realize the method for lithium ion battery cathode surface modification as described above by electrophoretic deposition Graphene, described Graphene stable dispersions is the one in Graphene-alcohol dispersion liquid, Graphene-isopropyl alcohol dispersion liquid, Graphene-acetone dispersion liquor, Graphene-N-methyl pyrrole network alkane ketone, Graphene-dioctyl phthalate.
Good effect of the present invention is as follows:
(1) Graphene that cathode surface deposits brings out electrode/electrolyte interface and generates stable SEI film, and electrode cycle performance is significantly improved.
(2) Graphene enhances the conductivity of electrode in the deposition of electrode surface, and the initial specific capacities of electrode is improved.
(3) method of Graphene electrophoretic deposition modified cathode is the modification for preparing shaping cathode sheet, the problem of the reduction lithium ion battery volumetric specific energy that graphene coated cathode powder material can be avoided as far as possible to cause.Electrophoretic deposition modified technique process is simple simultaneously, and production cost is low, is convenient to large-scale application.
Accompanying drawing explanation
Fig. 1 is that the present invention realizes the method flow diagram of lithium ion battery cathode surface modification by electrophoretic deposition Graphene;
Fig. 2 is graphenic surface rear LiNi before modified in the embodiment of the present invention 1 0.5mn 1.5o 4the scanning electron microscope image (SEM) of negative electrode;
Fig. 3 is original LiNi in the embodiment of the present invention 1 0.5mn 1.5o 4with Graphene modification LiNi 0.5mn 1.5o 4first charge-discharge curve synoptic diagram;
Fig. 4 is original LiNi in the embodiment of the present invention 1 0.5mn 1.5o 4with Graphene modification LiNi 0.5mn 1.5o 4the cycle performance curve synoptic diagram of electrode;
Fig. 5 is the original LiNi of the present invention 0.5mn 1.5o 4electrode and electrophoretic deposition Graphene modification LiNi 0.5mn 1.5o 4the SEI membrane impedance R of electrode sEIwith electro transfer impedance R ctwith the change of circulation cycle.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below technical scheme in the present invention be clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
As one of preferred technical scheme, the concrete steps that the present invention realizes cathode surface Graphene method of modifying are as follows:
(1) Graphene-alcohol dispersion liquid is prepared
By graphite oxide ultrasonic disperse standby for 0.15gHummers legal system, (ultrasonic power is 427W, ultrasonic time is 1 hour) in 150mL deionized water, obtain dispersion liquid A, again 1.35g p-phenylenediamine (PPD) is dissolved in 150mL dimethyl formamide and obtains solution B, after dispersion liquid A and solution B mixing, add hot reflux 24h at 90 DEG C, clean once with acetone eccentric cleaning three times, suction filtration.Then by a certain amount of Graphene product, a certain amount of ethanol solution ultrasonic disperse (ultrasonic power is 100W, and ultrasonic time is 30 minutes), obtaining concentration is the Graphene alcohol dispersion liquid that 2.5mg/mL is stable.
(2) negative electrode is prepared
Be that 80:10:10 takes a certain amount of active material of cathode, carbon black, PVDF according to the mass ratio of the addition of the amount of active material of cathode, carbon black, Kynoar (PVDF), active material of cathode is mixed with carbon black and stirs 20min, then appropriate N-methyl pyrrole network alkane ketone (NMP) is added, stir 2h, add binding agent PVDF again, stir 12h, obtain uniform slurry, scraper is utilized to be coated in uniformly by slurry on Al paper tinsel, at 50 DEG C of obtained negative electrodes after 5h is dried.
(3) electrophoretic deposition Graphene modified cathode
Obtained Graphene-alcohol dispersion liquid is added in electrolytic cell, using obtained negative electrode as electrophoresis negative pole, titanium sheet is as electrophoresis positive pole, electrode spacing 2cm, under the deposition voltage of 20V and the sedimentation time of 2min, Graphene is deposited on cathode surface, after drying at room temperature, namely obtain the negative electrode of Graphene modification.
Embodiment 1
(1) Graphene alcohol dispersion liquid is prepared
By graphite oxide ultrasonic disperse standby for 0.15gHummers legal system, (ultrasonic power is 427W, ultrasonic time is 1 hour) in 150mL deionized water, obtain dispersion liquid A, again 1.35g p-phenylenediamine (PPD) is dissolved in 150mL dimethyl formamide and obtains solution B, after dispersion liquid A and solution B mixing, reflux heating 24h at 90 DEG C, cleans once with acetone eccentric cleaning three times, suction filtration.Then by a certain amount of Graphene product, a certain amount of ethanol solution ultrasonic disperse (ultrasonic power is 100W, and ultrasonic time is 30 minutes), obtaining concentration is Graphene-alcohol dispersion liquid that 2.5mg/mL is stable.
(2) LiNi is prepared 0.5mn 1.5o 4negative electrode
According to LiNi 0.5mn 1.5o 4the mass ratio of the addition of the amount of active material of cathode, carbon black, Kynoar (PVDF) is that 80:10:10 takes a certain amount of LiNi 0.5mn 1.5o 4powder, carbon black, PVDF, by LiNi 0.5mn 1.5o 4mix with carbon black and stir 20min, then adding appropriate N-methyl pyrrole network alkane ketone (NMP), stirring 2h, add binding agent PVDF again, stir 12h, obtain uniform slurry, scraper is utilized to be coated in uniformly by slurry on Al paper tinsel, at 50 DEG C of obtained LiNi after 5h is dried 0.5mn 1.5o 4negative electrode.
(3) electrophoretic deposition prepares Graphene modification LiNi 0.5mn 1.5o 4negative electrode
Obtained Graphene-alcohol dispersion liquid is added in electrolytic cell, with obtained LiNi 0.5mn 1.5o 4negative electrode is as electrophoresis negative pole, and titanium sheet is as electrophoresis positive pole, and electrode spacing 2cm, is deposited on cathode surface by Graphene under the deposition voltage of 20V and the sedimentation time of 2min, after drying at room temperature, namely obtains the LiNi of Graphene modification 0.5mn 1.5o 4negative electrode.
Embodiment 2
(1) synthesizing graphite alkene isopropyl alcohol dispersion liquid
By graphite oxide ultrasonic disperse standby for 0.15gHummers legal system, (ultrasonic power is 427W, ultrasonic time is 1 hour) in 150mL deionized water, obtain dispersion liquid A, again 1.35g p-phenylenediamine (PPD) is dissolved in 150mL dimethyl formamide and obtains solution B, after dispersion liquid A and solution B mixing, reflux heating 24h at 90 DEG C, cleans once with acetone eccentric cleaning three times, suction filtration.Then by a certain amount of Graphene product, a certain amount of aqueous isopropanol ultrasonic disperse (ultrasonic power is 100W, and ultrasonic time is 30 minutes), obtaining concentration is Graphene-isopropyl alcohol dispersion liquid that 1.5mg/mL is stable.
(2) Li (Ni is prepared 1/3co 1/3mn 1/3) O 2negative electrode
According to Li (Ni 1/3co 1/3mn 1/3) O 2the mass ratio of the addition of the amount of active material of cathode, carbon black, PVDF is that 80:10:10 takes a certain amount of LiNi 0.5mn 1.5o 4powder, carbon black, PVDF, by Li (Ni 1/3co 1/3mn 1/3) O 2mix with carbon black and stir 20min, then adding appropriate NMP, stirring 2h, then add binding agent PVDF, stirring 12h, obtain uniform slurry, utilize scraper to be coated in uniformly by slurry on Al paper tinsel, at 50 DEG C of obtained Li (Ni after 5h is dried 1/3co 1/3mn 1/3) O 2negative electrode.
(3) electrophoretic deposition prepares Graphene modification Li (Ni 1/3co 1/3mn 1/3) O 2negative electrode
Obtained Graphene-isopropyl alcohol dispersion liquid is added in electrolytic cell, with obtained Li (Ni 1/3co 1/3mn 1/3) O 2electrode is as electrophoresis negative pole, and stainless steel substrates is as electrophoresis positive pole, and electrode spacing 20cm, is deposited on Li (Ni by Graphene under the deposition voltage of 1000V and the sedimentation time of 5min 1/3co 1/3mn 1/3) O 2on electrode, after drying at room temperature, namely obtain the Li (Ni of Graphene modification 1/3co 1/3mn 1/3) O 2electrode.
Embodiment 3
(1) synthesizing graphite alkene acetone dispersion liquor
By graphite oxide ultrasonic disperse standby for 0.15gHummers legal system, (ultrasonic power is 427W, ultrasonic time is 1 hour) in 150mL deionized water, obtain dispersion liquid A, again 1.35g p-phenylenediamine (PPD) is dissolved in 150mL dimethyl formamide and obtains solution B, after dispersion liquid A and solution B mixing, reflux heating 24h at 90 DEG C, cleans once with acetone eccentric cleaning three times, suction filtration.Then by a certain amount of Graphene product, ultrasonic disperse (ultrasonic power is 100W, and ultrasonic time is 30 minutes) in a certain amount of acetone, obtaining concentration is Graphene-acetone dispersion liquor that 0.5mg/mL is stable.
(2) LiNi is prepared 0.8co 0.15al 0.05o 2electrode.
According to LiNi 0.8co 0.15al 0.05o 2the mass ratio of the addition of the amount of active material of cathode, carbon black, PVDF is that 60:30:10 takes a certain amount of LiNi 0.8co 0.15al 0.05o 2, carbon black, PVDF.By LiNi 0.8co 0.15al 0.05o 2mix with carbon black and stir 20min, then adding appropriate NMP, stirring 2h, then add binding agent PVDF, stirring 12h, obtain uniform slurry, utilize scraper to be coated in uniformly by slurry on Al paper tinsel, at 50 DEG C of obtained LiNi after 5h is dried 0.8co 0.15al 0.05o 2electrode.
(3) electrophoretic deposition Graphene modification LiNi 0.8co 0.15al 0.05o 2electrode.
Obtained Graphene acetone dispersion liquor is added in electrolytic cell, with obtained LiNi 0.8co 0.15al 0.05o 2electrode is as electrophoresis negative pole, and Au sheet is as electrophoresis positive pole, and electrode spacing 1cm, is deposited on LiNi by Graphene under the deposition voltage of 1000V and the sedimentation time of 1min 0.8co 0.15al 0.05o 2on electrode, after drying at room temperature, namely obtain the LiNi of Graphene modification 0.8co 0.15al 0.05o 2electrode.
Embodiment 4:
(1) the 1st step preparing graphene dispersing solution is identical with (1) step of embodiment 1.
(2) according to LiFePO 4the mass ratio of the addition of the amount of active material of cathode, carbon black, PVDF is that 80:10:10 takes a certain amount of LiFePO 4powder, carbon black, PVDF, by LiFePO 4mix with carbon black and stir 20min, then adding appropriate NMP, stirring 2h, then add binding agent PVDF, stirring 12h, obtain uniform slurry, utilize scraper to be coated in uniformly by slurry on Al paper tinsel, at 50 DEG C of obtained LiFePO after 5h is dried 4negative electrode.
(3) obtained Graphene-alcohol dispersion liquid is added in electrolytic cell, with obtained LiFePO 4negative electrode is as electrophoresis negative pole, and Pt sheet is as electrophoresis positive pole, and electrode spacing 3cm, is deposited on cathode surface by Graphene under the deposition voltage of 20V and the sedimentation time of 30min, after drying at room temperature, namely obtains the LiFePO of Graphene modification 4negative electrode.
Embodiment 5:
(1) the 1st step preparing graphene dispersing solution is identical with (1) step of embodiment 1.
(2) according to LiCoO 2the mass ratio of the addition of the amount of active material of cathode, carbon black, PVDF is that 80:10:10 takes a certain amount of LiCoO 2powder, carbon black, PVDF, by LiFePO 4mix with carbon black and stir 20min, then adding appropriate NMP, stirring 2h, then add binding agent PVDF, stirring 12h, obtain uniform slurry, utilize scraper to be coated in uniformly by slurry on Al paper tinsel, at 50 DEG C of obtained LiCoO after 5h is dried 2negative electrode.
(3) obtained Graphene-isopropyl alcohol dispersion liquid is added in electrolytic cell, with obtained LiCoO 2electrode is as electrophoresis negative pole, and graphite flake is as electrophoresis positive pole, and electrode spacing 20cm, is deposited on Li (Ni by Graphene under the deposition voltage of 5V and the sedimentation time of 600min 1/3co 1/3mn 1/3) O 2on electrode, after drying at room temperature, namely obtain the Li (Ni of Graphene modification 1/3co 1/3mn 1/3) O 2electrode.
Fig. 1 is that the present invention realizes the method flow diagram of lithium ion battery cathode surface modification by electrophoretic deposition Graphene;
Fig. 2 is graphenic surface rear LiNi before modified in the embodiment of the present invention 1 0.5mn 1.5o 4the scanning electron microscope image (SEM) of electrode; As can be seen from Fig. 2 graphenic surface before modified after contrast, electrophoresis method can make Graphene be deposited on electrode surface, Graphene sedimentary deposit has the hole of discrete inequality.
Fig. 3 is original LiNi in the embodiment of the present invention 1 0.5mn 1.5o 4with Graphene modification LiNi 0.5mn 1.5o 4the first charge-discharge curve synoptic diagram of electrode; As seen from Figure 3, after surface electrical deposited graphite alkene, LiNi 0.5mn 1.5o 4specific discharge capacity significantly improve.
Fig. 4 is original LiNi in the embodiment of the present invention 1 0.5mn 1.5o 4with Graphene modification LiNi 0.5mn 1.5o 4the cycle performance curve synoptic diagram of electrode, as seen from Figure 4, after surface electrical deposited graphite alkene, LiNi 0.5mn 1.5o 4electrode capacity after the circulation of 1000 cycles still has higher conservation rate, and cycle performance obviously improves.
Fig. 5 is the original LiNi of the present invention 0.5mn 1.5o 4electrode and electrophoretic deposition Graphene modification LiNi 0.5mn 1.5o 4the SEI membrane impedance R of electrode sEIwith electro transfer impedance R ctwith the change of circulation cycle; As seen from Figure 5, Graphene modification LiNi 0.5mn 1.5o 4the Initial R of electrode sEIand R ctall to be less than original electrodes.And along with increasing of circulation cycle, Graphene modification LiNi 0.5mn 1.5o 4the amplification of electrode two kinds of impedances is all significantly less than original LiNi 0.5mn 1.5o 4electrode.Show that the Graphene of surface deposition can reduce electrode polarization, and bring out electrode/electrolyte interface and generate stable SEI film.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (5)

1. one kind realizes the method for lithium ion battery cathode surface modification by electrophoretic deposition Graphene, it is characterized in that: described method of modifying adds in tiselius apparatus by Graphene stable dispersions, using coated lithium ion battery cathode as electrophoresis negative pole, inert metal sheet or graphite flake are as electrophoresis positive pole, electrode keeps certain spacing, under suitable deposition voltage and sedimentation time, Graphene is deposited on lithium ion battery cathode surface, namely obtains the lithium ion battery cathode of graphenic surface modification.
2. the method being realized lithium ion battery cathode surface modification by electrophoretic deposition Graphene as claimed in claim 1, it is characterized in that: electrode spacing is 1-20cm, deposition voltage is 2-1000V, and sedimentation time is 1-600min.
3. the as claimed in claim 1 method being realized lithium ion battery cathode surface modification by electrophoretic deposition Graphene, be is characterized in that: the active material for the preparation of lithium ion battery cathode is one or more of llowing group of materials:
LiFePO 4, LiCoPO 4, Li 3v 2(PO 4) 3, LiFe xmn 1-xpO 4(0<x<1), Li 2mnSiO 4, Li 2feSiO 4, LiCoO 2, LiNiO 2, LiMnO 2, LiMn 2o 4, LiNi 1-xco xo 2(0<x<1), LiNi 1-xmn xo 2(0<x<1), LiCo 1-xmn xo 2(0<x<1), LiM xmn 2-xo 4(M=Ni, Co, Fe, Cr, Cu, Al, Ti, Zr, Ge and Sn, 0<x<2), LiNi 1-xal xo 2one or more combination in one or more combination in one or more combination in (0<x≤0.6), above-mentioned active material various heterogeneous ion doping material separately, above-mentioned active material non-graphite alkene surface coating modification material, Li ani xco ym zo 2wherein, one or more combination in M=Mn, Al, Fe, Mg, Cu, Sr, Ga, In, Ge, Zr, Cr, La, Ce, Ti, Ca, V, B, Be, Y, Mo, Tb, Ho, Tm, Nb, Sn, Zn, Pr, Si, 0.95≤a≤1.25,0<x<1.0,0<y<1.0,0<z<1.0, x+y+z=1, Li ani xco ym zo 2one or more combination in non-graphite alkene coating modification material.
4. the method being realized lithium ion battery cathode surface modification by electrophoretic deposition Graphene as claimed in claim 1, be is characterized in that: described inert metal sheet is the one in Ti sheet, Pd sheet, Au sheet, Pt sheet, Pb sheet, stainless steel substrates.
5. the method being realized lithium ion battery cathode surface modification by electrophoretic deposition Graphene as claimed in claim 1, be is characterized in that: described Graphene stable dispersions is the one in Graphene-alcohol dispersion liquid, Graphene-isopropyl alcohol dispersion liquid, Graphene-acetone dispersion liquor, Graphene-N-methyl pyrrole network alkane ketone, Graphene-dioctyl phthalate.
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