CN105514344B - The method that lithium ion battery cathode surface is modified is realized by electrophoretic deposition graphene - Google Patents

The method that lithium ion battery cathode surface is modified is realized by electrophoretic deposition graphene Download PDF

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CN105514344B
CN105514344B CN201510854496.3A CN201510854496A CN105514344B CN 105514344 B CN105514344 B CN 105514344B CN 201510854496 A CN201510854496 A CN 201510854496A CN 105514344 B CN105514344 B CN 105514344B
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graphene
lithium ion
ion battery
battery cathode
cathode
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CN105514344A (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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    • 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
    • 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
    • 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 present invention provides a kind of method for realizing that lithium ion battery cathode surface is modified by electrophoretic deposition graphene, the method of modifying is that graphene stable dispersions are added in tiselius apparatus, using coated lithium ion battery cathode as electrophoresis cathode, inert metal piece is as electrophoresis anode, electrode keeps certain spacing, graphene is deposited on lithium ion battery cathode surface to get the lithium ion battery cathode being modified to graphene surface under deposition voltage appropriate and sedimentation time.The present invention can effectively improve the initial specific capacities of electrode and improve cycle performance.This method technical process is simple, and production cost is low.

Description

The method that lithium ion battery cathode surface is modified is realized by electrophoretic deposition graphene
Technical field
The present invention relates to technical field of lithium ion, more particularly to one kind passing through electrophoretic deposition graphene and realizing lithium ion The method that cell cathode surface is modified.
Background technology
Lithium ion battery is due to having many advantages, such as that monomer voltage is high, self discharge bigger than energy is small and memory-less effect, in pen Remember that the fields such as this computer, mobile phone, wearable device, electric vehicle are widely used.But lithium ion battery is in charge and discharge Capacity can gradually decay in cyclic process, shorten its service life.To reduce use cost, cycle performance of lithium ion battery also needs It is continuously improved.
In order to improve the cycle performance of lithium ion battery, the means often taken for cathode researcher have surface to change Property, the bulk phase-doped xenogenesis element of cathode material.It is that (such as sol-gal process and solvent are evaporated using solwution method that wherein surface, which is modified, Method) or the methods of atomic layer deposition deposit out-phase material on cathode material surface, can also be realized in cathode using atomic layer deposition Whole pole piece uniform deposition out-phase material.The out-phase material deposited have inhibit in charging process cathode and electrolyte it Between side reaction, slow down the decomposition of electrolyte and form stable interfacial reaction film (i.e. in electrode/electrolyte interface Solid-electrolyte interphase layer, SEI film) function, while also have inhibit cathode material be electrolysed The function of HF impurity dissolution in liquid.Therefore surface is modified the stability for improving cathode, and then can improve following for full battery Ring performance.Graphene is a kind of carbon material with two-dimension plane structure, has the advantages that high conductivity and high chemical stability, It is suitable as the coating modification layer material of the various cathode materials of lithium ion battery.Existing research report is all from cathode material powder Body sets out, using graphene dispersing solution or graphite oxide dispersion, packet of the final realization graphene in cathode powder material surface It covers.For example, cathode material powder is added in graphite oxide solution, after graphite oxide is coated on cathode material particle surface, Deoxidation and reduction is restored or heated using solution reduction agent, converts graphite oxide to graphene, and graphene coated cathode is made The composite material of material granule.The composite material is mixed with binder and conductive additive and is coated in aluminum foil current collector, most The cathode of graphene modification is obtained afterwards.However, the gap structure of surface deposition graphene can reduce the tap density of composite material, This will lead to the reduction of lithium ion battery energy density per unit volume.
Invention content
It is an object of the invention to solve the defect of the above-mentioned prior art, using the electrophoretic deposition technique of graphene solution, Graphene is deposited in coated cathode surface, realizes and the graphene of cathode entirety pole piece is modified, increase cathode Electric conductivity can effectively improve the initial specific capacities of electrode and improve cycle performance.This method technical process is simple, production cost It is low.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A method of realizing that lithium ion battery cathode surface is modified by electrophoretic deposition graphene, the method for modifying It is that graphene stable dispersions are added in tiselius apparatus, using coated lithium ion battery cathode as electrophoresis cathode, inertia gold Belong to piece or graphite flake as electrophoresis anode, electrode keeps certain spacing, by stone under deposition voltage appropriate and sedimentation time Black alkene is deposited on lithium ion battery cathode surface to get the lithium ion battery cathode being modified to graphene surface.
Further, the side of lithium ion battery cathode surface modification is realized as described above by electrophoretic deposition graphene Method, electrode spacing 1-20cm, deposition voltage 2-1000V, sedimentation time are 1-600 min.
Further, the side of lithium ion battery cathode surface modification is realized as described above by electrophoretic deposition graphene Method is used to prepare one or more lithium ion battery cathode or that active material is llowing group of materials：
LiFePO4、LiCoPO4、Li3V2(PO4)3、LiFexMn1-xPO4, wherein 0 ＜ x ＜ 1, Li2FeSiO4、LiCoO2、 LiNiO2、LiMnO2、LiMn2O4、LiNi1-xCoxO2, wherein 0 ＜ x ＜ 1, LiNi1-xMnxO2, wherein 0 ＜ x ＜ 1, LiCo1- xMnxO2, wherein 0 ＜ x ＜ 1, LiMxMn2-xO4, wherein M=Ni, Co, Fe, Cr, Cu, Al, Ti, Zr, Ge and Sn, 0 ＜ x ＜ 2, LiNi1-xAlxO2, wherein 0 x≤0.6 ＜, Li2MnSiO4In it is one or more combine, above-mentioned active material it is respective various One or more in heterogeneous ion doping material combine, in above-mentioned active material non-graphite alkene surface coating modification material One or more combination, LiaNixCoyMzO2, wherein M=Mn, Al, Fe, Mg, Cu, Sr, Ga, In, Ge, Zr, Cr, La, Ce, One or more combinations in 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, LiaNixCoyMzO2Non-graphite alkene coating modification material, wherein M =Mn, A1, Fe, Mg, Cu, Sr, Ga, In, Ge, Zr, Cr, La, Ce, Ti, Ca, V, B, Be, Y, Mo, Tb, Ho, Tm, Nb, Sn, One or more combinations in Zn, Pr, Si, 0.95≤a≤1.25,0 ＜ x ＜, 1.0,0 ＜ y ＜, 1.0,0 ＜ z ＜ 1.0, x+y + z=1.
Further, the side of lithium ion battery cathode surface modification is realized as described above by electrophoretic deposition graphene Method, the inert metal piece are one kind in Ti pieces, Pd pieces, Au pieces, Pt pieces, Pb pieces, stainless steel substrates.
Further, the side of lithium ion battery cathode surface modification is realized as described above by electrophoretic deposition graphene Method, the graphene stable dispersions are graphene-alcohol dispersion liquid, graphene-isopropanol dispersion liquid, graphene-acetone point One kind in dispersion liquid, graphene-N- methyl pyrrole networks alkanone, graphene-dioctyl phthalate.
The positive effect of the present invention is as follows：
(1) graphene of cathode surface deposition induces the SEI films that electrode/electrolyte interface generates stabilization so that electrode Cycle performance is significantly improved.
(2) graphene enhances the electric conductivity of electrode in the deposition of electrode surface so that the initial specific capacities of electrode obtain It improves.
(3) method of graphene electrophoretic deposition modified cathode is to be directed to the modification for having prepared molding cathode sheet, can to the greatest extent The problem of reduction lithium ion battery energy density per unit volume that can be avoided that caused by graphene coated cathode powder material.Electrophoresis simultaneously Deposition modified technique process is simple, and production cost is low, is convenient for large-scale application.
Description of the drawings
Fig. 1 is the method flow diagram that the present invention realizes that lithium ion battery cathode surface is modified by electrophoretic deposition graphene；
Fig. 2 be the embodiment of the present invention 1 in graphene surface before modified after LiNi0.5Mn1.5O4The scanning electron microscopy of cathode Mirror image (SEM)；
Fig. 3 is original LiNi in the embodiment of the present invention 10.5Mn1.5O4It is modified LiNi with graphene0.5Mn1.5O4Fill for the first time Discharge curve schematic diagram；
Fig. 4 is original LiNi in the embodiment of the present invention 10.5Mn1.5O4It is modified LiNi with graphene0.5Mn1.5O4Electrode follows Ring performance curve schematic diagram；
Fig. 5 is the original LiNi of the present invention0.5Mn1.5O4Electrode and electrophoretic deposition graphene are modified LiNi0.5Mn1.5O4Electrode SEI membrane impedances RSEIWith electronics transfer impedance RctWith the variation of cycle cycle.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other without creative efforts Embodiment shall fall within the protection scope of the present invention.
As one of preferred technical solution, the present invention realizes the specific steps of cathode surface graphene method of modifying such as Under：
(1) graphene-alcohol dispersion liquid is prepared
(ultrasonic power 427W, ultrasonic time are 1 small to graphite oxide ultrasonic disperse prepared by 0.15g Hummers methods When) dispersion liquid A is obtained in 150mL deionized waters, then 1.35g p-phenylenediamine is dissolved in 150mL dimethylformamides and is obtained To solution B, after dispersion liquid A and solution B are mixed, be heated to reflux at 90 DEG C for 24 hours, with acetone eccentric cleaning three times, filter cleaning Once.Then by a certain amount of graphite ene product, a certain amount of ethanol solution ultrasonic disperse (ultrasonic power 100W, Ultrasonic time is 30 minutes), obtain the graphene alcohol dispersion liquid that a concentration of 2.5mg/mL stablizes.
(2) cathode is prepared
Mass ratio according to the amount of active material of cathode, the addition of carbon black, Kynoar (PVDF) is 80: 10: 10 A certain amount of active material of cathode, carbon black, PVDF are weighed, active material of cathode and carbon black are mixed and stirred for 20min, then added Enter appropriate N- methyl pyrrole network alkanone (NMP), stir 2h, add binder PVDF, stir 12h, obtain uniform slurry, utilizes Slurry is uniformly coated on A1 foils by scraper, and cathode is made after 5h is dried at 50 DEG C.
(3) electrophoretic deposition graphene modified cathode
Graphene obtained-alcohol dispersion liquid is added in electrolytic cell, using cathode obtained as electrophoresis cathode, titanium sheet is made For electrophoresis anode, graphene is deposited on cathode table by electrode spacing 2cm under the deposition voltage of 20V and the sedimentation time of 2min Face, to get the cathode being modified to graphene after drying at room temperature.
Embodiment 1
(1) graphene alcohol dispersion liquid is prepared
(ultrasonic power 427W, ultrasonic time are 1 small to graphite oxide ultrasonic disperse prepared by 0.15g Hummers methods When) dispersion liquid A is obtained in 150mL deionized waters, then 1.35g p-phenylenediamine is dissolved in 150mL dimethylformamides and is obtained To solution B, after dispersion liquid A and solution B are mixed, be heated at reflux at 90 DEG C for 24 hours, with acetone eccentric cleaning three times, filter cleaning Once.Then by a certain amount of graphite ene product, a certain amount of ethanol solution ultrasonic disperse (ultrasonic power 100W, Ultrasonic time is 30 minutes), obtain graphene-alcohol dispersion liquid that a concentration of 2.5mg/mL stablizes.
(2) LiNi is prepared0.5Mn1.5O4Cathode
According to LiNi0.5Mn1.5O4The quality of the amount of active material of cathode, the addition of carbon black, Kynoar (PVDF) Than weighing a certain amount of LiNi for 80: 10: 100.5Mn1.5O4Powder, carbon black, PVDF, by LiNi0.5Mn1.5O4It mixes and stirs with carbon black 20min is mixed, appropriate N- methyl pyrrole network alkanone (NMP) is then added, stirs 2h, adds binder PVDF, 12h is stirred, obtains Slurry is uniformly coated on A1 foils using scraper, LiNi is made after 5h is dried at 50 DEG C by uniform slurry0.5Mn1.5O4 Cathode.
(3) electrophoretic deposition prepares graphene and is modified LiNi0.5Mn1.5O4Cathode
Graphene obtained-alcohol dispersion liquid is added in electrolytic cell, with LiNi obtained0.5Mn1.5O4Cathode is as electricity Swimming cathode, titanium sheet is as electrophoresis anode, electrode spacing 2cm, by graphene under the deposition voltage of 20V and the sedimentation time of 2min Cathode surface is deposited on, to get the LiNi being modified to graphene after drying at room temperature0.5Mn1.5O4Cathode.
Embodiment 2
(1) synthesizing graphite alkene isopropanol dispersion liquid
(ultrasonic power 427W, ultrasonic time are 1 small to graphite oxide ultrasonic disperse prepared by 0.15g Hummers methods When) dispersion liquid A is obtained in 150mL deionized waters, then 1.35g p-phenylenediamine is dissolved in 150mL dimethylformamides and is obtained To solution B, after dispersion liquid A and solution B are mixed, be heated at reflux at 90 DEG C for 24 hours, with acetone eccentric cleaning three times, filter cleaning Once.Then by a certain amount of graphite ene product, in a certain amount of aqueous isopropanol ultrasonic disperse, (ultrasonic power 100W surpasses The sound time is 30 minutes), obtain graphene-isopropanol dispersion liquid that a concentration of 1.5mg/mL stablizes.
(2) Li (Ni are prepared1/3Co1/3Mn1/3)O2Cathode
According to Li (Ni1/3Co1/3Mn1/3)O2The amount of active material of cathode, the addition of carbon black, PVDF mass ratio be 80: Weigh a certain amount of LiNi at 10: 100.5Mn1.5O4Powder, carbon black, PVDF, by Li (Ni1/3Co1/3Mn1/3)O2It mixes and stirs with carbon black 20min is mixed, appropriate NMP is then added, stirs 2h, adds binder PVDF, 12h is stirred, obtains uniform slurry, is utilized Slurry is uniformly coated on A1 foils by scraper, and Li (Ni are made after 5h is dried at 50 DEG C1/3Co1/3Mn1/3)O2Cathode.
(3) electrophoretic deposition prepares graphene and is modified Li (Ni1/3Co1/3Mn1/3)O2Cathode
Graphene obtained-isopropanol dispersion liquid is added in electrolytic cell, with Li (Ni obtained1/3Co1/3Mn1/3)O2Electricity Pole is as electrophoresis cathode, and stainless steel substrates are as electrophoresis anode, electrode spacing 20cm, in the deposition voltage of 1000V and sinking for 5min Graphene is deposited on Li (Ni under the product time1/3Co1/3Mn1/3)O2On electrode, to get being modified to graphene after drying at room temperature Li(Ni1/3Co1/3Mn1/3)O2Electrode.
Embodiment 3
(1) synthesizing graphite alkene acetone dispersion liquor
(ultrasonic power 427W, ultrasonic time are 1 small to graphite oxide ultrasonic disperse prepared by 0.15g Hummers methods When) dispersion liquid A is obtained in 150mL deionized waters, then 1.35g p-phenylenediamine is dissolved in 150mL dimethylformamides and is obtained To solution B, after dispersion liquid A and solution B are mixed, be heated at reflux at 90 DEG C for 24 hours, with acetone eccentric cleaning three times, filter cleaning Once.Then by a certain amount of graphite ene product, ultrasonic disperse (the ultrasonic power 100W, when ultrasonic in a certain amount of acetone Between be 30 minutes), obtain graphene-acetone dispersion liquor that a concentration of 0.5mg/mL stablizes.
(2) LiNi is prepared0.8Co0.15Al0.05O2Electrode.
According to LiNi0.8Co0.15Al0.05O2The amount of active material of cathode, the addition of carbon black, PVDF mass ratio be 60: Weigh a certain amount of LiNi at 30: 100.8Co0.15Al0.05O2, carbon black, PVDF.By LiNi0.8Co0.15Al0.0 5O2It is mixed with carbon black And 20min is stirred, appropriate NMP is then added, stirs 2h, adds binder PVDF, stirs 12h, obtains uniform slurry, Slurry is uniformly coated on A1 foils using scraper, LiNi is made after 5h is dried at 50 DEG C0.8Co0.15Al0.0 5O2Electrode.
(3) electrophoretic deposition graphene is modified LiNi0.8Co0.15Al0.05O2Electrode.
Graphene acetone dispersion liquor obtained is added in electrolytic cell, with LiNi obtained0.8Co0.15Al0.05O2Electrode is made For electrophoresis cathode, Au pieces are as electrophoresis anode, 1 cm of electrode spacing, under the deposition voltage of 1000V and the sedimentation time of 1min Graphene is deposited on LiNi0.8Co0.15Al0.05O2On electrode, to get being modified to graphene after drying at room temperature LiNi0.8Co0.15Al0.05O2Electrode.
Embodiment 4：
(1) the 1st step for preparing graphene dispersing solution is identical as (1) step of embodiment 1.
(2) according to LiFePO4The amount of active material of cathode, the addition of carbon black, PVDF mass ratio be 80: 10: 10 claim Take a certain amount of LiFePO4Powder, carbon black, PVDF, by LiFePO4It is mixed and stirred for 20min with carbon black, appropriate NMP is then added, 2h is stirred, binder PVDF is added, 12h is stirred, obtains uniform slurry, slurry is uniformly coated in Al foils using scraper On, LiFePO is made after 5h is dried at 50 DEG C4Cathode.
(3) graphene obtained-alcohol dispersion liquid is added in electrolytic cell, with LiFePO obtained4Cathode is as electrophoresis Cathode, Pt pieces are as electrophoresis anode, electrode spacing 3cm, by graphene under the deposition voltage of 20V and the sedimentation time of 30min Cathode surface is deposited on, to get the LiFePO being modified to graphene after drying at room temperature4Cathode.
Embodiment 5：
(1) the 1st step for preparing graphene dispersing solution is identical as (1) step of embodiment 1.
(2) according to LiCoO2The amount of active material of cathode, the addition of carbon black, PVDF mass ratio be to weigh at 80: 10: 10 A certain amount of LiCoO2Powder, carbon black, PVDF, by LiFePO4It is mixed and stirred for 20min with carbon black, appropriate NMP is then added, is stirred 2h adds binder PVDF, stirs 12h, obtains uniform slurry, is uniformly coated in slurry on Al foils using scraper, LiCoO is made after 5h is dried at 50 DEG C2Cathode.
(3) graphene obtained-isopropanol dispersion liquid is added in electrolytic cell, with LiCoO obtained2Electrode is as electrophoresis Cathode, graphite flake is as electrophoresis anode, electrode spacing 20cm, by graphite under the deposition voltage of 5V and the sedimentation time of 600min Alkene is deposited on Li (Ni1/3Co1/3Mn1/3)O2On electrode, to get the Li (Ni being modified to graphene after drying at room temperaturel/3Co1/ 3Mn1/3)O2Electrode.
Fig. 1 is the method flow diagram that the present invention realizes that lithium ion battery cathode surface is modified by electrophoretic deposition graphene；
Fig. 2 be the embodiment of the present invention 1 in graphene surface before modified after LiNi0.5Mn1.5O4The scanning electron microscopy of electrode Mirror image (SEM)；By Fig. 2 graphene surfaces before modified after comparison it can be seen from electrophoresis method graphene can be made to be deposited on Electrode surface has the hole of discrete unevenness in graphene sedimentary.
Fig. 3 is original LiNi in the embodiment of the present invention 10.5Mn1.5O4It is modified LiNi with graphene0.5Mn1.5O4The head of electrode Secondary charging and discharging curve schematic diagram；As seen from Figure 3, after surface electro-deposition graphene, LiNi0.5Mn1.5O4Specific discharge capacity It significantly improves.
Fig. 4 is original LiNi in the embodiment of the present invention 10.5Mn1.5O4It is modified LiNi with graphene0.5Mn1.5O4Electrode follows Ring performance curve schematic diagram, as seen from Figure 4, after surface electro-deposition graphene, LiNi0.5Mn1.5O4Electrode passes through 1000 weeks Capacity still has higher conservation rate, cycle performance to be obviously improved after secondary cycle.
Fig. 5 is the original LiNi of the present invention0.5Mn1.5O4Electrode and electrophoretic deposition graphene are modified LiNi0.5Mn1.5O4Electrode SEI membrane impedances RSEIWith electronics transfer impedance RctWith the variation of cycle cycle；As seen from Figure 5, graphene is modified LiNi0.5Mn1.5O4The Initial R of electrodeSEIAnd RctBoth less than original electrodes.And with increasing for cycle cycle, graphene changes Property LiNi0.5Mn1.5O4The amplification of two kinds of impedances of electrode is all significantly less than original LiNi0.5Mn1.5O4Electrode.Show that surface deposits Graphene can reduce electrode polarization, and induce electrode/electrolyte interface and generate stable SEI films.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features； And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and Range.

Claims (5)

1. a kind of method for realizing that lithium ion battery cathode surface is modified by electrophoretic deposition graphene, it is characterised in that：It is described Method of modifying be by graphene stable dispersions be added tiselius apparatus in, using coated lithium ion battery cathode as electrophoresis bear Pole, inert metal piece or graphite flake keep certain spacing as electrophoresis anode, electrode, in deposition voltage appropriate and deposition Between under graphene is deposited on lithium ion battery cathode surface to get the lithium ion battery cathode being modified to graphene surface.
2. the method that the modification of lithium ion battery cathode surface is realized by electrophoretic deposition graphene as described in claim 1, It is characterized in that：Electrode spacing is 1-20cm, deposition voltage 2-1000V, sedimentation time 1-600min.
3. the method that the modification of lithium ion battery cathode surface is realized by electrophoretic deposition graphene as described in claim 1, It is characterized in that：The active material for being used to prepare lithium ion battery cathode is the one or more of llowing group of materials：
LiFePO4、LiCoPO4、Li3V2(PO4)3、LiFexMn1-xPO4, wherein 0 ＜ x ＜ 1, Li2FeSiO4、LiCoO2、LiNiO2、 LiMnO2、LiMn2O4、LiNi1-xCoxO2, wherein 0 ＜ x ＜ 1, LiNi1-xMnxO2, wherein 0 ＜ x ＜ 1, LiCo1-xMnxO2, wherein 0 ＜ x ＜ 1, LiMxMn2-xO4, wherein M=Ni, Co, Fe, Cr, Cu, Al, Ti, Zr, Ge and Sn, 0 ＜ x ＜ 2, LiNi1-xAlxO2, Wherein 0 x≤0.6 ＜, Li2MnSiO4In it is one or more combine, the respective various heterogeneous ion dopings of above-mentioned active material One or more in material combine, are in above-mentioned active material non-graphite alkene surface coating modification material one or more Combination, LiaNixCoyMzO2, wherein M=Mn, Al, Fe, Mg, Cu, Sr, Ga, In, Ge, Zr, Cr, La, Ce, Ti, Ca, V, B, Be, Y, one or more combinations in 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, LiaNixCoyMzO2Non-graphite alkene coating modification material, wherein M=Mn, Al, Fe, Mg, One kind in Cu, Sr, Ga, In, Ge, Zr, Cr, La, Ce, Ti, Ca, V, B, Be, Y, Mo, Tb, Ho, Tm, Nb, Sn, Zn, Pr, Si Or a variety of combinations, 0.95≤a≤1.25,0 ＜ x ＜, 1.0,0 ＜ y ＜, 1.0,0 ＜ z ＜ 1.0, x+y+z=1.
4. the method that the modification of lithium ion battery cathode surface is realized by electrophoretic deposition graphene as described in claim 1, It is characterized in that：The inert metal piece is one kind in Ti pieces, Pd pieces, Au pieces, Pt pieces, Pb pieces, stainless steel substrates.
5. the method that the modification of lithium ion battery cathode surface is realized by electrophoretic deposition graphene as described in claim 1, It is characterized in that：The graphene stable dispersions are graphene-alcohol dispersion liquid, graphene-isopropanol dispersion liquid, graphene- One kind in acetone dispersion liquor, graphene-N-Methyl pyrrolidone, graphene-dioctyl phthalate.
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