CN104241615A - Method for preparing graphene composite ternary material by adopting monohydric alcohol solvothermal method - Google Patents

Method for preparing graphene composite ternary material by adopting monohydric alcohol solvothermal method Download PDF

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CN104241615A
CN104241615A CN201410376422.9A CN201410376422A CN104241615A CN 104241615 A CN104241615 A CN 104241615A CN 201410376422 A CN201410376422 A CN 201410376422A CN 104241615 A CN104241615 A CN 104241615A
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graphene
ternary material
lini
legal system
monohydric alcohol
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CN104241615B (en
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杨伟
王胜伟
王瑛
王玉强
赵成龙
陈欣
宋春华
冯涛
王新鹏
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Shandong Yuhuang New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/36—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
    • 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 belongs to the field of an anode material for a lithium ion battery, and particularly relates to a method for preparing a graphene composite ternary material by adopting a monohydric alcohol solvothermal method. According to the method for preparing the graphene composite ternary material by adopting the monohydric alcohol solvothermal method, the ternary material is LiNixCoyMnzO2, wherein the sum of x, y and z is 1, x is larger than or equal to 0.2 and less than or equal to 0.6, y is larger than or equal to 0.1 and less than or equal to 0.4, and z is larger than or equal to 0.2 and larger than or equal to 0.5; the chemical general formula of the graphene composite ternary material is Graphene/LiNixCoyMnzO2. The method has the advantages that (1) the ternary material LiNixCoyMnzO2 is relatively sensitive to water, and monohydric alcohol which replaces water to serve as a solvent is a good choice because monohydric alcohol forms a subcritical state easily, and is nonflammable, low in price and weak in toxicity under the conditions that the temperature is lower than 220 DEG C and the pressure is not larger than 3 MPa; (2) the graphene composite ternary material prepared with the method is excellent in electrochemical performance, and has the rate capability better than that of a traditional composite material; (3) the preparation process is relatively simple, the cost is low, and the preparation is suitable for large-scale industrial production.

Description

A kind of hot legal system of monoalcohol solvent that adopts is for the method for Graphene complex ternary material
Technical field
The invention belongs to field of lithium ion battery anode, particularly the hot legal system of a kind of monoalcohol solvent is for the method for Graphene complex ternary material.
Background technology
Lithium ion battery is a kind of novel secondary battery of alternative lead-acid battery, has high-energy-density, can discharge and recharge often, the advantages such as security performance is good, environmentally friendly.Lithium ion battery is primarily of positive electrode, and negative material, electrolyte and barrier film are formed, and wherein positive electrode constrains lithium ion battery overall performance to a great extent and promotes further, and therefore, the developmental research for positive electrode is more and more paid attention to.
In recent years, anode material for lithium-ion batteries (the cobalt acid lithium LiCoO of layer structure 2, LiMn2O4 LiMnO 2, lithium nickelate LiNiO 2) become study hotspot, LiCoO 2irreversible capacity loss in charge and discharge process is little, good cycling stability, but it is subject to cobalt resource restriction and spontaneous overcharges restriction, can only be used for high-end small-capacity cells; LiMnO 2lower cost, but its capacity is also low, repeatedly easily causes structural collapse, bad stability after circulation; LiNiO 2actual specific capacity is 170mAhg -1, compare LiCoO 2large 20 ~ 40mAhg -1, and its cost is lower, but synthesis condition is harsh, and overcharge safety is poor.Easily form the feature of solid solution in conjunction with the respective pluses and minuses of above-mentioned three kinds of materials and they separately, synthesize ternary material LiNi xco ymn zo 2(x+y+z=1), it is with low cost, security performance good, actual specific capacity is greater than LiNiO 2deng advantage enjoy researcher to like.But also there are some problems, such as first charge-discharge efficiency is low, structural stability is poor, high rate performance can not play under poorly conductive, high-pressure solid.
Graphene is a kind of material of monoatomic layer laminated structure, there is electron transport ability strong, mechanical strength is high, and pliability is good and thermal conductivity good, is regarded as other conductive agent (acetylene blacks alternative, flaky graphite alkene, hard carbon etc.) preferred material, can effectively improve electronics and ionic conductivity compared to other conductive agents above-mentioned after Graphene and positive electrode compound, use amount is few, superior performance, therefore grapheme composite positive electrode material has become the another bright spot improving cell integrated performance.
Summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides the method for the hot legal system of a kind of monoalcohol solvent for Graphene complex ternary material, and the Graphene complex ternary material that the method is prepared has higher energy density, also has good high rate performance simultaneously.
The present invention is achieved through the following technical solutions:
The hot legal system of monoalcohol solvent is for a method for Graphene complex ternary material, and described ternary material is LiNi xco ymn zo 2, x+y+z=1,0.2≤x≤0.6,0.1≤y≤0.4,0.2≤z≤0.5; Graphene complex ternary materials chemistry general formula is Graphene/ LiNi xco ymn zo 2, it is characterized in that: comprise following preparation process:
(1) process in early stage: by ternary material LiNi xco ymn zo 2, Graphene is placed in baking oven, dry 1 ~ 3 h at 120 ~ 200 DEG C; Grind respectively after cooling, put into drier for subsequent use;
(2), under room temperature, weigh step (1) gained graphene powder, be well-dispersed in the reactor that anhydrous monoalcohol solvent is housed, prepare graphene dispersing solution;
(3) LiNi is determined xco ymn zo 2with the mass percent of Graphene compound, weigh step (1) gained LiNi xco ymn zo 2powder, is divided in the reactor adding step (2) for 2-6 time, and sealing is stirred, and makes LiNi xco ymn zo 2fully mix with Graphene;
(4) reactor is put into heater, setting reaction temperature and reaction time, reacted rear and naturally cooled, suction filtration, washing, oven dry, obtain the compound of Graphene and ternary material;
(5) step (4) gained compound is sintered in an inert atmosphere, naturally cross ground 200 mesh sieves after cooling and obtain final Graphene complex ternary material Graphene/ LiNi xco ymn zo 2.
The described anhydrous monohydric alcohol of step (2) is the mixed liquor of one or more of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol and the tert-butyl alcohol.
The mass concentration of step (2) gained graphene dispersing solution is 0.3 ~ 6mg/ml.
Graphene described in step (3) and the mass percent of ternary material compound are 0.3 ~ 10:100, preferably 0.3 ~ 3:100.
Washing process described in step (4) uses monohydric alcohol used in step (2) to wash.
Step (4) described heater is the heater that baking oven or oil bath pan or reactor carry.
Reaction temperature described in step (4) is 150 ~ 220 DEG C, and the reaction time is 3 ~ 24 h.
Inert atmosphere described in step (5) is the one of nitrogen, helium or argon gas.
Sintering temperature described in step (5) is 200 ~ 600 DEG C, and sintering time is 2 ~ 6 h.
The hot legal system of monoalcohol solvent of the present invention is for the method for Graphene complex ternary material, and its advantage is: 1) due to ternary material LiNi xco ymn zo 2more responsive for water, monohydric alcohol replaces water to be a kind of well selection as solvent, because temperature is less than 220 DEG C, when pressure is not more than 3 MPa, monohydric alcohol easily forms subcritical state, nonflammable, low price, and toxicity is weak; 2) by Graphene complex ternary positive electrode excellent electrochemical performance prepared by the present invention, its high rate performance is better than traditional composite material; 3) preparation process is comparatively simple, with low cost, is applicable to large-scale industrial production.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described in further detail, and protection scope of the present invention is not restriction with specific embodiment, but is limited by claim.
Accompanying drawing 1 is wide-angle x-ray diffraction instrument (XRD) collection of illustrative plates of embodiment 1 and comparative example 1;
Accompanying drawing 2 is field emission scanning electron microscope (SEM) photo under the different amplification of embodiment 3;
Accompanying drawing 3 is transmission scanning electron microscope (TEM) photo of embodiment 3;
Accompanying drawing 4 is embodiment 1 and the different multiplying discharge curve comparing 1;
Accompanying drawing 5 is the different multiplying discharge curve of embodiment 2 and embodiment 3;
Accompanying drawing 6 is field emission scanning electron microscope (SEM) photo of embodiment 4;
Accompanying drawing 7 is field emission scanning electron microscope (SEM) photo of embodiment 7.
embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
Embodiment 1:
By commodity ternary material LiNi 0.5co 0.3mn 0.2o 2(523 type), commercial graphite alkene carries out process in early stage: by LiNi 0.5co 0.3mn 0.2o 2, Graphene is in 120 DEG C of baking ovens, and dry 3 h, till carrying out respectively being ground to and agglomeration not occurring, then put into drier for subsequent use after cooling respectively; Utilize the above-mentioned Graphene of balance precise 0.1000 g, be scattered in the reactor filling 50 ml anhydrous isopropyl alcohols, put into magneton, utilize ultrasonic assistant to disperse; Utilize balance precise 10.0021 g ternary material, Graphene and LiNi 0.5co 0.3mn 0.2o 2mass percent is 1:100, dividing adds in the liner of reactor 3 times, stirs 30 min, is taken out by magneton, closed reaction still, put it in the baking oven of 180 DEG C, after reacting 12 h, naturally cool, then take out inner liner of reaction kettle and carry out suction filtration, by washed with isopropyl alcohol three times, after oven dry, obtain Graphene and LiNi 0.5co 0.3mn 0.2o 2compound, gained compound is put into tube type resistance furnace at N 2heat-agglomerating in atmosphere, it is 5 DEG C/min that setting program heats up, and sintering temperature is 400 DEG C, and sintering time is 4 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi 0.5co 0.3mn 0.2o 2sample.
Adopt wide-angle x-ray diffraction instrument (XRD, Bruker D8, German Bruker-axs company) analyzing crystal phase structure, crystal parameters, the microstructures such as crystallite dimension, from accompanying drawing 1, the compound of Graphene is for ternary material LiNi 0.5co 0.3mn 0.2o 2do not cause structural change, there is no the peak of other impurity, little to its Effects on Microstructure.
Electrochemistry is tested by button battery, and the button simulated battery positive electrode for electrochemical property test is the Graphene complex ternary material Graphene/ LiNi that embodiment 1 obtains 0.5co 0.3mn 0.2o 2mass ratio is according to positive electrode: conductive agent acetylene black (SP): binding agent PVDF: solvent N-methyl pyrilidone (NMP) is 94.5:3:2.5:60, after slurry mixes, be applied in current collector aluminum foil, dry 3 h at 120 DEG C, electronic twin rollers (MR-100A, the brilliant intelligence of Shenzhen section reaches) compressing tablet, carry out cut-parts to weigh, compacted depth be 65 um(wherein aluminum foil thickness be 24 um), compacted density is 3.59 g/cm 3, surface density is 150.33g/m 2, simulated battery is assembled in the glove box of argon shield and carries out, and negative pole is metal lithium sheet, and Celgard2300 capillary polypropylene is barrier film, and LiPF6/EC+DMC (volume ratio 1:1, Beijing Inst. of Chemical Reagent) solution of 1 mol/L is electrolyte.Electro-chemical test condition: activate 2 times with 0.2C rate charge-discharge, charging/discharging voltage is 2.75-4.3v.
Embodiment 2:
By commodity ternary material LiNi 0.5co 0.3mn 0.2o 2(523 type), Graphene carries out process in early stage: by LiNi 0.5co 0.3mn 0.2o 2, Graphene in 150 DEG C of baking ovens, dry 2h, till carrying out respectively being ground to and agglomeration not occurring, then puts into drier for subsequent use after cooling respectively; Utilize balance precise 0.1001 g Graphene, be scattered in and fill in 50 ml absolute ethyl alcohols in reactor, put into magneton, utilize ultrasonic assistant to disperse; Utilize balance precise 10.0002 g LiNi 0.5co 0.3mn 0.2o 2, Graphene and LiNi 0.5co 0.3mn 0.2o 2mass percent is 1:100, dividing adds in inner liner of reaction kettle 4 times, stirs 30 min, is taken out by magneton, closed reaction still, putting it into temperature is in the baking oven of 180 DEG C, after reacting 12 h, naturally cools, take out liner and carry out suction filtration, carry out washing three times with ethanol, then dry, obtain Graphene and LiNi 0.5co 0.3mn 0.2o 2compound; Gained compound is put into tube type resistance furnace at N 2heat in atmosphere, it is 5 DEG C/min that setting program heats up, and sintering temperature is 400 DEG C, and sintering time is 4 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi 0.5co 0.3mn 0.2o 2sample.
Electrochemistry is tested by button battery, the Graphene complex ternary material Graphene/ LiNi that the button simulated battery positive electrode for electrochemical property test is obtained by embodiment 2 0.5co 0.3mn 0.2o 2sample, mass ratio is according to positive electrode: conductive agent acetylene black (SP): binding agent PVDF: solvent N-methyl pyrilidone (NMP) is 94.5:3:2.5:60, after its slurry mixes, be applied in current collector aluminum foil, 120 DEG C of drying 3 h, electronic twin rollers (MR-100A, the brilliant intelligence of Shenzhen section reaches) compressing tablet, carry out cut-parts to weigh, compacted depth be 65 um(wherein aluminum foil thickness be 24 um), compacted density is 3.52 g/cm 3, surface density is 147.03g/m 2.
Embodiment 3:
By commodity ternary material LiNi 0.5co 0.3mn 0.2o 2(523 type), Graphene carries out process in early stage: by LiNi 0.5co 0.3mn 0.2o 2, Graphene in 180 DEG C of baking ovens, dry 2h, till carrying out respectively being ground to and agglomeration not occurring, then puts into drier for subsequent use after cooling respectively; Utilize balance precise 0.0999 g Graphene, be scattered in and fill in 50 ml anhydrous isopropyl alcohol reactors, put into magneton, utilize ultrasonic assistant to disperse; Utilize balance precise 9.9992 g LiNi 0.5co 0.3mn 0.2o 2, Graphene and LiNi 0.5co 0.3mn 0.2o 2mass percent is 1:100, dividing adds in inner liner of reaction kettle 4 times, stirs 30 min, is taken out by magneton, closed reaction still, putting it into temperature is in the baking oven of 200 DEG C, after reacting 24 h, naturally cools, take out liner and carry out suction filtration, carry out washing three times with isopropyl alcohol, then dry, obtain Graphene and LiNi 0.5co 0.3mn 0.2o 2compound; Gained compound is put into tube type resistance furnace at N 2heat in atmosphere, it is 5 DEG C/min that setting program heats up, and sintering temperature is 600 DEG C, and sintering time is 4 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi 0.5co 0.3mn 0.2o 2sample.
Its sample combining case is analyzed from field emission scanning electron microscope (SEM) and transmission scanning electron microscope (TEM).From accompanying drawing 2, the method is prepared Graphene complex ternary material and is comparatively uniformly dispersed, and more strip Graphene can closely be coated on ternary material surface, shows as coated form.
Electrochemistry is tested by button battery, the material sample that button simulated battery positive electrode for electrochemical property test has embodiment obtained, its positive electrode, conductive agent acetylene black (SP), binding agent PVDF, solvent N-methyl pyrilidone (NMP) is 94.5:3:2.5:60 according to mass ratio, after its slurry mixes, be applied in current collector aluminum foil, 120 DEG C of drying 3 h, electronic twin rollers (MR-100A, the brilliant intelligence of Shenzhen section reaches) compressing tablet, carry out cut-parts to weigh, compacted depth be 65 um(wherein aluminum foil thickness be 24 um), compacted density is 3.59 g/cm3, surface density is 144.11g/m2.
Embodiment 4:
By commodity ternary material LiNi 0.5co 0.3mn 0.2o 2(523 type), Graphene carries out process in early stage: by LiNi 0.5co 0.3mn 0.2o 2, Graphene in 150 DEG C of baking ovens, dry 2h, till carrying out respectively being ground to and agglomeration not occurring, then puts into drier for subsequent use after cooling respectively; Utilize balance precise 0.3001g Graphene, be scattered in and fill in 50 ml absolute ethyl alcohols in reactor, put into magneton, utilize ultrasonic assistant to disperse; Utilize balance precise 10.0012 g LiNi 0.5co 0.3mn 0.2o 2, Graphene and LiNi 0.5co 0.3mn 0.2o 2mass percent is 3:100, dividing adds in inner liner of reaction kettle 6 times, stirs 30 min, is taken out by magneton, closed reaction still, putting it into temperature is in the baking oven of 180 DEG C, after reacting 12 h, naturally cools, take out liner and carry out suction filtration, carry out washing three times with ethanol, then dry, obtain Graphene and LiNi 0.5co 0.3mn 0.2o 2compound; Gained compound is put into tube type resistance furnace heat in an ar atmosphere, it is 5 DEG C/min that setting program heats up, and sintering temperature is 400 DEG C, and sintering time is 6 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi 0.5co 0.3mn 0.2o 2sample.
Its sample combining case is analyzed from field emission scanning electron microscope (SEM).Have Fig. 6 known, the method is prepared Graphene complex ternary material and is obtained more strip Graphene and can closely be coated on ternary material surface; Its large stretch of Graphene is also around ternary material, and it shows as coated form.
Embodiment 5:
By commodity ternary material LiNi 1/3co 1/3mn 1/3o 2(111 type), Graphene carries out process in early stage: by LiNi 1/3co 1/3mn 1/3o 2, Graphene in 150 DEG C of baking ovens, dry 2h, till carrying out respectively being ground to and agglomeration not occurring, then puts into drier for subsequent use after cooling respectively; Utilize balance precise 0.0301 g Graphene, be scattered in and fill in 50 ml absolute ethyl alcohols in reactor, put into magneton, utilize ultrasonic assistant to disperse; Utilize balance precise 10.0012 g LiNi 1/3co 1/3mn 1/3o 2, Graphene and LiNi 1/3co 1/3mn 1/3o 2mass percent is 0.3:100, divides and adds in inner liner of reaction kettle 2 times, stir 30 min, taken out by magneton, closed reaction still, putting it into set temperature is in the oil bath pan of 150 DEG C, open and stir, reaction time is 6 h, after reaction terminates nature cooling, takes out liner and carries out suction filtration, with the tert-butyl alcohol, ethanol carries out washing three times, after oven dry, obtains Graphene and LiNi 1/3co 1/3mn 1/3o 2compound; Gained compound is put into tube type resistance furnace heat in He atmosphere, it is 5 DEG C/min that setting program heats up, and sintering temperature is 500 DEG C, and sintering time is 4 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi 1/3co 1/3mn 1/3o 2sample.
Embodiment 6:
By commodity ternary material LiNi0 0.4co 0.4mn 0.2o 2(442 type), Graphene carries out process in early stage: by LiNi0 0.4co 0.4mn 0.2o 2, Graphene in 150 DEG C of baking ovens, dry 2h, till carrying out respectively being ground to and agglomeration not occurring, then puts into drier for subsequent use after cooling respectively; Utilize balance precise 0.0300 g Graphene, be scattered in and fill in 50 ml anhydrous isopropyl alcohols in reactor; Utilize balance precise 9.9989g LiNi0 0.4co 0.4mn 0.2o 2, Graphene and LiNi 0.5co 0.3mn 0.2o 2mass percent is 0.3:100, divides and adds reactor 4 times, stir 30 min, closed reaction still, setting reaction temperature 220 DEG C, after reacting 12 h, cools naturally, take out liner and carry out suction filtration, carry out washing three times with isopropyl alcohol, then dry, obtain Graphene and LiNi0 0.4co 0.4mn 0.2o 2compound; Gained compound is put into tube type resistance furnace at N 2heat in atmosphere, it is 5 DEG C/min that setting program heats up, and sintering temperature is 200 DEG C, and sintering time is 6 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi0 0.4co 0.4mn 0.2o 2sample.
Embodiment 7:
By commodity ternary material LiNi 0.5co 0.3mn 0.2o 2(523 type), commercial graphite alkene carries out process in early stage: by LiNi 0.5co 0.3mn 0.2o 2, Graphene is in 120 DEG C of baking ovens, and dry 3 h, till carrying out respectively being ground to and agglomeration not occurring, then put into drier for subsequent use after cooling respectively; Utilize the above-mentioned Graphene of balance precise 0.3001 g, be scattered in the reactor filling 25 ml anhydrous isopropyl alcohols and 25 ml absolute ethyl alcohols, put into magneton, utilize ultrasonic assistant to disperse; Utilize balance precise 10.0021 g ternary material, Graphene and LiNi 0.5co 0.3mn 0.2o 2mass percent is 3:100, divides and adds in the liner of reactor 3 times, stir 30 min, magneton is taken out, closed reaction still, puts it in the baking oven of 180 DEG C, after reacting 24 h, naturally cool, then take out inner liner of reaction kettle and carry out suction filtration, with isopropyl alcohol, ethanol washs once respectively, after oven dry, obtain Graphene and LiNi 0.5co 0.3mn 0.2o 2compound, gained compound is put into tube type resistance furnace at N 2heat-agglomerating in atmosphere, it is 5 DEG C/min that setting program heats up, and sintering temperature is 400 DEG C, and sintering time is 4 h, and after cooling, ground 200 mesh sieves obtain Graphene complex ternary material Graphene/ LiNi 0.5co 0.3mn 0.2o 2sample.
Its sample combining case is analyzed from field emission scanning electron microscope (SEM).From accompanying drawing 7, the method prepares Graphene complex ternary material Graphene/ LiNi 0.5co 0.3mn 0.2o 2large stretch of Graphene is also around ternary material, and along with the reaction time extends, second particle occurs that some are broken, can find out that primary particle is attached on graphene film from the SEM figure of accompanying drawing 7.
Comparative example 1
By commodity ternary material LiNi 0.5co 0.3mn 0.2o 2(523 type), conductive agent acetylene black (SP), binding agent PVDF, solvent N-methyl pyrilidone (NMP) are 94.5:3:2.5:60 according to mass ratio, after its slurry mixes, be applied in current collector aluminum foil, 120 DEG C of drying 3 h, electronic twin rollers (MR-100A, the brilliant intelligence of Shenzhen section reaches) compressing tablet, carry out cut-parts to weigh, compacted depth be 65 um(wherein aluminum foil thickness be 24 um), compacted density is 3.59 g/cm3, and surface density is 150.33g/m2.Simulated battery is assembled in the glove box of argon shield and carries out, and negative pole is metal lithium sheet, and Celgard2300 capillary polypropylene is barrier film, and LiPF6/EC+DMC (volume ratio 1:1, Beijing Inst. of Chemical Reagent) solution of 1mol/L is electrolyte.Electro-chemical test condition: activate 2 times with 0.2C rate charge-discharge, charging/discharging voltage is 2.75-4.3V.

Claims (9)

1. the hot legal system of monoalcohol solvent is for a method for Graphene complex ternary material, and described ternary material is LiNi xco ymn zo 2, x+y+z=1,0.2≤x≤0.6,0.1≤y≤0.4,0.2≤z≤0.5; Graphene complex ternary materials chemistry general formula is Graphene/ LiNi xco ymn zo 2, it is characterized in that: comprise following preparation process:
(1) process in early stage: by ternary material LiNi xco ymn zo 2, Graphene is placed in baking oven, dry 1 ~ 3 h at 120 ~ 200 DEG C; Grind respectively after cooling, put into drier for subsequent use;
(2), under room temperature, weigh step (1) gained graphene powder, be well-dispersed in the reactor that anhydrous monoalcohol solvent is housed, prepare graphene dispersing solution;
(3) LiNi is determined xco ymn zo 2with the mass percent of Graphene compound, weigh step (1) gained LiNi xco ymn zo 2powder, is divided in the reactor adding step (2) for 2-6 time, and sealing is stirred, and makes LiNi xco ymn zo 2fully mix with Graphene;
(4) reactor is put into heater, setting reaction temperature and reaction time, reacted rear and naturally cooled, suction filtration, washing, oven dry, obtain the compound of Graphene and ternary material;
(5) sintered in an inert atmosphere by step (4) gained compound, after cooling, ground 200 mesh sieves obtain final Graphene complex ternary material Graphene/ LiNi naturally xco ymn zo 2.
2. the hot legal system of a kind of monoalcohol solvent according to claim 1 is for the method for Graphene complex ternary material, it is characterized in that: the described anhydrous monohydric alcohol of step (2) is the mixed liquor of one or more of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol and the tert-butyl alcohol.
3. the hot legal system of a kind of monoalcohol solvent according to claim 1 is for the method for Graphene complex ternary material, it is characterized in that: the mass concentration of step (2) gained graphene dispersing solution is 0.3 ~ 6mg/ml.
4. the hot legal system of a kind of monoalcohol solvent according to claim 1 is for the method for Graphene complex ternary material, it is characterized in that: the Graphene described in step (3) and the mass percent of ternary material compound are 0.3 ~ 10:100, preferably 0.3 ~ 3:100.
5. the hot legal system of a kind of monohydric alcohol according to claim 1 molten scope agent is for the method for Graphene complex ternary material, it is characterized in that: the washing process described in step (4) uses the monohydric alcohol in step (2) to wash.
6. the hot legal system of a kind of monoalcohol solvent according to claim 1 is for the method for Graphene complex ternary material, it is characterized in that: step (4) described heater is the heater that baking oven or oil bath pan or reactor carry.
7. the hot legal system of a kind of monoalcohol solvent according to claim 1 is for the method for Graphene complex ternary material, it is characterized in that: the reaction temperature described in step (4) is 150 ~ 220 DEG C, and the reaction time is 3 ~ 24 h.
8. the hot legal system of a kind of monoalcohol solvent according to claim 1 is for the method for Graphene complex ternary material, it is characterized in that: the inert atmosphere described in step (5) is the one of nitrogen, helium or argon gas.
9. the hot legal system of a kind of monoalcohol solvent according to claim 1 is for the method for Graphene complex ternary material, it is characterized in that: the sintering temperature described in step (5) is 200 ~ 600 DEG C, and sintering time is 2 ~ 6 h.
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