CN105742627A - Preparation method for LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z>/graphene composite cathode material - Google Patents

Preparation method for LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z>/graphene composite cathode material Download PDF

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CN105742627A
CN105742627A CN201610241001.4A CN201610241001A CN105742627A CN 105742627 A CN105742627 A CN 105742627A CN 201610241001 A CN201610241001 A CN 201610241001A CN 105742627 A CN105742627 A CN 105742627A
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preparation
lithium
positive electrode
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朱继平
祝杰
姚海宁
王娟
张阳阳
王飞鸿
张春芳
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Hefei University of Technology
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Hefei University 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
    • H01M4/36—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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method for a LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z>/graphene composite cathode material. A bromine-doping lithium cobalt nickel manganese oxide is prepared by a combustion method. The preparation method comprises the following steps of mixing a nickel source, a cobalt source, a manganese source, a bromine source, a lithium salt and a combustion-supporting agent according to a certain mole ratio; adding a solvent and stirring the mixture; preparing a LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z> cathode material by a high-temperature solid phase method; fully mixing the LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z> cathode material with graphene oxide; adding an appropriate amount of a reducing agent; and transferring the obtained product to a reaction kettle for reaction at a certain temperature for a certain time to obtain LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z>/graphene composite cathode material. The material prepared according to the method has the advantages of relatively high specific capacity, favorable high-rate performance and excellent cycle performance, and can be applied to the fields of various portable electronic devices, an electromobile, an energy storage device and the like.

Description

A kind of LiNixCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material
Technical field
The invention belongs to field of lithium ion battery anode, particularly relate to one bromine Y-oxides doping cobalt manganese lithium positive pole material Material, and use the preparation method of graphene coated on its basis.
Background technology
Lithium ion battery makes it set at portable electronic due to advantages such as its capacity are high, have extended cycle life, security performance is good The many-sides such as standby, electric automobile, national defense industry are gathered around and are had broad application prospects, it has also become the research heat the most widely paid close attention to Point.And positive electrode is the important component part of lithium ion battery, being always the emphasis researched and developed of people, the quality of positive electrode is certainly Performance and the price of final lithium ion battery are determined.
Study more and commercialization positive electrode at present and include stratiform transition metal oxide LiCoO2、LiNiO2、 There is the LiMn of spinel structure2O4And their doped compound and there is the LiFePO of olivine structural4.Wherein LiCoO2 It is used widely in compact battery, but expensive, and toxicity is relatively big, and heat stability is relatively low, and overcharging resisting ability is poor, And there is safety issue, so Recent study person are seeking to substitute LiCoO2Other positive electrodes.LiNiO2Cost Relatively low, capacity is higher, but prepares pure rock-steady structure LiNiO2Difficulty, LiNiO2Charge/discharge capacity decay is fast, safety relatively Difference, and Reversible Cycle poor-performing.Spinelle LiMn2O4Cheap, safety good, overcharging resisting performance is good, but its capacity Under low and high temperature, poor heat stability and charge/discharge capacity decay limit it soon and are widely popularized.LiFePO4 Its structural stability and heat are steady The features such as qualitative height, normal-temperature circulating performance are excellent, and the aboundresources of Fe and P, the advantage such as environmentally friendly.But it also has scarce Point, as low in voltage platform, tap density is low, ionic conductivity is poor, poor performance at low temperatures etc., thus govern the energy of lithium ion battery Metric density and power density.
Ternary layered series material LiNixCoyMn1-x-yO2Combine LiCoO2Good chemical property, LiNiO2Height Specific capacity, LiMn2O4High security and the feature such as low cost and paid close attention to widely.At LiNixCoyMn1-x-yO2System In, LiNi1/3Col/3Mnl/3O2It is to study the most ripe, the widest positive electrode of range of application at present, there is higher reversible ratio Capacity, more preferable cycle performance, low cost, to the advantage such as environmental hazard is little it is considered to be the most promising lithium ion battery just One of pole material.About LiNixCoyMn1-x-yO2Preparation method and aspect of performance document report the most.Its preparation method Mainly there are high temperature solid-state method, coprecipitation, sol-gal process, spray drying method etc..High temperature solid-state method synthesis technique is simple, reaction The defects such as condition is easily controlled, it is easy to accomplish industrialization, but its product grain is relatively large, particle diameter distribution concordance difference, shadow Ring its performance.Coprecipitation has that synthesis temperature is low, product grain pattern is good and the advantage such as product chemistry function admirable, but Its preparation process is relative complex, and process is wayward, loss etc. easily occurs.Sol-gal process has that synthesis temperature is low, product The advantages such as particle diameter is little and is evenly distributed, form is easily controllable, but technical process is more complicated, and raw material is usually organic chemistry material, Production cost is high, it is difficult to industrialized production.It is high that spray drying method prepares product purity, particle size uniformity, and its shortcoming is to exist Bigger pollution problem, preparative-scale is little, it is difficult to carry out industrialized production.Therefore in the urgent need to one reproducible, technique is simple Single, with low cost preparation method.
Graphene is as a kind of new carbon, since 2004 are found, due to the six of its two dimension monolayer The cellular void structure in angle and the physico-chemical property of excellence, such as high specific surface area, high electronic conductivity, superior mechanical property With good chemical stability etc., and it is widely used in lithium ion battery.Many researchs in recent years show that Graphene exists Composite positive pole not only increases the ability of positive electrode storage lithium, it is also possible to form conductive network and promote its electric conductivity, with Time contribute to shorten lithium ion the evolving path, make the high rate charge-discharge performance of positive electrode have greatly improved, these are right For cobalt nickel oxide manganses lithium the most important.Cobalt nickel oxide manganses lithium and Graphene complex method great majority are to use cobalt nickel oxide manganses at present Lithium is directly mixed with Graphene by magnetic agitation, and this simple mechanical mixture makes lithium titanate mix not with cobalt nickel oxide manganses lithium Enough uniform, and adhesive force is more weak, it is impossible to give full play to the advantages such as Graphene high conductivity, thus make cobalt nickel oxide manganses lithium/graphite The big high rate performance of alkene composite is the best, does not still meets the business of cobalt nickel oxide manganses lithium/graphene composite material Change requirement.
Summary of the invention
Use bromine Y-oxides doping cobalt manganese lithium anode material it is desirable to provide a kind of, and use Graphene on its basis The preparation method of cladding, to be solved technical problem is that ternary layered positive electrode LiNixCoyMn1-x-yO2Poor repeatability and times Rate performance, provides a kind of technical process simple simultaneously, consumes energy low, with short production cycle, eco-friendly lithium ion cell positive material The preparation method of material.
The present invention solves technical problem and adopts the following technical scheme that
One bromine Y-oxides doping cobalt manganese lithium anode material of the present invention, and use the preparation side of graphene coated on its basis The feature of method is: allows Br enter in cobalt nickel oxide manganses lithium lattice, replaces the O on portion2-.The most again with bromine doping oxidation Nickel cobalt manganese lithium obtains through reducing agent reduction after mixing with graphene oxide, and its chemical general formula is LiNixCoyMnl-x-yBrzO2-z/ Graphene, (0 < x < 0.6,0 < y < 0.6,0 < z < 0.1, it is abbreviated as LiNixCoyMnl-x-yBrzO2-z /G。
The feature of lithium ion battery bromine Y-oxides doping cobalt manganese lithium/grapheme composite positive electrode material of the present invention is: logical Cross combustion method and prepare LiNixCoyMnl-x-yBrzO2-zPositive electrode, then with the oxidation stone prepared by the Hummers method improved Ink alkene is sufficiently mixed, and moving to reaction kettle for reaction certain time after adding appropriate reducing agent obtains LiNixCoyMnl-x-yBrzO2-z / G composite positive pole.
A kind of preparation method of LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, it is characterised in that: Allow bromine enter in cobalt nickel oxide manganses lithium lattice, replace the O2-on portion, then by bromine Y-oxides doping cobalt manganese lithium and oxidation Prepare through hydro-thermal method after Graphene mixing, comprise the steps:
(1) nickel source, cobalt source, manganese source, bromine source and lithium salts and combustion adjuvant are pressed certain mixed in molar ratio, add in solvent orange 2 A Row stirring, the most successively drying, heat up, be incubated, be cooled to room temperature after grind and cross after 400 mesh sieves to obtain LiNixCoyMnl-x- YBrzO2-z positive electrode, wherein 0 < x < 0.6,0 < y < 0.6,0 < z < 0.1.
(2) graphite oxide is joined ultrasonic disperse 0.5 ~ 5h in solvent B, obtain graphene oxide solution；
(3) LiNixCoyMnl-x-yBrzO2-z prepared by above-mentioned (1) is dissolved in dehydrated alcohol, makes its point by magnetic agitation Dissipate uniformly, then be added dropwise over above-mentioned graphene oxide solution and appropriate reducing agent wherein, and continue to stir 0.5 ~ 3h；
(4) the above-mentioned suspension containing LiNixCoyMnl-x-yBrzO2-z and graphene oxide is moved to containing in politef In the stainless steel autoclave of lining, successive reaction 2 ~ 24h at 100 DEG C ~ 200 DEG C, washs after being cooled to room temperature, is centrifuged, is dried, i.e. Available LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, its feature exists In, described cobalt source is one or more in cobalt carbonate, cobalt acetate, cobalt nitrate；
Described nickel source is one or more in nickelous carbonate, nickel acetate, nickel nitrate；
Described manganese source is one or more in manganese carbonate, manganese acetate, manganese nitrate；
Described bromine source is one or more in lithium bromide, ammonium bromide, addition be described cobalt oxide nickel manganese lithium quality 1 ~ 10%；
Described lithium salts is one or more in lithium carbonate, Quilonorm (SKB), lithium nitrate, Lithium hydrate；
Described combustion adjuvant is one or more in glycine, tartaric acid, citric acid etc., its consumption and transition metal ions Mol ratio is (0.5 ~ 2): 1；
Described solvent orange 2 A is ethylene glycol, acetone or deionized water.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, its feature exists In: step (1) is dry, heat up, heat preservation method refers to: is dried 8 ~ 12 hours at 70 ~ 90 DEG C, then is warming up to 300 ~ 600 DEG C also It is incubated 4 ~ 8 hours, then is warming up to 700 ~ 950 DEG C of insulations 10 ~ 18 hours.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, it is characterised in that: The heating rate heated up described in step (1) is 4 DEG C/about min.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, its feature exists In, the preparation method of described graphite oxide comprises the following steps:
(1) adding volume ratio in the flask equipped with 2.8-3.2g graphite powder and 17-19g potassium permanganate mixture is 8-10:1's Concentrated sulphuric acid and the mixture of phosphoric acid;
(2) said mixture is heated to 50 ~ 70 DEG C of stirring 8 ~ 24h；
(3) again said mixture being cooled to room temperature, be poured slowly on the ice cube frozen in advance, this ice cube is by about 400ml The mass fraction of water and 8 ~ 10ml is the hydrogenperoxide steam generator composition of about 30%, stands a period of time until ice cube melts completely Change；
(4) it is dried to obtain graphite oxide after being respectively washed with water, dilute hydrochloric acid, ethanol again.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, its feature exists In, the one in the mixed solvent that solvent B is deionized water, dehydrated alcohol, water and ethanol of described graphite oxide.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, its feature exists In, ultrasonic after the mass fraction of graphene oxide solution that obtains be 0.5% ~ 2wt%.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, its feature exists In, the compound consumption of described Graphene accounts for the 0.5% ~ 15% of LiNixCoyMnl-x-yBrzO2-z mass.
The preparation method of described LiNixCoyMnl-x-yBrzO2-z/grapheme composite positive electrode material, its feature exists In, reducing agent used is the one in hydrazine hydrate, sodium borohydride, aluminum hydride, sodium sulfite, HI, HBr, dehydrated alcohol, iron powder Or several, its consumption is (1 ~ 20) with the mass ratio of graphene oxide: 1.
Compared with prior art, the present invention has the beneficial effect that:
1, composite positive pole of the present invention is a kind of more height ratio capacity, the LiNi of more preferable high rate performancexCoyMnl-x-yBrzO2-z /G Composite positive pole.
2, the present invention uses combustion method to prepare LiNixCoyMnl-x-yBrzO2-zCan not only be more evenly distributed, granule thinner Little target product, and the temperature and time of subsequent heat treatment can be reduced, greatly reduce energy consumption.
3, present invention employs LiNixCoyMnl-x-yBrzO2-zIt is placed in instead with the mixed liquor of graphene oxide and reducing agent Answer successive reaction 2 ~ 24h at still 60 ~ 150 DEG C, fully graphene oxide can not only be reduced to Graphene by this condition, and Under the conditions of this, recombination energy improves LiNixCoyMnl-x-yBrzO2-zAnd the adhesive force between Graphene, makes LiNixCoyMnl-x- yBrzO2-zIt is dispersed between graphene sheet layer one conductive network of formation, such that it is able to improve the specific capacity of lithium ion battery And high rate performance.
4, present invention process design is simple, the highest to equipment requirements, it is easy to accomplish industrialized production.
Accompanying drawing explanation
Fig. 1 is the LiNi of embodiment 1 preparation1/3Co1/3Mn1/3O2And LiNi1/3Co1/3Mn1/3Br0.05O1.95XRD figure spectrum.
Fig. 2 is the LiNi of embodiment 2 preparation1/3Co1/3Mn1/3Br0.05O1.95And LiNi1/3Co1/3Mn1/3Br0.05O1.95/ G's XRD figure is composed.
Fig. 3 is the LiNi of embodiment 3 preparation1/3Co1/3Mn1/3Br0.03O1.97/ G is first charge-discharge curve under 0.2C.
Fig. 4 is the LiNi of embodiment 4 preparation1/3Co1/3Mn1/3Br0.03O1.95The cycle performance figure of/G composite positive pole.
Fig. 5 is the LiNi of embodiment 4 preparation1/3Co1/3Mn1/3Br0.05O1.95The FE-SEM figure of/G.
Fig. 6 is the LiNi of embodiment 4 preparation1/3Co1/3Mn1/3Br0.05O1.95And LiNi1/3Co1/3Mn1/3Br0.05O1.95/ G's Electrochemical impedance spectroscopy (EIS).
Detailed description of the invention
In order to further appreciate that present disclosure feature and beneficial effect, below by concrete example with reference The present invention is described in further detail.
Embodiment 1:
In the present embodiment, the preparation method of lithium ion battery bromine Y-oxides doping cobalt manganese lithium anode material is according to following steps Prepare:
A, weigh the manganese acetate of cobaltous acetate 2.4909g, 0.01mol of nickel acetate 2.4884g, 0.01mol into 0.01mol 2.4509g, wherein in order to make up the loss of lithium under high temperature, makes lithium source excess 5%, weighs 3.2136g lithium acetate, 4.5027g winestone Acid, measures 100ml ethylene glycol with graduated cylinder, these materials carries out under normal temperature condition magnetic agitation and makes its mix homogeneously, then will After temperature is raised to 150 DEG C of stirring 6h, 80 DEG C are dried 8 hours and are ground in an oven, are then placed on crucible and are built in Muffle In stove stove, in air atmosphere, it is warming up to 450 DEG C with the heating rate of 4 DEG C/min, is incubated 6 hours, is further continued for being warming up to 850 DEG C, it is incubated 10 hours, then cools to room temperature with the furnace, take out sample regrinding and obtain LiNi1/3Co1/3Mn1/3O2。
B, weigh the manganese acetate of cobaltous acetate 2.4909g, 0.01mol of nickel acetate 2.4884g, 0.01mol into 0.01mol 2.4509g, wherein in order to make up the loss of lithium under high temperature, makes lithium source excess 5%, weighs 3.0606g lithium acetate, 0.1572g bromination Lithium and 4.5027g tartaric acid, measure 100ml ethylene glycol with graduated cylinder, these materials carries out under normal temperature condition magnetic agitation and makes Its mix homogeneously, then after temperature is raised to 150 DEG C of stirring 6h, 80 DEG C are dried 8 hours and be ground in an oven, are then placed on Crucible is built in Muffle furnace stove, is warming up to 450 DEG C with the heating rate of 4 DEG C/min in air atmosphere, is incubated 6 hours, then It is continuously heating to 850 DEG C, is incubated 10 hours, then cool to room temperature with the furnace, take out sample regrinding and obtain LiNi1/3Co1/ 3Mn1/3Br0.05O1.95。
The LiNi that experiment is prepared1/3Co1/3Mn1/3O2And LiNi1/3Co1/3Mn1/3Br0.05O1.95X-ray diffraction Spectrogram is shown in Fig. 1.From figure 1 it appears that the LiNi of preparation1/3Co1/3Mn1/3Br0.05O1.95Positive electrode is with unadulterated LiNi1/3Co1/3Mn1/3O2The XRD figure peak shape of material is identical, miscellaneous peak does not occur, and this is probably Br and enters LiNi1/3Col/3Mnl/ 3O2In lattice, replace the O on portion2-, this explanation doping has no effect on main body layer structure.
By prepared LiNi1/3Co1/3Mn1/3O2Mix by the mass ratio of 8:1:1 with acetylene black and Kynoar PVDF Uniformly, it is rolled into the film of thick 120 μm, after 120 DEG C of vacuum drying 10 hours, as the positive pole of experiment half-cell；Use l mol/L LiPF6/ vinyl carbonate (EC)-diethyl carbonate (DEC) (volume ratio 1:1 of EC Yu DEC) electrolyte, dry In the glove box of dry full argon, using metal lithium sheet as negative pole, it is assembled into battery.With the LiNi prepared by the present embodiment1/ 3Co1/3Mn1/3O2For positive pole, the button cell with lithium sheet as negative pole, in 2.5 ~ 4.3V voltage range, with constant current under 0.1C multiplying power- Constant-voltage charge, under 0.2C multiplying power, during constant-current discharge, first discharge specific capacity is 157.64mAh/g, but capacity after 50 circulations It is only 123.1mAh/g.
Embodiment 2:
In the present embodiment the preparation method of lithium ion battery bromine Y-oxides doping cobalt manganese lithium/grapheme composite positive electrode material be by Prepare according to following steps:
A, weigh the manganese acetate of cobaltous acetate 2.4909g, 0.01mol of nickel acetate 2.4884g, 0.01mol into 0.01mol 2.4509g, wherein in order to make up the loss of lithium under high temperature, makes lithium source excess 5%, weighs 3.0606g lithium acetate, 0.1572g bromination Lithium and 6.3042g citric acid, measure 100ml ethylene glycol with graduated cylinder, these materials carries out under normal temperature condition magnetic agitation and makes Its mix homogeneously, then after temperature is raised to 150 DEG C of stirring 6h, 80 DEG C are dried 8 hours and be ground in an oven, are then placed on Crucible is built in Muffle furnace stove, is warming up to 450 DEG C with the heating rate of 4 DEG C/min in air atmosphere, is incubated 6 hours, then It is continuously heating to 850 DEG C, is incubated 10 hours, then cool to room temperature with the furnace, take out sample regrinding and obtain LiNi1/3Co1/ 3Mn1/3Br0.05O1.95。
B, by by the above-mentioned LiNi prepared1/3Co1/3Mn1/3Br0.05O1.95Weigh 1.94g, be dissolved in the anhydrous second of 20ml Magnetic agitation in alcohol；And add 3% graphite oxide 0.06g, ultrasonic disperse obtains graphene oxide solution in deionized water, It is added drop-wise to LiNi subsequently1/3Co1/3Mn1/3Br0.05O1.95Suspension in, add appropriate dehydrated alcohol and make reducing agent, fully Move in reactor to react 3h after mixing at 120 DEG C, be cooled to room temperature and gains are dried i.e. can get LiNi1/3Co1/ 3Mn1/3Br0.05O1.95/ G composite positive pole.
The LiNi that experiment is prepared1/3Co1/3Mn1/3Br0.05O1.95And LiNi1/3Co1/3Mn1/3Br0.05O1.95The X-of/G X ray diffraction spectrogram is shown in Fig. 2.From figure 2 it can be seen that the LiNi of preparation1/3Co1/3Mn1/3Br0.03O1.95/ G anode composite material Material and LiNi1/3Co1/3Mn1/3Br0.03O1.95The XRD figure peak shape of material is identical, miscellaneous peak does not occur, and this is probably Br and enters LiNi1/3Col/3Mnl/3O2In lattice, replace the O on portion2-, and the addition of Graphene has no effect on main body layer structure.
With LiNi prepared by the present embodiment1/3Co1/3Mn1/3Br0.05O1.95/ G is positive pole, the button electricity with lithium sheet as negative pole Pond, in 2.5 ~ 4.3V voltage range, with constant current-constant-voltage charge under 0.1C multiplying power, discharges during constant-current discharge under 0.2C multiplying power first Specific capacity is 167.2mAh/g, but capacity is 133mAh/g after 50 circulations.
Embodiment 3:
In the present embodiment the preparation method of lithium ion battery bromine Y-oxides doping cobalt manganese lithium/grapheme composite positive electrode material be by Prepare according to following steps:
A, weigh the manganese acetate of cobaltous acetate 2.4909g, 0.01mol of nickel acetate 2.4884g, 0.01mol into 0.01mol 2.4509g, wherein in order to make up the loss of lithium under high temperature, makes lithium source excess 5%, weighs 3.1172g lithium acetate, 0.0944g bromination Lithium and 4.5027g tartaric acid, measure 100ml ethylene glycol with graduated cylinder, these materials carries out under normal temperature condition magnetic agitation and makes Its mix homogeneously, then after temperature is raised to 150 DEG C of stirring 6h, 80 DEG C are dried 8 hours and be ground in an oven, are then placed on Crucible is built in Muffle furnace stove, is warming up to 450 DEG C with the heating rate of 4 DEG C/min in air atmosphere, is incubated 6 hours, then It is continuously heating to 850 DEG C, is incubated 10 hours, then cool to room temperature with the furnace, take out sample regrinding and obtain LiNi1/3Co1/ 3Mn1/3Br0.03O1.97。
B, by by the above-mentioned LiNi prepared1/3Co1/3Mn1/3Br0.03O1.97Weigh 1.94g, be dissolved in the anhydrous second of 20ml Magnetic agitation in alcohol；And adding the graphite oxide 0.06g of gross mass 3%, ultrasonic disperse obtains graphene oxide in deionized water Solution, is added drop-wise to LiNi subsequently1/3Co1/3Mn1/3Br0.03O1.97Suspension in, add appropriate dehydrated alcohol and make reducing agent, Move in reactor to react 3h after being sufficiently mixed at 120 DEG C, be cooled to room temperature and gains are dried i.e. can get LiNi1/ 3Co1/3Mn1/3Br0.03O1.97/ G composite positive pole.
The composite positive pole prepared by the present embodiment is assembled into battery, and concrete grammar is with embodiment 1, at 2.5 ~ 4.3V electricity Pressure scope, with constant current-constant-voltage charge under 0.1C multiplying power, under 0.2C multiplying power, during constant-current discharge, first discharge specific capacity is 171.7mAh/g, and capacity is maintained at 138.32mAh/g after 50 circulations, capability retention is 79.6%.It is specifically shown in Fig. 3 Implement the LiNi of 3 preparations1/3Co1/3Mn1/3Br0.03O1.97/ G is first charge-discharge curve under 0.2C.
Embodiment 4:
In the present embodiment, the Preparation Method of preparing of lithium ion battery bromine Y-oxides doping cobalt manganese lithium/grapheme composite positive electrode material is Prepare according to following steps:
A, weigh the manganese acetate of cobaltous acetate 2.4909g, 0.01mol of nickel acetate 2.4884g, 0.01mol into 0.01mol 2.4509g, wherein in order to make up the loss of lithium under high temperature, makes lithium source excess 5%, weighs 3.0606g lithium acetate, 0.1572g bromination Lithium and 4.5027g tartaric acid, measure 100ml ethylene glycol with graduated cylinder, these materials carries out under normal temperature condition magnetic agitation and makes Its mix homogeneously, then after temperature is raised to 150 DEG C of stirring 6h, 80 DEG C are dried 8 hours and be ground in an oven, are then placed on Crucible is built in Muffle furnace stove, is warming up to 450 DEG C with the heating rate of 4 DEG C/min in air atmosphere, is incubated 6 hours, then It is continuously heating to 850 DEG C, is incubated 10 hours, then cool to room temperature with the furnace, take out sample regrinding and obtain LiNi1/3Co1/ 3Mn1/3Br0.05O1.95。
B, by by the above-mentioned LiNi prepared1/3Co1/3Mn1/3Br0.05O1.95Weigh 1.94g, be dissolved in the anhydrous second of 20ml Magnetic agitation in alcohol；And adding the graphite oxide 0.06g of gross mass 3%, ultrasonic disperse obtains graphene oxide in deionized water Solution, is added drop-wise to LiNi subsequently1/3Co1/3Mn1/3Br0.05O1.95Suspension in, add appropriate dehydrated alcohol and make reducing agent, Move in reactor to react 6h after being sufficiently mixed at 120 DEG C, be cooled to room temperature and gains are dried i.e. can get LiNi1/ 3Co1/3Mn1/3Br0.05O1.95/ G composite positive pole.
The composite positive pole prepared by the present embodiment is assembled into battery, and concrete grammar is with embodiment 1, at 2.5 ~ 4.3V electricity Pressure scope, with constant current-constant-voltage charge under 0.1C multiplying power, under 0.2C multiplying power, during constant-current discharge, reversible capacity reaches first 181.3mAh/g, its coulombic efficiency reaches 90.1%, LiNi prepared by the present embodiment1/3Co1/3Mn1/3Br0.05O1.95/ G anode composite The cycle performance figure of material is shown in Fig. 4.And capacity is maintained at 145.8mAh/g after 50 circulations, capability retention is 80.4%.Figure 5 for implementing the LiNi of 4 preparations1/3Co1/3Mn1/3Br0.05O1.95The FE-SEM figure of/G, the flaky texture in figure is Graphene. The LiNi of 4 preparations implemented by picture 61/3Co1/3Mn1/3Br0.05O1.95And LiNi1/3Co1/3Mn1/3Br0.05O1.95The electrochemistry of/G material Impedance spectrum (EIS).From fig. 6 it can be seen that LiNi1/3Co1/3Mn1/3Br0.05O1.95The impedance of/G is less, special electric charge transfer electricity Resistance Rct.This may can improve electronic conductivity and the dissolving of suppression transition metal ions owing to graphene coated, thus carries Its chemical property high.
Embodiment 5:
In the present embodiment, lithium ion battery bromo element is according to following step to the preparation method that cobalt nickel oxide manganses lithium is doped Suddenly prepare:
A, weigh the manganese acetate of cobaltous acetate 2.4909g, 0.01mol of nickel acetate 2.4884g, 0.01mol into 0.01mol 2.4509g, wherein in order to make up the loss of lithium under high temperature, makes lithium source excess 5%, weighs 3.0606g lithium acetate, 0.1572g bromination Lithium and 2.5221g glycine, measure 100ml ethylene glycol with graduated cylinder, these materials carries out under normal temperature condition magnetic agitation and makes Its mix homogeneously, then after temperature is raised to 150 DEG C of stirring 6h, 80 DEG C are dried 8 hours and be ground in an oven, are then placed on Crucible is built in Muffle furnace stove, is warming up to 450 DEG C with the heating rate of 4 DEG C/min in air atmosphere, is incubated 6 hours, then It is continuously heating to 850 DEG C, is incubated 10 hours, then cool to room temperature with the furnace, take out sample regrinding and obtain LiNi1/3Co1/ 3Mn1/3Br0.05O1.95。
B, by by the above-mentioned LiNi prepared1/3Co1/3Mn1/3Br0.05O1.95Weigh 1.94g, be dissolved in the anhydrous second of 20ml Magnetic agitation in alcohol；And adding the graphite oxide 0.06g of gross mass 3%, ultrasonic disperse obtains graphene oxide in deionized water Solution, is added drop-wise to LiNi subsequently1/3Co1/3Mn1/3Br0.05O1.95Suspension in, add appropriate dehydrated alcohol and make reducing agent, Move in reactor to react 6h after being sufficiently mixed at 120 DEG C, be cooled to room temperature and gains are dried i.e. can get LiNi1/ 3Co1/3Mn1/3Br0.05O1.95/ G composite positive pole.
The composite positive pole prepared by the present embodiment is assembled into battery, and concrete grammar, with embodiment 1, records it at 0.2C Under first discharge specific capacity reach 179.6mAh/g, and capacity is maintained at 142.32mAh/g after 50 circulations, and capacity keeps Rate is 79.24%.

Claims (9)

1. a LiNixCoyMnl-x-yBrzO2-z The preparation method of/grapheme composite positive electrode material, it is characterised in that: make bromine first Element enters in cobalt nickel oxide manganses lithium lattice, replaces the O on portion2-, then by bromine Y-oxides doping cobalt manganese lithium and oxidation stone Prepare through hydro-thermal method after ink alkene mixing, comprise the steps:
(1) nickel source, cobalt source, manganese source, bromine source and lithium salts and combustion adjuvant are pressed certain mixed in molar ratio, add in solvent orange 2 A Row stirring, the most successively drying, heat up, be incubated, be cooled to room temperature after grind and cross after 400 mesh sieves to obtain LiNixCoyMnl-x- yBrzO2-zPositive electrode, wherein 0 < x < 0.6,0 < y < 0.6,0 < z < 0.1；
(2) graphite oxide is joined ultrasonic disperse 0.5 ~ 5h in solvent B, obtain graphene oxide solution；
(3) LiNi prepared by above-mentioned (1)xCoyMnl-x-yBrzO2-zIt is dissolved in dehydrated alcohol, makes it disperse all by magnetic agitation Even, then it is added dropwise over above-mentioned graphene oxide solution and appropriate reducing agent wherein, and continue to stir 0.5 ~ 3h；
(4) by above-mentioned containing LiNixCoyMnl-x-yBrzO2-zAnd the suspension of graphene oxide moves to containing teflon-lined In stainless steel autoclave, successive reaction 2 ~ 24h at 100 DEG C ~ 200 DEG C, wash after being cooled to room temperature, be centrifuged, be dried, To LiNixCoyMnl-x-yBrzO2-z/ grapheme composite positive electrode material.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, its Being characterised by, described cobalt source is one or more in cobalt carbonate, cobalt acetate, cobalt nitrate；
Described nickel source is one or more in nickelous carbonate, nickel acetate, nickel nitrate；
Described manganese source is one or more in manganese carbonate, manganese acetate, manganese nitrate；
Described bromine source is one or more in lithium bromide, ammonium bromide, addition be described cobalt oxide nickel manganese lithium quality 1 ~ 10%；
Described lithium salts is one or more in lithium carbonate, Quilonorm (SKB), lithium nitrate, Lithium hydrate；
Described combustion adjuvant is one or more in glycine, tartaric acid, citric acid etc., its consumption and transition metal ions Mol ratio is (0.5 ~ 2): 1；
Described solvent orange 2 A is ethylene glycol, acetone or deionized water.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, its It is characterised by: described being dried of step (1) is to be dried 8 ~ 12 hours at 70 ~ 90 DEG C；Described insulation is to be warming up to 300 ~ 600 DEG C and protect Temperature 4 ~ 8 hours, then it is warming up to 700 ~ 850 DEG C of insulations 12 ~ 18 hours.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, it is special Levy and be: the heating rate of step (1) described intensification is 4 DEG C/min.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, its Being characterised by, the preparation method of described graphite oxide comprises the following steps:
(1) adding volume ratio in the flask equipped with 2.8 ~ 3.2g graphite powder and 17-19g potassium permanganate mixture is 8 ~ 10:1's Concentrated sulphuric acid and the mixture of phosphoric acid;
(2) said mixture is heated to 50 ~ 70 DEG C of stirring 8 ~ 24h；
(3) again said mixture being cooled to room temperature, be poured slowly on the ice cube frozen in advance, this ice cube is by about 400ml The mass fraction of water and 8 ~ 10ml is the hydrogenperoxide steam generator composition of about 30%, stands a period of time until ice cube melts completely Change；
(4) it is dried to obtain graphite oxide after being respectively washed with water, dilute hydrochloric acid, ethanol again.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, its It is characterised by, the one in the mixed solvent that solvent B is deionized water, dehydrated alcohol, water and ethanol of described graphite oxide.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, its Be characterised by, ultrasonic after the mass fraction of graphene oxide solution that obtains be 0.5% ~ 2wt%.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, its Being characterised by, the compound consumption of described Graphene accounts for LiNixCoyMnl-x-yBrzO2-zThe 0.5% ~ 15% of quality.
LiNi the most according to claim 1xCoyMnl-x-yBrzO2-zThe preparation method of/grapheme composite positive electrode material, its Being characterised by, reducing agent used is in hydrazine hydrate, sodium borohydride, aluminum hydride, sodium sulfite, HI, HBr, dehydrated alcohol, iron powder One or more, the mass ratio of its consumption and graphene oxide is (1 ~ 20): 1.
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