CN105206799A - Preparation method of porous metal doped lithium manganate/graphene lithium battery positive electrode material - Google Patents

Preparation method of porous metal doped lithium manganate/graphene lithium battery positive electrode material Download PDF

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CN105206799A
CN105206799A CN201510512538.5A CN201510512538A CN105206799A CN 105206799 A CN105206799 A CN 105206799A CN 201510512538 A CN201510512538 A CN 201510512538A CN 105206799 A CN105206799 A CN 105206799A
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porous
graphene
lithium battery
preparation
warming
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朱申敏
石一杉
宾珩
朱呈岭
李尧
张荻
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Shanghai Jiaotong University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a porous metal doped lithium manganate/graphene lithium battery positive electrode material. The method includes the steps that 1, a sol-gel method is adopted for preparing a precursor of porous LiM0.2Mn1.8O4, and the precursor is put into a muffle furnace to be calcined at constant temperature to obtain porous LiM0.2Mn1.8O4; 2, graphene oxide is taken and added into deionized water to prepare a graphene oxide solution with the mass concentration of 0.05-0.1 g/mL; 3, porous LiM0.2Mn1.8O4 is put into the graphene oxide solution, the mixture is subjected to magnetic stirring, ultrasonic dispersion and drying and then transferred into a tube furnace to be calcined at constant temperature, and the porous metal doped lithium manganate/graphene lithium battery positive electrode material is obtained. Compared with the prior art, the preparation method is simple, and the raw materials are easy to get; the prepared material is good in crystallinity and uniform in particle size, and the size is about 30 nm; serving as a lithium battery positive electrode material, the prepared material is good in electrochemical stability, high in specific discharge capacity and good in rate performance and cycle performance.

Description

The preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery
Technical field
The invention belongs to technical field of electrochemistry, relate to the preparation method of a kind of porous metals adulterated lithium manganate/Graphene anode material of lithium battery.
Background technology
In anode material for lithium-ion batteries, LiMn2O4 is one of more promising material, compare traditional positive electrodes such as cobalt acid lithium, the advantages such as LiMn2O4 has aboundresources, cost is low, pollution-free, fail safe is good, good rate capability, it is desirable power battery anode material, but dissolving and the Jahn-Teller effect of Mn can be there is in LiMn2O4 in charge and discharge process, lattice is made to produce distortion, lattice structure is unstable, cause electroactive some lost, specific capacity declines, and especially under high temperature (>55 DEG C), cycle performance is poor.
For this problem above-mentioned, can at LiMn 2o 4in system, suitably adopt transition metal moieties to substitute manganese atom, the cycle performance of electrode can be improved, and extend the life-span of electrode, thus be conducive to the raising of battery performance.This is the introducing due to transition metal atoms, the crystal field interaction of crystal Atom can be strengthened, suppress the atomic migration and the structural phase transition that are unfavorable for de-lithium process in electrochemical reaction process, make stable lattice, and improve material property, as energy density, cycle performance etc., and the chemical property that material system shows in embedding lithium/de-lithium reaction can be changed, and there is higher voltage (more than 4V, even reaching 5V).But the replacement of too much transition metal, then can cause the change of electrode material thing phase, even can generate cenotype, change the structure of lattice, hinder the diffusion of lithium ion in lattice, the capacity of electrode is significantly reduced, is unfavorable for the raising of electrode material performance.
As everyone knows, the structure of the active material in electrode and pattern very large to the Electrochemical Performances of electrode.Such as, when the granularity of active material is excessive, then the specific surface of active material is too small, less with the contact of electrolyte, is unfavorable for the diffusion of lithium ion, is unfavorable for making full use of of active material; And when the crystal grain of active material is less, lithium ion is diffused into active material surface distance from active material center shortens, thus diffusion rate is comparatively large, and active material can be fully used thus, and electric discharge performance is comparatively excellent.But when the particle size of active material too small (as nano-scale range), then the specific area of material can be made relatively large, and when preparing electrode coating material, these material granules are easily reunited; When preparing electrode slice, active material is difficult to be evenly distributed in electrode slice surface, and this also can have a negative impact to the performance of battery.In addition, particle size is too small, and System of Detecting Surface Defects For Material then can increase, so that electrode polarization rate is larger.
Consider in conjunction with above-mentioned many factors, porous powder material both can ensure the particle diameter of particle, can promote again dispersed at electrode surface of material.Porous powder material has higher specific area, shorter lithium ion diffusion length, and electrolyte easily enters positive electrode center by loose structure, electronics and lithium ion can be spread conveniently by electrolyte, and then effectively improve the conductivity of positive electrode.Porous powder material can optimize granular size and structure and morphology simultaneously, in order to improve chemical property and the conductance of material, becomes the emphasis of research gradually.In order to obtain loose structure, the method that can adopt at present mainly contains soft template method, die version method, solwution method etc., improves the specific area of material, can improve electrode performance further with the feature of loose structure.But when adopting template, can obtain the satisfactory material of structure, but in order to prevent loose structure from caving in, sintering temperature can not be too high, this also makes grain crystalline not ideal enough.
Although adopt the feature of loose structure can ensure the particle diameter of particle, can promote again dispersed at electrode surface of material, the conductivity of material self still needs further raising.And numerous in order to improve in the material of electric conductivity, Graphene receives much concern because it has high-specific surface area, high conductivity and high mechanical properties.Graphene at room temperature can stable existence, is easy to modify, and very easily modification-COOH on its two dimensional surface, the oxy radicals such as-OH, therefore, are suitable as the carrier material of nano particle very much.
Application number be 201510152217.9 Chinese invention patent disclose a kind of porous metals adulterated lithium manganate/carbon composite lithium ion battery positive electrode and preparation method, the method comprises the following steps: be dissolved in by surfactant in absolute ethyl alcohol, stirring obtains gel, then by lithium nitrate, the nitrate of doping metals nitrate and manganese adds wherein, fully stirs, dry in air dry oven after mixing, calcine in Muffle furnace further, obtained porous adulterated lithium manganate material LiM 0.2mn 1.8o 4, by this LiM 0.2mn 1.8o 4dispersed in glucose solution, calcine in nitrogen atmosphere after forced air drying, obtain metal-doped mangaic acid lithium/carbon composite material LiM 0.2mn 1.8o 4/ C, wherein M refers to doping metals.Adopt glucose as carbon source in the technical scheme of this patent disclosure, in order to improve the conductivity of material, but glucose needs experience high temperature carbonization process, needs 450-600 DEG C, and the more difficult control of homogeneity of the carbon-coating formed after charing, be difficult at LiM 0.2mn 1.8o 4form stable three-dimensional conductive network between particle, and the carbon-coating formed is more crisp, it is to LiM 0.2mn 1.8o 4nano particle inhibitory action of change in volume in charge and discharge process is limited, is unfavorable for reducing the powder phenomenon-tion in electrode reaction, and this is also unfavorable for reducing impedance, therefore, is further improved.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and provide one to have excellent specific discharge capacity, the preparation method of the porous metals adulterated lithium manganate/Graphene anode material of lithium battery of high rate performance and cycle performance.
Object of the present invention can be achieved through the following technical solutions:
The preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery, the method specifically comprises the following steps:
(1) sol-gel process is adopted to prepare porous LiM 0.2mn 1.8o 4presoma, then presoma is placed in Muffle furnace, in air atmosphere, Muffle furnace is warming up to 500-700 DEG C with 2-5 DEG C/min, constant temperature process 2-4h, i.e. obtained porous LiM 0.2mn 1.8o 4;
(2) get graphene oxide, and add in deionized water, be made into the graphene oxide solution that mass concentration is 0.05-0.1g/mL;
(3) by porous LiM obtained for step (1) 0.2mn 1.8o 4be placed in graphene oxide solution, magnetic agitation, ultrasonic disperse, after drying, be transferred in tube furnace, in argon gas atmosphere, tube furnace is warming up to 250-400 DEG C with 2-5 DEG C/min, constant temperature process 2-5h, i.e. obtained described porous metals adulterated lithium manganate/Graphene anode material of lithium battery;
Wherein, M is doping metals, and this doping metals is the one in iron, cobalt, nickel, zinc or copper.
Sol-gel process described in step (1) prepares porous LiM 0.2mn 1.8o 4presoma specifically comprise the following steps:
A surfactant is dissolved in absolute ethyl alcohol by (), the mass concentration of control surface activating agent is 0.05-0.1g/mL, and under room temperature condition, magnetic agitation 12-24h, i.e. obtained gel;
B () is by Mn (NO 3) 24H 2o, LiNO 3and doping metals nitrate is 9:5:1 in molar ratio, join in the obtained gel of step (a), control LiNO 3molar concentration in gel is 0.05-0.5mol/L, is uniformly mixed, dry, i.e. obtained porous LiM 0.2mn 1.8o 4presoma.
Described surfactant is selected from the one in commercially available P123, F127 or cetyl amine bromide.
Graphene oxide described in step (2) adopts following methods to be prepared from: under ice-water bath condition, in 40-80ml concentrated sulfuric acid solution, add 1-2gNaNO 3, 2-4g crystalline flake graphite and 3-9g potassium permanganate, be warming up to 10-15 DEG C, stir 1h, be warming up to 35-40 DEG C again, keep 1h, subsequently, add 60-120ml deionized water, slowly be warming up to 100 DEG C, then drip 5% hydrogen peroxide solution, stir 1-2h, and repeatedly wash with the dilute hydrochloric acid solution of 5%, by centrifugal filtration, then under 60-80 DEG C of condition vacuumize 48h, namely obtained described graphene oxide.
The time of the magnetic agitation described in step (3) is 10-30min, and the time of ultrasonic disperse is 10-30min.
Drying condition described in step (3) is: in air dry oven, in 65-78 DEG C of forced air drying 24-48h.
Graphene and porous metals adulterated lithium manganate are carried out compound by the present invention, the introducing of Graphene, the conductivity of porous metals adulterated lithium manganate can not only be significantly improved, can also prevent porous metals adulterated lithium manganate crystal grain from reuniting, porous metals adulterated lithium manganate uniform crystal particles is dispersed in graphenic surface, and meanwhile, Graphene can also be played a supporting role to loose structure, suppress the dissolving of electrode material manganese in charge and discharge process, and then effectively improve the electrochemical stability of material system.
Compare glucose carbon source, the Graphene of curling is LiM 0.2mn 1.8o 4particle provides three-dimensional conductive network, and this greatly can improve the conductivity of material, and then improves its high rate performance; Secondly, LiM 0.2mn 1.8o 4nano particle evenly and be dispersed in securely on Graphene, can suppress the change in volume in charge and discharge process, and then decrease the powder phenomenon-tion in electrode reaction; Again, less LiM 0.2mn 1.8o 4nanoparticle size, shortens the diffusion length of lithium ion at crystals, makes the reaction of active material more abundant; Finally, the introducing of Graphene increases the specific area of material, material is had with electrolyte and contacts more fully, be conducive to the generation of electrochemical reaction.
Compared with prior art, the present invention has following characteristics:
1) owing to adopting sol-gel process to prepare porous LiM 0.2mn 1.8o 4presoma, process conditions are gentle, are easy to manipulation, by heat treatment, obtained porous LiM 0.2mn 1.8o 4there is high specific surface area, pore structure is stablized, and is conducive to the diffusion length shortening lithium ion, and facilitates electrolyte to enter material internal by loose structure, electronics and lithium ion can be spread conveniently by electrolyte, be conducive to the conductivity and the high rate performance that improve material system;
2) adopt Graphene and porous metals adulterated lithium manganate to carry out compound, can effectively prevent porous metals adulterated lithium manganate crystal grain from reuniting, suppress the dissolving of material system manganese in charge and discharge process, and the conductivity of material system can be improved further;
3) preparation method is simple, and raw material is easy to get, and obtained material has good crystallinity, even particle size, and size is at about 30nm, and good as anode material of lithium battery electrochemical stability, specific discharge capacity is high, has excellent high rate performance and cycle performance.
Accompanying drawing explanation
Fig. 1 is the ESEM spectrogram of porous metals adulterated lithium manganate/Graphene anode material of lithium battery that the present invention obtains.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Molal weight is that the high molecular polymer P123 of 5800 is dissolved in appropriate absolute ethyl alcohol by the first step, constantly stirs and obtain the P123 gel that the dispersed concentration of 20mL is 0.05g/mL under room temperature.
Second step, solid Mn (NO 3) 24H 2o, LiNO 3, Fe (NO 3) 39H 2o adds according to the ratio of mol ratio 9:5:1, LiNO 3amount be 0.05mol.
3rd step, by said mixture at room temperature middling speed magnetic agitation 12h.
4th step, by the colloidal sol 60 DEG C of forced air drying 24h in air dry oven mixed.
5th step, dried mixture in air atmosphere Muffle furnace 2 DEG C/min is warming up to 500 DEG C, insulation 2h.
6th step, adds 1gNaNO3 and 2g crystalline flake graphite in 40ml concentrated sulfuric acid solution; Add 3g potassium permanganate, be warming up to 10 DEG C, stir 1h; Be warmed up to 35 DEG C, keep 1h; Slowly be warming up to 100 DEG C after adding 60ml deionized water, drip 5% hydrogen peroxide solution, stir 1h; Repeatedly wash with the dilute hydrochloric acid solution of 5%; After centrifugal filtration, 60 DEG C of vacuumize 48h, obtained graphene oxide.The graphene oxide 1g that said method is obtained is dissolved in 10mL deionized water and obtains graphene oxide solution.
7th step, fully mixes sample with graphene oxide solution, magnetic agitation 20min, then ultrasonic disperse 20min.
8th step, by the mixture 60 DEG C of forced air drying 24h in air dry oven obtained.
9th step, calcine in dried sample argon gas atmosphere in tube furnace, 2 DEG C/min is warming up to 250 DEG C and keeps 2h.
By test analysis such as XRD, SEM, electro-chemical tests, the porous metals Fe2O3 doping LiMn2O4 prepared/Graphene anode material of lithium battery (LiFe 0.2mn 1.8o 4/ G), grain size is the lower specific discharge capacity of 15-25nm, 0.1C electric discharge is general LiMn 2o 41.1 times, circulation 50 circle after decay to 84.6% of initial capacity.
The ESEM spectrogram of porous metals adulterated lithium manganate/Graphene anode material of lithium battery that the present embodiment obtains as shown in Figure 1.LiFe 0.2mn 1.8o 4uniform particles is distributed on the graphene sheet layer of curling.
Embodiment 2
Molal weight is that the high molecular polymer P123 of 5800 is dissolved in appropriate absolute ethyl alcohol by the first step, constantly stirs and obtain the P123 gel that the dispersed concentration of 20mL is 0.08g/mL under room temperature.
Second step, solid Mn (NO 3) 24H 2o, LiNO 3, Fe (NO 3) 39H 2o adds according to the ratio of mol ratio 9:5:1, LiNO 3amount be 0.1mol.
3rd step, by said mixture at room temperature middling speed magnetic agitation 16h.
4th step, by the colloidal sol 70 DEG C of forced air drying 36h in air dry oven mixed.
5th step, dried mixture in air atmosphere Muffle furnace 3 DEG C/min is warming up to 600 DEG C, insulation 3h.
6th step, adds 1.5gNaNO3 and 3g crystalline flake graphite in 60ml concentrated sulfuric acid solution; Add 6g potassium permanganate, be warming up to 10 DEG C, stir 1h; Be warmed up to 35 DEG C, keep 1h; Slowly be warming up to 100 DEG C after adding 60ml deionized water, drip 5% hydrogen peroxide solution, stir 1h; Repeatedly wash with the dilute hydrochloric acid solution of 5%; After centrifugal filtration, 60 DEG C of vacuumize 48h, obtained graphene oxide.The graphene oxide 1g that said method is obtained is dissolved in 15mL deionized water and obtains graphene oxide solution.
7th step, fully mixes sample with graphene oxide solution, magnetic agitation 10min, then ultrasonic disperse 10min.
8th step, by the mixture 60 DEG C of forced air drying 24h in air dry oven obtained.
9th step, calcine in dried sample argon gas atmosphere in tube furnace, 3 DEG C/min is warming up to 300 DEG C and keeps 3h.
By test analysis such as XRD, SEM, electro-chemical tests, the porous metals Fe2O3 doping LiMn2O4 prepared/Graphene anode material of lithium battery (LiFe 0.2mn 1.8o 4/ G), grain size is the lower specific discharge capacity of 25-40nm, 0.1C electric discharge is general LiMn 2o 41.3 times, circulation 50 circle after decay to 92.3% of initial capacity.
Embodiment 3
Molal weight is that the high molecular polymer P123 of 5800 is dissolved in appropriate absolute ethyl alcohol by the first step, constantly stirs and obtain the P123 gel that the dispersed concentration of 20mL is 0.1g/mL under room temperature.
Second step, solid Mn (NO 3) 24H 2o, LiNO 3, Fe (NO 3) 39H 2o adds according to the ratio of mol ratio 9:5:1, LiNO 3amount be 0.5mol.
3rd step, by said mixture at room temperature middling speed magnetic agitation 24h.
4th step, by the colloidal sol 80 DEG C of forced air drying 48h in air dry oven mixed.
5th step, dried mixture in air atmosphere Muffle furnace 5 DEG C/min is warming up to 700 DEG C, insulation 4h.
6th step, adds 2gNaNO3 and 4g crystalline flake graphite in 60ml concentrated sulfuric acid solution; Add 9g potassium permanganate, be warming up to 15 DEG C, stir 1h; Be warmed up to 35 DEG C, keep 1h; Slowly be warming up to 100 DEG C after adding 120ml deionized water, drip 5% hydrogen peroxide solution, stir 2h; Repeatedly wash with the dilute hydrochloric acid solution of 5%; After centrifugal filtration, 60 DEG C of vacuumize 48h, obtained graphene oxide.The graphene oxide 1g that said method is obtained is dissolved in 15mL deionized water and obtains graphene oxide solution.
7th step, fully mixes sample with graphene oxide solution, magnetic agitation 20min, then ultrasonic disperse 20min.
8th step, by the mixture 60 DEG C of forced air drying 24h in air dry oven obtained.
9th step, calcine in dried sample argon gas atmosphere in tube furnace, 5 DEG C/min is warming up to 400 DEG C and keeps 5h.
By test analysis such as XRD, SEM, electro-chemical tests, the porous metals Fe2O3 doping LiMn2O4 prepared/Graphene anode material of lithium battery (LiFe 0.2mn 1.8o 4/ G), grain size is the lower specific discharge capacity of 40-50nm, 0.1C electric discharge is general LiMn 2o 41.4 times, circulation 50 circle after decay to 96.8% of initial capacity.
Embodiment 4
The preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery, specifically comprises the following steps:
(1) sol-gel process is adopted to prepare porous LiCo 0.2mn 1.8o 4presoma, then presoma is placed in Muffle furnace, in air atmosphere, Muffle furnace is warming up to 700 DEG C with 5 DEG C/min, constant temperature process 2h, i.e. obtained porous LiCo 0.2mn 1.8o 4;
(2) get graphene oxide, and add in deionized water, be made into the graphene oxide solution that mass concentration is 0.05g/mL;
(3) by porous LiCo obtained for step (1) 0.2mn 1.8o 4be placed in graphene oxide solution, magnetic agitation, ultrasonic disperse, after drying, be transferred in tube furnace, in argon gas atmosphere, tube furnace is warming up to 400 DEG C with 5 DEG C/min, constant temperature process 2h, i.e. obtained described porous metals adulterated lithium manganate/Graphene anode material of lithium battery.
Wherein, in step (1), sol-gel process prepares porous LiCo 0.2mn 1.8o 4presoma specifically comprise the following steps:
A F127 is dissolved in absolute ethyl alcohol by (), the mass concentration of control F127 is 0.05g/mL, and under room temperature condition, magnetic agitation 24h, i.e. obtained gel;
B () is by Mn (NO 3) 24H 2o, LiNO 3and doping metals nitrate is 9:5:1 in molar ratio, join in the obtained gel of step (a), control LiNO 3molar concentration in gel is 0.05mol/L, is uniformly mixed, dry, i.e. obtained porous LiCo 0.2mn 1.8o 4presoma.
In step (2), graphene oxide adopts following methods to be prepared from: under ice-water bath condition, in 80ml concentrated sulfuric acid solution, add 2gNaNO 3, 4g crystalline flake graphite and 9g potassium permanganate, be warming up to 10 DEG C, stir 1h, be warming up to 40 DEG C again, keep 1h, subsequently, add 120ml deionized water, slowly be warming up to 100 DEG C, then drip 5% hydrogen peroxide solution, stir 1h, and repeatedly wash with the dilute hydrochloric acid solution of 5%, by centrifugal filtration, then under 80 DEG C of conditions vacuumize 48h, namely obtained described graphene oxide.
In step (3), the time of magnetic agitation is 30min; The time of ultrasonic disperse is 30min; Drying condition is: in air dry oven, in 78 DEG C of forced air drying 24h.
Embodiment 5
The preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery, specifically comprises the following steps:
(1) sol-gel process is adopted to prepare porous LiNi 0.2mn 1.8o 4presoma, then presoma is placed in Muffle furnace, in air atmosphere, Muffle furnace is warming up to 500 DEG C with 2 DEG C/min, constant temperature process 4h, i.e. obtained porous LiNi 0.2mn 1.8o 4;
(2) get graphene oxide, and add in deionized water, be made into the graphene oxide solution that mass concentration is 0.1g/mL;
(3) by porous LiNi obtained for step (1) 0.2mn 1.8o 4be placed in graphene oxide solution, magnetic agitation, ultrasonic disperse, after drying, be transferred in tube furnace, in argon gas atmosphere, tube furnace is warming up to 250 DEG C with 2 DEG C/min, constant temperature process 5h, i.e. obtained described porous metals adulterated lithium manganate/Graphene anode material of lithium battery.
Wherein, in step (1), sol-gel process prepares porous LiNi 0.2mn 1.8o 4presoma specifically comprise the following steps:
A cetyl amine bromide is dissolved in absolute ethyl alcohol by (), the mass concentration controlling cetyl amine bromide is 0.5g/mL, and under room temperature condition, magnetic agitation 12h, i.e. obtained gel;
B () is by Mn (NO 3) 24H 2o, LiNO 3and doping metals nitrate is 9:5:1 in molar ratio, join in the obtained gel of step (a), control LiNO 3molar concentration in gel is 0.5mol/L, is uniformly mixed, dry, i.e. obtained porous LiNi 0.2mn 1.8o 4presoma.
In step (2), graphene oxide adopts following methods to be prepared from: under ice-water bath condition, in 40ml concentrated sulfuric acid solution, add 1gNaNO 3, 2g crystalline flake graphite and 3g potassium permanganate, be warming up to 15 DEG C, stir 1h, be warming up to 35 DEG C again, keep 1h, subsequently, add 60ml deionized water, slowly be warming up to 100 DEG C, then drip 5% hydrogen peroxide solution, stir 2h, and repeatedly wash with the dilute hydrochloric acid solution of 5%, by centrifugal filtration, then under 60 DEG C of conditions vacuumize 48h, namely obtained described graphene oxide.
In step (3), the time of magnetic agitation is 20min; The time of ultrasonic disperse is 20min; Drying condition is: in air dry oven, in 65 DEG C of forced air drying 48h.
Embodiment 6
The preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery, specifically comprises the following steps:
(1) sol-gel process is adopted to prepare porous LiZn 0.2mn 1.8o 4presoma, then presoma is placed in Muffle furnace, in air atmosphere, Muffle furnace is warming up to 600 DEG C with 3 DEG C/min, constant temperature process 3h, i.e. obtained porous LiZn 0.2mn 1.8o 4;
(2) get graphene oxide, and add in deionized water, be made into the graphene oxide solution that mass concentration is 0.08g/mL;
(3) by porous LiZn obtained for step (1) 0.2mn 1.8o 4be placed in graphene oxide solution, magnetic agitation, ultrasonic disperse, after drying, be transferred in tube furnace, in argon gas atmosphere, tube furnace is warming up to 300 DEG C with 3 DEG C/min, constant temperature process 4h, i.e. obtained described porous metals adulterated lithium manganate/Graphene anode material of lithium battery.
Wherein, in step (1), sol-gel process prepares porous LiZn 0.2mn 1.8o 4presoma specifically comprise the following steps:
A cetyl amine bromide is dissolved in absolute ethyl alcohol by (), the mass concentration controlling cetyl amine bromide is 0.08g/mL, and under room temperature condition, magnetic agitation 20h, i.e. obtained gel;
B () is by Mn (NO 3) 24H 2o, LiNO 3and doping metals nitrate is 9:5:1 in molar ratio, join in the obtained gel of step (a), control LiNO 3molar concentration in gel is 0.3mol/L, is uniformly mixed, dry, i.e. obtained porous LiZn 0.2mn 1.8o 4presoma.
In step (2), graphene oxide adopts following methods to be prepared from: under ice-water bath condition, in 60ml concentrated sulfuric acid solution, add 1.5gNaNO 3, 3g crystalline flake graphite and 4g potassium permanganate, be warming up to 12 DEG C, stir 1h, be warming up to 38 DEG C again, keep 1h, subsequently, add 100ml deionized water, slowly be warming up to 100 DEG C, then drip 5% hydrogen peroxide solution, stir 1h, and repeatedly wash with the dilute hydrochloric acid solution of 5%, by centrifugal filtration, then under 68 DEG C of conditions vacuumize 48h, namely obtained described graphene oxide.
In step (3), the time of magnetic agitation is 15min; The time of ultrasonic disperse is 25min; Drying condition is: in air dry oven, in 68 DEG C of forced air drying 36h.
Embodiment 7
The preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery, specifically comprises the following steps:
(1) sol-gel process is adopted to prepare porous LiCu 0.2mn 1.8o 4presoma, then presoma is placed in Muffle furnace, in air atmosphere, Muffle furnace is warming up to 640 DEG C with 4 DEG C/min, constant temperature process 4h, i.e. obtained porous LiCu 0.2mn 1.8o 4;
(2) get graphene oxide, and add in deionized water, be made into the graphene oxide solution that mass concentration is 0.06g/mL;
(3) by porous LiCu obtained for step (1) 0.2mn 1.8o 4be placed in graphene oxide solution, magnetic agitation, ultrasonic disperse, after drying, be transferred in tube furnace, in argon gas atmosphere, tube furnace is warming up to 360 DEG C with 4 DEG C/min, constant temperature process 5h, i.e. obtained described porous metals adulterated lithium manganate/Graphene anode material of lithium battery.
Wherein, in step (1), sol-gel process prepares porous LiCu 0.2mn 1.8o 4presoma specifically comprise the following steps:
A F127 is dissolved in absolute ethyl alcohol by (), the mass concentration of control F127 is 0.06g/mL, and under room temperature condition, magnetic agitation 18h, i.e. obtained gel;
B () is by Mn (NO 3) 24H 2o, LiNO 3and doping metals nitrate is 9:5:1 in molar ratio, join in the obtained gel of step (a), control LiNO 3molar concentration in gel is 0.2mol/L, is uniformly mixed, dry, i.e. obtained porous LiCu 0.2mn 1.8o 4presoma.
In step (2), graphene oxide adopts following methods to be prepared from: under ice-water bath condition, in 60ml concentrated sulfuric acid solution, add 1.8gNaNO 3, 3.6g crystalline flake graphite and 7.2g potassium permanganate, be warming up to 15 DEG C, stir 1h, be warming up to 36 DEG C again, keep 1h, subsequently, add 80ml deionized water, slowly be warming up to 100 DEG C, then drip 5% hydrogen peroxide solution, stir 1h, and repeatedly wash with the dilute hydrochloric acid solution of 5%, by centrifugal filtration, then under 75 DEG C of conditions vacuumize 48h, namely obtained described graphene oxide.
In step (3), the time of magnetic agitation is 15min; The time of ultrasonic disperse is 15min; Drying condition is: in air dry oven, in 70 DEG C of forced air drying 30h.

Claims (6)

1. the preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery, it is characterized in that, the method specifically comprises the following steps:
(1) sol-gel process is adopted to prepare porous LiM 0.2mn 1.8o 4presoma, then presoma is placed in Muffle furnace, in air atmosphere, Muffle furnace is warming up to 500-700 DEG C with 2-5 DEG C/min, constant temperature process 2-4h, i.e. obtained porous LiM 0.2mn 1.8o 4;
(2) graphene oxide solution that mass concentration is 0.05-0.1g/mL is made into;
(3) by porous LiM obtained for step (1) 0.2mn 1.8o 4be placed in graphene oxide solution, magnetic agitation, ultrasonic disperse, after drying, be transferred in tube furnace, in argon gas atmosphere, tube furnace is warming up to 250-400 DEG C with 2-5 DEG C/min, constant temperature process 2-5h, i.e. obtained described porous metals adulterated lithium manganate/Graphene anode material of lithium battery;
Wherein, M is doping metals, and this doping metals is the one in iron, cobalt, nickel, zinc or copper.
2. the preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery according to claim 1, is characterized in that, the sol-gel process described in step (1) prepares porous LiM 0.2mn 1.8o 4presoma specifically comprise the following steps:
A surfactant is dissolved in absolute ethyl alcohol by (), the mass concentration of control surface activating agent is 0.05-0.1g/mL, and under room temperature condition, magnetic agitation 12-24h, i.e. obtained gel;
B () is by Mn (NO 3) 24H 2o, LiNO 3and doping metals nitrate is 9:5:1 in molar ratio, join in the obtained gel of step (a), control LiNO 3molar concentration in gel is 0.05-0.5mol/L, is uniformly mixed, dry, i.e. obtained porous LiM 0.2mn 1.8o 4presoma.
3. the preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery according to claim 2, is characterized in that, described surfactant is selected from the one in commercially available P123, F127 or cetyl amine bromide.
4. the preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery according to claim 1, it is characterized in that, graphene oxide described in step (2) adopts following methods to be prepared from: under ice-water bath condition, to in 40-80ml concentrated sulfuric acid solution, add 1-2gNaNO 3, 2-4g crystalline flake graphite and 3-9g potassium permanganate, be warming up to 10-15 DEG C, stir 1h, be warming up to 35-40 DEG C again, keep 1h, subsequently, add 60-120ml deionized water, slowly be warming up to 100 DEG C, then drip 5% hydrogen peroxide solution, stir 1-2h, and repeatedly wash with the dilute hydrochloric acid solution of 5%, by centrifugal filtration, then under 60-80 DEG C of condition vacuumize 48h, namely obtained described graphene oxide.
5. the preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery according to claim 1, is characterized in that, the time of the magnetic agitation described in step (3) is 10-30min, and the time of ultrasonic disperse is 10-30min.
6. the preparation method of porous metals adulterated lithium manganate/Graphene anode material of lithium battery according to claim 1, is characterized in that, the drying condition described in step (3) is: in air dry oven, in 65-78 DEG C of forced air drying 24-48h.
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