CN104167532B - The graphite flake of a kind of sandwich structure/mangano-manganic oxide composite nano materials, preparation method and apply its lithium ion battery - Google Patents
The graphite flake of a kind of sandwich structure/mangano-manganic oxide composite nano materials, preparation method and apply its lithium ion battery Download PDFInfo
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Abstract
The invention discloses the graphite flake/mangano-manganic oxide composite nano materials of a kind of sandwich structure, preparation method and apply its lithium ion battery, wherein embodiment of the method is as follows: weigh expanded graphite and DMF by 0.5 5g/L proportioning, expanded graphite is put into and DMF is carried out ultrasonic 14 hours, obtain graphite flake solution；Add the deionized water that ratio is 1:1 1:9 with DMF, stir；Weighing concentration is 5 60g/L the four hydration manganese acetates relative to solvent DMF, wherein manganese is II valency, is dissolved in solvent, stirs；Above solution puts into hydro-thermal tank, heats up, furnace cooling after insulation；After being cooled to room temperature, with centrifuge, black deposit is cleaned；The black deposit cleaned is baked to sample drying at 50 80 DEG C.The present invention is used for providing a kind of simple method to obtain uniform Mn on non-oxidized graphite sheet surface3O4Nanometer particle film, is suitable for volume production.
Description
Technical field
The invention belongs to lithium-ion energy storage Material Field, the graphite flake of a kind of sandwich structure/mangano-manganic oxide composite nano materials, preparation method and apply its lithium ion battery.
Background technology
Graphene has the specific surface area of good electric conductivity and super large, uses grapheme material to replace traditional material with carbon element for lithium ion battery and the electrode of ultracapacitor, and it has shown good capacity characteristic and charge-discharge characteristic.But single Graphene also exists the shortcoming such as easily reunion, cyclical stability difference as electrode.Therefore preparing metal-oxide as electrode at graphenic surface is nearest study hotspot.
The storage lithium mechanism of transition metal oxide MO is different from conventional lithium ion battery mechanism, and during Li+ embeds, Li Yu MO occurs redox reaction, generates Li2O；During Li+ deviates from, Li2O Yu M can regeneration Li and MO, therefore it has bigger storage energy.But metal-oxide is during the lithium ion removal lithium embedded repeated, and there is serious change in volume effect.What research was more at present is to reduce bulk effect by the following method: one is to prepare nano-metal-oxide；Two is to form porous oxide；Three is to be prepared as complex chemical compound with CNT or Graphene.Wherein, mangano-manganic oxide Mn3O4Oxide has a high theoretical capacity of effect, meanwhile, its because having that good environment friendly, discharge potential be low, advantage of lower cost and receive significant attention.At present, existing graphene oxide or reduced graphene prepare Mn3O4Report, it is thus achieved that preferably lithium ion performance.But Mn3O4The highest in the distribution density of graphenic surface.The process preparing graphene oxide is complicated, wherein prepares graphene oxide effect on environment very big, and manufacturing cycle is long.
For above deficiency, the present invention uses very simple method to be prepared for a kind of graphite flake, and graphite flake has the graphite linings composition of multilamellar, although the number of plies is more, but preparation is simple, can be prepared for Mn with large-scale production on two faces of graphite flake3O4Film layer, thus sandwich structure consisting.This Mn3O4Film layer is made up of nano-particle, and nanoparticle size is little, has certain space each other, thus has gathered current several method improving storage lithium performance.Higher reversible capacity, cyclical stability and the life-span etc. can be obtained.
Summary of the invention
For solving the problems referred to above, it is an object of the invention to provide a kind of simple method and obtain uniform Mn on non-oxidized graphite sheet surface3O4Nanometer particle film, film thickness direction is less than 100nm, even particle size, individual particle size, at below 20nm, has certain space each other, and space is less than 10nm, it is evenly distributed on two surfaces of graphite flake, forming sandwich structure with graphite flake, this structure can eliminate the direct contact between graphite flake, does not haves agglomeration.Mn3O4Owing to diameter is little, size is uniform, and distribution density is big, it is possible to obtain higher storage lithium performance.And graphite flake is not through oxidation processes, therefore can guarantee that the electric conductivity of maximum.
A further object of the present invention is to provide the graphite flake/mangano-manganic oxide composite nano materials of the sandwich structure prepared by above method.
A further object of the present invention is to provide the lithium battery using the graphite flake/mangano-manganic oxide composite nano materials of this sandwich structure to make negative pole.
For achieving the above object, the technical scheme is that
The preparation method of the graphite flake of a kind of sandwich structure/mangano-manganic oxide composite nano materials, comprises the following steps:
S10, weighs expanded graphite and dimethylformamide DMF by 0.5-5g/L proportioning, expanded graphite is put into and carries out in DMF ultrasonic 1-4 hour, obtain graphite flake solution；
S20, adds deionized water, and deionization is 1:1-1:9 with the ratio of DMF, stirs；
S30, weighs four hydration manganese acetates, and wherein manganese is II valency, and four hydration manganese acetates are 5-60g/L relative to the concentration of solvent DMF, four hydration manganese acetates is dissolved in solvent, stirs；
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume fraction of hydro-thermal tank is 1/5-1/2, is warmed up to 100-150 DEG C with the programming rate of 1 DEG C/minute-10 DEG C/minute, temperature retention time 1.5h-10h, rear furnace cooling；
S50, after being cooled to room temperature, pours out solution, is cleaned by black deposit with centrifuge, cleans and uses water and ethanol respectively to clean 3-5 time；
S60, is baked to sample drying by the black deposit cleaned at 50-80 DEG C.
And, the graphite flake of a kind of sandwich structure/mangano-manganic oxide composite nano materials, the graphite flake of described sandwich structure/mangano-manganic oxide composite nano materials is prepared by such as said method, graphite flake surface and mangano-manganic oxide Mn3O4Nano-particular film sandwich structure consisting, graphite flake is in central core, and both sides are less than the Mn of 100nm by film thickness direction3O4Nano-particular film forms, and individual particle size, at below 20nm, has the space less than 10nm each other.
Preferably, the number of plies of described graphite flake is less than 100 layers.
And, a kind of lithium ion battery, including negative pole, the material of described negative pole is above-mentioned graphite flake/mangano-manganic oxide composite nano materials.
Compared with prior art, beneficial effects of the present invention is as follows:
(1) graphite flake surface and Mn3O4Nano-particular film sandwich structure consisting, graphite flake is in central core, and both sides are by the Mn less than 100 nanometers3O4Nano-particular film forms.The sandwich stabilisation systems that graphite flake and oxide composition is new, it is to avoid again the piling up and the reunion of oxide nano particles of graphite flake.
(2) between the oxide particle prepared by, space is the least, and oxide particle density is the highest, is conducive to improving the storage lithium performance of material.
(3) this Mn3O4Nano-particle advantages of good crystallization, size is uniform, and size, at below 20nm, has space each other, and space is at 1-10nm.Owing to particle size is little, and between there is certain space, it is possible to reduce Mn3O4Bulk effect in charge and discharge process.Meanwhile, the space between oxide nano particles can be that electrolyte ion provides passage at whole composite, promotes the quick transmission of ion.
(4) x ray diffraction can be clearly visible (002) diffraction maximum of graphite linings, although the graphite flake of preparation is less than 100 layers of graphite linings composition, but this method preparation process is simple, is suitable for volume production.This method there is not requirement for the number of plies of graphite linings, prepares composite by ultrasonic method, predominantly commercial production.If the graphite flake that the method prepares changes Graphene into, equally preparing the sandwich composite of the present invention, and performance is improved, but the preparation process of Graphene is complicated, production cost is high, is unsuitable for the large-scale production under current state.
(5) graphite flake prepared by embodiment of the present invention method is not owing to carrying out oxidizer treatment, and the degree of oxidation of graphite flake is low.Thus in processing procedure below, it is not necessary to using reducing agents such as adding hydrazine to carry out reduction treatment, hydrazine has toxic action to environment.And can guarantee that the structural intergrity of graphite, thus ensure optimal electrical conductance.
(6) due to graphite flake be Multi-layer graphite composition, the Multi-layer graphite Rotating fields of graphite flake still keeps the original structure of graphite, therefore, it is possible to store certain lithium ion.
(7) the composite 50mA/g of embodiment of the present invention charge and discharge lithium capacity first is 900mA h/g, and stablizing capacity is 550mA h/g；100mA/g charge and discharge lithium capacity is 450mA h/g.
Accompanying drawing explanation
Fig. 1 is the flow chart of steps of the graphite flake/mangano-manganic oxide composite nano materials preparation method of the sandwich structure of the embodiment of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the graphite flake/mangano-manganic oxide composite nano materials of the sandwich structure of the embodiment of the present invention；
Fig. 3 be the sandwich structure of the embodiment of the present invention graphite flake/mangano-manganic oxide composite nano materials in the transmission electron microscope picture of graphite flake；
Fig. 4 is the low power transmission electron microscope picture of the graphite flake/mangano-manganic oxide composite nano materials of the sandwich structure of the embodiment of the present invention；
Fig. 5 is the high power transmission electron microscope picture of the graphite flake/mangano-manganic oxide composite nano materials of the sandwich structure of the embodiment of the present invention；
Fig. 6 is the XRD figure spectrum of the graphite flake/mangano-manganic oxide composite nano materials of the sandwich structure of the embodiment of the present invention；
Fig. 7 is the charge and discharge lithium cycle performance figure under the different charge-discharge magnifications of the graphite flake/mangano-manganic oxide composite nano materials of the sandwich structure of the embodiment of the present invention；
Fig. 8 is the CV figure of graphite flake/first three under 50mA/g of mangano-manganic oxide composite nano materials time of the sandwich structure of the embodiment of the present invention.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
On the contrary, the present invention contains any replacement made in the spirit and scope of the present invention, amendment, equivalent method and scheme being defined by the claims.Further, in order to make the public that the present invention to be had a better understanding, in below the details of the present invention being described, detailed describe some specific detail sections.The description not having these detail sections for a person skilled in the art can also understand the present invention completely.
Seeing Fig. 1, show the flow chart of steps of the graphite flake/mangano-manganic oxide composite nano materials preparation method of the sandwich structure of the embodiment of the present invention, it comprises the following steps:
S10, weighs expanded graphite and dimethylformamide DMF by 0.5-5g/L proportioning, expanded graphite is put into and carries out in DMF ultrasonic 1-4 hour, obtain graphite flake solution；
S20, adds deionized water, and deionization is 1:1-1:9 with the ratio of DMF, stirs；
S30, weighs four hydration manganese acetates, and wherein manganese is II valency, it is called for short four hydrations manganese acetate (II), four hydrations manganese acetate (II) are 5-60g/L relative to the concentration of solvent DMF, four hydrations manganese acetate (II) are dissolved in solvent, stir；
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume fraction of hydro-thermal tank is 1/5-1/2, i.e. reaction solution volume accounts for the 20%-50% of hydro-thermal tank cumulative volume, it is warmed up to 100-150 DEG C with the programming rate of 1 DEG C/minute-10 DEG C/minute, temperature retention time 1.5h-10h, rear furnace cooling；
S50, after being cooled to room temperature, pours out solution, is cleaned by black deposit with centrifuge, cleans and uses water and ethanol respectively to clean 3-5 time；
S60, is baked to sample drying by the black deposit cleaned at 50-80 DEG C.
By the description of procedure made above, the preparation process of the graphite flake of the sandwich structure of the embodiment of the present invention/mangano-manganic oxide composite nano materials is simple, and controllability is good, and suitable amount metaplasia is produced.Meanwhile, graphite flake prepared by this method is not owing to carrying out oxidizer treatment, and the degree of oxidation of graphite flake is low, thus in processing procedure below, it is not necessary to using reducing agents such as adding hydrazine to carry out reduction treatment, hydrazine has toxic action to environment.And can guarantee that the structural intergrity of graphite, thus ensure optimal electrical conductance.
Simultaneously, corresponding with embodiment of the method, further embodiment of this invention provides the graphite flake/mangano-manganic oxide composite nano materials of the sandwich structure prepared by said method, see Fig. 2 to Fig. 6, wherein Fig. 2 is scanning electron microscope (SEM) photograph, Fig. 3 is the transmission electron microscope picture of graphite flake, Fig. 4 is low power transmission electron microscope picture, Fig. 5 is high power transmission electron microscope picture, Fig. 6 is XRD figure spectrum, by above picture it appeared that the graphite flake/mangano-manganic oxide of the sandwich structure of the embodiment of the present invention has a following architectural feature: graphite flake surface and mangano-manganic oxide Mn3O4Nano-particular film sandwich structure consisting, graphite flake is in central core, and both sides are less than the Mn of 100nm by film thickness direction3O4Nano-particular film forms, and individual particle size, at below 20nm, has the space less than 10nm each other.In a further preferred embodiment, the number of plies of graphite flake is less than 100 layers, and the graphite flake suitable amount metaplasia of this kind of specification is produced.Those skilled in the art, it is understood that the graphite flake of multilamellar can change into the Graphene of monolayer, equally prepare the sandwich composite of the present invention, and performance is improved, but the preparation process of Graphene is complicated, production cost is high, is not suitable for the quantization of current stage and produces.
By the architectural characteristic of above graphite flake/mangano-manganic oxide composite nano materials, further embodiment of this invention provides a kind of lithium battery, and including negative pole, wherein the material of negative pole is graphite flake as above/mangano-manganic oxide composite nano materials.General method is used to test after making the test battery of composite, see Fig. 7 for filling lithium cycle performance figure, Fig. 8 is the CV figure of first three under 50mA/g time, the lithium ion battery 50mA/g charge and discharge lithium capacity first understanding the embodiment of the present invention is 900mA h/g, and stablizing capacity is 550mA h/g；100mA/g charge and discharge lithium capacity is 450mA h/g, and the capacity under other charge-discharge velocity is shown in Fig. 7, and charge and discharge efficiency is high.
Below by by the preparation process of alum ink sheet/mangano-manganic oxide composite nano materials for multiple specific embodiments.Hydro-thermal tank used in specific embodiment is market and buys, and its typical volume is 20ml, 50ml, 100ml and 250ml.In specific embodiment, the cumulative volume of mixed solution can cover reaction solution volume by ratio adjustment and account for the 20%-50% of hydro-thermal tank cumulative volume.
Embodiment 1
Weigh expanded graphite 4mg and DMF8ml, expanded graphite is put into DMF and carries out ultrasonic 1 hour, obtain graphite flake solution.Weigh deionized water 2ml, add graphite and obtain solution, stir.Weigh four hydration manganese acetate (II) 40mg, four hydrations manganese acetate (II) are dissolved in mixed solvent, stirred conjunction and dissolved.Above solution is put into the hydro-thermal tank that volume is 20ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 50%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 120 DEG C with the programming rate of 1 DEG C/minute, temperature retention time 1.5h, rear furnace cooling.With centrifuge, microparticle is carried out, cleans and use alcoholic solution and water respectively to clean 5 times, at 50 DEG C, be baked to sample drying, i.e. obtain graphite flake/mangano-manganic oxide composite nano materials sample.
Embodiment 2
Weigh expanded graphite 40mg and DMF8ml, expanded graphite is put into DMF and carries out ultrasonic 2 hours, obtain graphite flake solution.Weigh deionized water 8ml, add graphite flake solution, stir.Weighing four hydration manganese acetate (II) 480mg, four hydrations manganese acetate (II) are dissolved in mixed solvent, stirring is to being completely dissolved.Above solution is put into the hydro-thermal tank that volume is 50ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 32%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 150 DEG C with the programming rate of 5 DEG C/minute, temperature retention time 5h, rear furnace cooling.With centrifuge, microparticle is carried out, cleans and use alcoholic solution and water respectively to clean 3 times.At 80 DEG C, it is baked to sample drying, i.e. obtains graphite flake/mangano-manganic oxide composite nano materials sample.
Embodiment 3
Weigh expanded graphite 60mg and DMF32ml, expanded graphite is put into DMF and carries out ultrasonic 3 hours, obtain graphite flake solution.Weigh deionized water 16ml, add graphite flake solution, stir.Weigh four hydration manganese acetate (II) 800mg, four hydrations manganese acetate (II) are dissolved in mixed solvent, stirred conjunction and dissolved.Above solution is put into the hydro-thermal tank that volume is 100ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 48%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 130 DEG C with the programming rate of 10 DEG C/minute, temperature retention time 10h, rear furnace cooling.With centrifuge, microparticle is carried out, cleans and use alcoholic solution and water respectively to clean 4 times.At 60 DEG C, it is baked to sample drying, i.e. obtains graphite flake/mangano-manganic oxide composite nano materials sample.
Embodiment 4
Weigh expanded graphite 80mg and DMF32ml, expanded graphite is put into DMF and carries out ultrasonic 4 hours, obtain graphite flake solution.Weigh deionized water 24ml, add graphite flake solution, stir.Weighing four hydration manganese acetate (II) 1200mg, manganese acetate is dissolved in mixed solvent, stirring is completely dissolved.Above solution is put into the hydro-thermal tank that volume is 250ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 22.4%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 140 DEG C with the programming rate of 5 DEG C/minute, temperature retention time 4h, rear furnace cooling.With centrifuge, microparticle is carried out, cleans and use alcoholic solution and each 5 times of water.At 70 DEG C, it is baked to sample drying, i.e. obtains graphite flake/mangano-manganic oxide composite nano materials sample.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (4)
1. a preparation method for the graphite flake of sandwich structure/mangano-manganic oxide composite nano materials, it is special
Levy and be, comprise the following steps:
S10, weighs expanded graphite and dimethylformamide DMF by 0.5-5g/L proportioning, expanded graphite is put
Enter DMF is carried out ultrasonic 1-4 hour, obtain graphite flake solution；
S20, adds deionized water, and deionization is 1:1-1:9 with the ratio of DMF, stirs；
S30, weighs four hydration manganese acetates, and wherein manganese is II valency, and four hydration manganese acetates are relative to solvent DMF
Concentration be 5-60g/L, by four hydration manganese acetates be dissolved in solvent, stir；
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume fraction of hydro-thermal tank is 1/5-1/2, with 1 DEG C
/ the programming rate of points-10 DEG C/minute is warmed up to 100-150 DEG C, temperature retention time 1.5h-10h, rear furnace cooling；
S50, after being cooled to room temperature, pours out solution, is cleaned by black deposit with centrifuge, and cleaning is adopted
Respectively clean 3-5 time with water and ethanol；
S60, is baked to sample drying by the black deposit cleaned at 50-80 DEG C.
2. the graphite flake of a sandwich structure/mangano-manganic oxide composite nano materials, it is characterised in that institute
State the graphite flake/mangano-manganic oxide composite nano materials of sandwich structure by the method for claim 1 system
Standby acquisition, graphite flake surface and mangano-manganic oxide Mn3O4Nano-particular film sandwich structure consisting, graphite flake
Being in central core, both sides are less than the Mn of 100nm by film thickness direction3O4Nano-particular film forms, single
Granular size, at below 20nm, has the space less than 10nm each other.
The graphite flake of sandwich structure the most according to claim 2/mangano-manganic oxide composite nano materials,
It is characterized in that, the number of plies of described graphite flake is less than 100 layers.
4. a lithium ion battery, including negative pole, it is characterised in that the material of described negative pole is that right such as is wanted
Seek the graphite flake described in 2 or 3/mangano-manganic oxide composite nano materials.
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| CN105355874A (en) * | 2015-11-03 | 2016-02-24 | 湖北工程学院 | Nitrogen-doped porous carbon ball/manganic manganous oxide nanometer composite electrode material and preparation method thereof |
| CN105609752A (en) * | 2016-02-02 | 2016-05-25 | 陕西科技大学 | Preparation method for nano-granular Mn3O4/Super P lithium ion battery negative electrode material |
| CN105514398B (en) * | 2016-03-04 | 2017-11-10 | 中国石油大学(华东) | A kind of graphite oxide/manganese oxide controllable nano composite for electrode of lithium cell |
| CN108365182B (en) * | 2017-12-28 | 2020-11-13 | 杭州电子科技大学 | Iron ion doped nano manganous manganic oxide/multilayer graphene composite material, preparation method thereof and lithium battery applying iron ion doped nano manganous manganic oxide/multilayer graphene composite material |
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| US3600231A (en) * | 1969-11-28 | 1971-08-17 | Esb Inc | Mercury cell |
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