CN109802115A - Lithium ion battery and negative electrode material and preparation method thereof - Google Patents
Lithium ion battery and negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to field of lithium ion battery, a kind of lithium ion battery and negative electrode material and preparation method thereof are disclosed.Method includes: to prepare graphene oxide, disperses the first solvent for graphene oxide, forms the first suspension；Graphene oxide powder is isolated from the first suspension, graphene oxide powder surface is in three-dimensional drape shape；Graphene oxide powder and graphite powder are mixed and are scattered in the second solvent, forms the second suspension；It is spray-dried the second suspension, obtains dry solid powder；Under an inert atmosphere, solid powder is toasted, it is cooling to get lithium ion battery negative material.
Description
Technical field
The present invention relates to field of lithium ion battery, a kind of lithium ion battery and negative electrode material and preparation method thereof are disclosed.
Background technique
From after lithium ion battery commercialization, because it is high with energy density, cell voltage is high, have extended cycle life with it is memoryless
The advantages that effect, not only rapidly becomes energy storage device and applies in the every field of life, and causes expert's research
The broad interest of persons.With the rapid development of the development of electronic electric equipment, especially electric car so that existing lithium from
Sub- battery is not able to satisfy energy demand in energy density and power density, therefore finds and prepare the material with high-energy density
It is extremely urgent problem.
With the promotion of battery energy density, due to the architectural characteristic of its own, the theoretical specific capacity of graphite only has
372mAh/g, and lithium ion transport rate is low, is far insufficient for the energy demand of rapid growth, while being compacted also can be increasingly
Height, this requires the stability of graphite cathode also to increase accordingly, and presently, adulterates and cladding is still a master of processing
Stream means, doping vario-property can be such that structure and surface state of the graphite cathode in cyclic process is protected later, enhance
The stability of circulation, in addition, the introducing of metal and nonmetalloid can also significantly improve the performance of cathode.
Graphene is the basic unit for constituting other carbon material structures, and graphene package structure has diversity, can be with shape
At the fullerene of zero dimension, one-dimensional carbon nanotube can be curled into, it is stackable at three-dimensional graphite.The theory of grapheme material compares table
Area is up to 2600m2/g, has heating conduction outstanding and ultimate strength, and the electron mobility of high speed at room temperature, these
Excellent property makes it have very big development prospect in terms of energy storage.
Patent [201610535236.4] disclosure of the invention is a kind of using anthracite as isotropic graphite/graphene of raw material
Composite microsphere negative electrode material and preparation method thereof.Resulting composite microsphere negative electrode material is will to be graphitized the graphite that anthracite obtains
Crystallite and graphene platelet are bonded the microballoon to form diameter at 10-20 microns.Comprise the concrete steps that by anthracite through crushing, removal of impurities,
It is obtained after high temperature graphitization, oxidation intercalation, mist projection granulating processing.Graphene forms continuous conductive mesh inside complex microsphere
Network not only improves the infiltration of electrolyte, is also beneficial to promote the lithium ion diffusion coefficient of composite material, improves its high rate performance.
The present inventor has found in carrying out research process of the invention, the patent using graphene as raw material, it is expensive, be unfavorable for
Industrial production.
A kind of graphene coated graphite/metal composite granule negative electrode material of patent [201810186801.X] disclosure of the invention and
Preparation method, wherein oxidation modification graphite material is doped to obtain graphite/metal the described method includes: first passing through metal
Then the polyacrylol oligomer solid of thermal oxide is uniformly mixed with graphite/metal composite granule, passes through later by composite granule
Baking, calcination processing, finally obtain graphene coated graphite/metal composite granule negative electrode material.It is made by the method for the invention
Graphene coated graphite/metal composite granule negative electrode material not only there is preferable chemical property, and its preparation is more square
Just, environment friendly and pollution-free, low in cost, and effectively increase cycle performance, battery of the graphite as lithium ion battery negative material
Capacity and coulombic efficiency.The present inventor has found in carrying out research process of the invention, the graphene which uses
Embedding lithium site is relatively smaller, and the infiltration effect of electrolyte is poor, promotes less effective to the cycle performance of battery.
Summary of the invention
The first purpose of the embodiment of the present invention is to provide a kind of lithium ion battery and negative electrode material and preparation method thereof, answers
Be conducive to improve the reversible capacity and circulating ratio of lithium ion battery with the technical solution.
In a first aspect, a kind of preparation method of lithium ion battery negative material provided in an embodiment of the present invention, comprising:
Graphene oxide is prepared,
The first solvent is dispersed by the graphene oxide, forms the first suspension；
The graphene oxide powder is isolated from first suspension, the graphene oxide powder surface is in three
Tie up accordion；
The graphene oxide powder and graphite powder are mixed and are scattered in the second solvent, forms the second suspension；
It is spray-dried second suspension, obtains dry solid powder；
Under an inert atmosphere, the solid powder is toasted, it is cooling to get lithium ion battery negative material.
Optionally, after isolating the graphene oxide powder in first suspension,
By surface in three-dimensional drape shape the graphene oxide powder and graphite powder mix be scattered in the second solvent it
Before,
Further include:
Surface is soaked in alkaline solution in the graphene oxide powder of three-dimensional drape shape, forms third suspension；
The graphene oxide powder is isolated from the third suspension, the three-dimensional of the graphene oxide powder is more
A plurality of hole portions are also formed on the fold of hole；
The graphene oxide powder and graphite powder are mixed and are scattered in the second solvent, specifically,
By the graphene oxide powder for being also formed with a plurality of hole portions on three-dimensional porous fold and the powdered graphite
Mixing is scattered in second solvent.
Optionally, after isolating the graphene oxide powder in first suspension,
By surface in three-dimensional drape shape the graphene oxide powder and graphite powder mix be scattered in the second solvent it
Before,
Further include:
Surface will be mixed in the graphene oxide powder of three-dimensional drape shape with the powdered graphite, mixing is impregnated
In the alkaline solution to scheduled duration, the alkaline solution is filtered out, cleans, obtains hybrid solid powder；
The graphene oxide powder and graphite powder are mixed and are scattered in the second solvent, specifically,
The hybrid solid powder is mixed and is scattered in second solvent.
Optionally, the graphite powder of mixing and the quality proportioning of the graphene oxide powder are: 1: (0.01~
0.28)。
Optionally, the graphite powder of mixing and the quality proportioning of the graphene oxide powder are: 1: (0.11~
0.16)。
Optionally, the graphite powder of mixing and the quality proportioning of the graphene oxide powder are: 1: 0.11.
Optionally, the graphite powder of mixing and the quality proportioning of the graphene oxide powder are: 1: 0.16.
Optionally, specifically using Hummers method liquid phase oxidation, the oxygen is synthesized with graphite powder synthesis graphene oxide
Graphite alkene.
Optionally, first solvent is deionized water or ethyl alcohol.
Optionally, the first solvent is dispersed by the graphene oxide, forms the first suspension, comprising:
First solvent is added in the graphene oxide, ultrasonic wave disperses first solvent to get described first
Suspension.
11, the preparation method of lithium ion battery negative material according to claim 1 or 2 or 3, characterized in that
Second solvent is deionized water or ethyl alcohol.
12, the preparation method of lithium ion battery negative material according to claim 1 or 2 or 3, characterized in that
The inert atmosphere are as follows: any or combination of nitrogen, argon gas, helium.
13, the preparation method of lithium ion battery negative material according to claim 1 or 2 or 3, characterized in that
Under an inert atmosphere, the solid powder is toasted, it is cooling to get lithium ion battery negative material, comprising:
The solid powder is placed in the inert atmosphere, rises the temperature of the inert atmosphere gradually from initial temperature
Temperature is maintained the inert atmosphere in the peak temperature scheduled duration, toasts the solid powder to peak temperature,
The temperature of the inert atmosphere is set to be cooled to predetermined low temperature level gradually from the peak temperature to get the lithium-ion electric
Pond graphite cathode material.
14, the preparation method of lithium ion battery negative material according to claim 13, characterized in that the peak value
Temperature are as follows: 700~900 DEG C any.
15, the preparation method of lithium ion battery negative material according to claim 14, characterized in that the peak value
Temperature are as follows: 850 DEG C.
16, the preparation method of lithium ion battery negative material according to claim 13, characterized in that make described lazy
The temperature of property atmosphere is gradually heated to peak temperature from initial temperature, specifically,
Make the temperature of the inert atmosphere from initial temperature, the peak temperature is warming up to the speed of 1~4 DEG C/min.
17, the preparation method of lithium ion battery negative material according to claim 16, characterized in that make described lazy
The temperature of property atmosphere is warming up to the peak temperature from initial temperature with the speed of 2 DEG C/min.
18, the preparation method of lithium ion battery negative material according to claim 13, characterized in that make described lazy
The temperature of property atmosphere is gradually cooled to predetermined low temperature level from the peak temperature, specifically,
Make the temperature of the inert atmosphere from the peak temperature, predetermined low temperature level is cooled to the speed of 1~4 DEG C/min.
19, the preparation method of lithium ion battery negative material according to claim 18, characterized in that make described lazy
The temperature of property atmosphere is gradually cooled to predetermined low temperature level from the peak temperature, specifically,
Make the temperature of the inert atmosphere from from the peak temperature, predetermined low temperature level is cooled to the speed of 2 DEG C/min.
20, the preparation method of lithium ion battery negative material according to claim 2 or 3, characterized in that
The alkaline solution are as follows: potassium hydroxide solution or sodium hydroxide solution.
21, the preparation method of lithium ion battery negative material according to claim 2 or 3, characterized in that
The concentration of the alkaline solution is 1~5mol/L.
22, the preparation method of lithium ion battery negative material according to claim 2 or 3, characterized in that
Impregnate a length of 12-16h when the immersion of the alkaline solution.
23, the preparation method of lithium ion battery negative material according to claim 22, characterized in that by described three
The graphene oxide powder of dimension accordion is soaked in a length of 14h when the immersion of alkaline solution.
24, lithium ion battery negative material made of a kind of any preparation method using claim 1 to 23.
25, a kind of lithium ion battery for applying negative electrode material described in claim 24.
Therefore the main material of the lithium ion battery negative material of the present embodiment is lower-cost graphite, in graphite
Periphery cladding as auxiliary material three-dimensional drape shape graphene, can be not necessarily to any conductive agent is added, that is, be greatly improved lithium from
The electric discharge gram volume of sub- battery improves the circulating ratio performance of battery.
Detailed description of the invention
Fig. 1 is the cryogenic property evaluation and test control of the sample of experimental example 1-10 and comparative example 1-3 that the embodiment of the present invention 1 provides
Figure.
Specific embodiment
Below in conjunction with specific attached drawing and embodiment, the present invention will be described in detail, herein illustrative examples of the invention
Attached drawing and explanation are used to explain the present invention, but not as a limitation of the invention.
Embodiment 1:
The preparation method for present embodiments providing a kind of lithium ion battery negative material, mainly comprises the steps that
1) graphene oxide is synthesized with graphite powder, the synthetic method of this step can be, but not limited to real using the prior art
It is existing, it is such as but not limited to using Hummers method, liquid phase oxidation synthesizes the graphene oxide of the present embodiment.Such as:
A certain amount of concentrated sulfuric acid is placed in ice-water bath after 4h, the graphite powder of predetermined amount is added, with vigorous stirring slowly
Potassium permanganate is added, maintenance system temperature does not surpass 20 DEG C, is put into 30-35 DEG C of water-bath after mixing evenly and reacts 2-5h, then plus
Enter deionized water, so that system temperature is no more than 85-98 DEG C, continues to stir 15min；Be separately added into 1400mL deionized water and
150mL30% (mass fraction) H2O2, filter immediately, filter cake is sufficiently washed with 1mol/LHCl cannot measure SO into filtrate2 4-, then
Neutrality is washed with deionized water into.After freeze-drying, gained sample is graphene oxide (being denoted as GO).
2) graphene oxide that step 1) synthesizes scheduled solvent is soaked in (to be denoted as the first solvent, can be, but not limited to
For deionized water or ethyl alcohol), decentralized processing (being such as but not limited to disperse using ultrasonic wave) is carried out, suspension is formed it into
(being denoted as the first suspension)；
3) the first suspension that step 2) obtains is spray-dried, obtains dry solid using spray dryer
Graphene oxide powder observes the graphene oxide powder under scanning electron microscope, it can be observed that it is three-dimensional drape
The graphene oxide powder of the three-dimensional drape shape is denoted as PGO1 by shape；
4) powdered graphite and graphene oxide powder PGO1 obtained above scheduled solvent is further soaked in (to be denoted as
Second solvent can be, but not limited to as deionized water or ethyl alcohol), it carries out decentralized processing and (is such as but not limited to using ultrasonic wave
Dispersion), form it into suspension (being denoted as the second suspension)；
In this step, the quality proportioning of the graphene oxide powder PGO1 of powdered graphite and the three-dimensional drape shape of addition
Are as follows: 1: (0.01~0.28).
5) the second suspension that step 4) obtains is spray-dried, obtains dry solid using spray dryer
Powder；
6) under inert atmosphere (normal pressure), then the solid powder that baking above-mentioned steps obtain carries out cooling up to this reality
The graphite negative material of lithium ion battery for applying example observes the solid powder under scanning electron microscope, it can be observed that it is
The graphene coated of three-dimensional drape shape is in graphite periphery.
As the signal of the present embodiment, the inert atmosphere that uses in this step is does not play any chemical reaction with solid powder
Gas, be such as but not limited to are as follows: nitrogen, argon gas, helium any or combination.
As the signal of the present embodiment, in this step under an inert atmosphere, baking, cooling technique are as follows:
61) it toasts, solid powder is placed in inert atmosphere, is gradually heated to the temperature of inert atmosphere from initial temperature
One scheduled peak temperature (being such as but not limited to for the peak temperature to be set as 700~900 DEG C, preferably 850 DEG C) maintains inertia
Atmosphere is in peak temperature scheduled duration, and the present inventor has found in carrying out research process of the invention, after being gradually warmed up using this
Keep the baking process of one section of duration, it can be ensured that sufficiently decomposed by the oxygen-containing group on the powdered graphite of graphene coated, really
It protects and is formed with hole portion structure abundant in fold place.
As the signal of this step, heating rate can be, but not limited to the heating rate using 1~4 DEG C/min, and preferably 2
DEG C/heating rate of min.
62) cooling, maintaining inert atmosphere to be cooled to the temperature of inert atmosphere gradually after peak temperature scheduled duration
Predetermined low temperature level to get the present embodiment graphite negative material of lithium ion battery.The present inventor is carrying out research process of the invention
Middle discovery, relative to the technical solution of instantaneous temperature reduction, using the cooling technique gradually to cool down of the present embodiment, it can be ensured that by stone
Oxygen-containing group on the powdered graphite of black alkene cladding sufficiently decomposes, it is ensured that relatively rich pore structure.Its further beneficial effect
It is detailed in experiment contrast analysis.
As the signal of this step, rate of temperature fall can be, but not limited to the cooling rate using 1~4 DEG C/min, and preferably 2
DEG C/cooling rate of min.
Therefore the main material of the lithium ion battery negative material of the present embodiment is lower-cost graphite, in graphite
Periphery cladding as auxiliary material three-dimensional drape shape graphene, can be not necessarily to any conductive agent is added, that is, be greatly improved lithium from
The electric discharge gram volume of sub- battery improves the circulating ratio performance of battery.
Embodiment 2:
As the signal of the present embodiment, the present inventor is during carrying out the present invention it has furthermore been found that can also be into one
Step after the step 3) of embodiment 1, step 4) take a step forward the following steps are included:
31) the graphene oxide powder PGO1 for the three-dimensional drape shape that step 3) obtains is soaked in alkaline solution (has
Certain corrosive weakly alkaline solution, be such as but not limited to are as follows: sodium hydroxide solution, potassium oxide solution, the wherein alkaline solution
Concentration can be, but not limited to impregnate scheduled duration for 1~5mol/L), which is about 12-16h, for example impregnates 14h, make
Alkaline solution reacts (i.e. weak corrosion reaction) with the oxygen-containing group of graphene oxide, in order to accelerate its reaction speed, can soak
It is stirred when bubble, it is made to be uniformly dispersed, the suspension that graphene oxide powder PGO1 soak is formed is denoted as third and is hanged
Supernatant liquid；
32) the third suspension that step 31) obtains is spray-dried, obtains solid powder using spray dryer
Obtained graphene oxide powder is observed under scanning electron microscope in end, it can be observed that it is formed on its three-dimensional drape
There is a plurality of hole portions (being denoted as three-dimensional porous accordion), the graphene oxide powder of the three-dimensional porous accordion is denoted as PGO2.
Correspondingly, the step 4) in embodiment 1 is carried out as follows:
41) by powdered graphite and above-mentioned steps 32) obtained graphene oxide powder PGO2 be further soaked in it is scheduled
Second solvent is carried out decentralized processing (being such as but not limited to be dispersed using ultrasonic wave), forms it into the second suspension.
The inert gas of the solid powder obtained after the subsequent spray drying to the second suspension, and spray drying dries
It is roasting and cooling with embodiment step 5), the record of step 6), this will not be repeated here.
The lithium ion battery negative material that the present embodiment obtains other than having the effect of embodiment 1, the present embodiment
Lithium ion battery negative material is to the effect of the electric discharge raising of gram volume, the raising of circulating ratio performance of lithium ion battery into one
Step improves.
Experimental data comparative analysis:
The application is further described below with reference to example.It should be understood that these embodiments are merely to illustrate the application and do not have to
In limitation scope of the present application.In the examples below, if used material and reagent can be from business without specified otherwise
Approach purchase obtains.
Experimental example 1
The 500mL concentrated sulfuric acid is placed in ice-water bath after 4h, the graphite powder of 15g is added, is slowly added to 45g with vigorous stirring
Potassium permanganate, maintenance system temperature do not surpass 20 DEG C, are put into 30-35 DEG C of water-bath after mixing evenly and react 2-5h, added
700mL deionized water continues to stir 15min so that system temperature is no more than 85-98 DEG C；It is separately added into 1400mL deionized water
It with 150mL30% (mass fraction) H2O2, filters immediately, filter cake is sufficiently washed with 1mol/LHCl cannot measure into filtrate
SO24-, then neutrality is washed with deionized water into.After freeze-drying, gained sample is denoted as graphene oxide PGO1.
The aqueous dispersion for configuring 0.25g/L graphene oxide, carries out spray drying experiment, gained on spray dryer
Sample is denoted as PGO1, obtained PGO1: C in mass ratio 0.01: 1 mixing dispersion.It is immersed in the sodium hydroxide of 5mol/L
In solution, and continue to stir 12h, filtering cleans and repeatedly removes sodium ion, obtains hybrid solid, again by above-mentioned hybrid solid
It is secondary it is fully dispersed form suspension in aqueous solution, then using spray drying obtain mixed-powder solid.
Mixed-powder solid is placed in atmosphere of inert gases, 850 DEG C is risen to the speed of 2 DEG C/min, is kept for 850 DEG C
Then 3h is cooled to room temperature with the speed of 2 DEG C/min, obtain the mixing negative electrode material that experimental example 1 obtains.
Resulting mixing negative electrode material under the low speed (300 turns/min) after ball milling 2 hours, by itself and Kynoar
(PVDF) negative collector electrode film is carried out after being made into slurry by 92: 8 mass ratio, obtains experiment pole piece.
Select metal lithium sheet as experiment to electrode.
Electrolyte is made of the LiPF6/ ethylene carbonate mixed carbonic acid diethylester of 1mol/L, wherein (1: 1), diaphragm is selected
Polypropylene microporous film is made as diaphragm and is assembled into 2032 formula button cell of composite material/lithium metal, to the button cell
Half-cell test is carried out, its performance as lithium cell negative pole material is evaluated.
Experimental example 2
The parameter of sample preparation is changed to 0.06: 1 except PGO: C mass ratio 0.01: 1, remaining is consistent with experimental example 2.
Experimental example 3
The parameter of sample preparation is changed to 0.11: 1 except PGO: C mass ratio 0.01: 1, remaining is consistent with experimental example 2.
Experimental example 4
The parameter of sample preparation is changed to 0.16: 1 except PGO: C mass ratio 0.01: 1, remaining is consistent with experimental example 2.
Experimental example 5
The parameter of sample preparation is changed to 0.21: 1 except PGO: C mass ratio 0.01: 1, remaining is consistent with experimental example 2.
Experimental example 6
The parameter of sample preparation is changed to 0.26: 1 except PGO: C mass ratio 0.01: 1, remaining is consistent with experimental example 2.
Experimental example 7
The sodium hydroxide solution of unused 5mol/L impregnates in sample preparation procedure, remaining is consistent with experimental example 2.
Experimental example 8
Graphene oxide PGO1 is first immersed in the hydroxide of 5mol/L after obtaining graphene oxide PGO1 by sample preparation
In sodium solution, and continue to stir 12h, filtering, multiple chlorohydric acid pickling removes sodium ion, obtains solid powder (by the solid powder
It is denoted as PGO2), solid powder PGO2: C in mass ratio 0.01: 1 is mixed into dispersion and forms suspension in aqueous solution, is then used
Spray drying obtains mixed-powder solid.Mixed-powder solid is placed in atmosphere of inert gases, is risen to the speed of 2 DEG C/min
850 DEG C, it is sintered 3h, obtains the mixing negative electrode material that experimental example 1 obtains.
Remaining is consistent with experimental example 2.
Experimental example 9
This experimental example the difference is that only with embodiment 1: this experimental example is to baking, the bosher for mixing negative electrode material
Skill is different from embodiment 1, remaining is consistent with experimental example 1.
Mixed-powder solid is placed in atmosphere of inert gases by this experimental example, rises to 700 DEG C with the speed of 1 DEG C/min, so
700 DEG C of sintering 3h are maintained afterwards, and room temperature is then down to the speed of 1 DEG C/min, obtains the mixing negative electrode material that experimental example 9 obtains.
Experimental example 10
This experimental example the difference is that only with embodiment 1: this experimental example is to baking, the bosher for mixing negative electrode material
Skill is different from embodiment 1, remaining is consistent with experimental example 1.
Mixed-powder solid is placed in atmosphere of inert gases by this experimental example, rises to 900 DEG C with the speed of 4 DEG C/min, so
900 DEG C of sintering 1h are maintained afterwards, and room temperature is then down to the speed of 4 DEG C/min, obtains the mixing negative electrode material that experimental example 10 obtains.
Comparative example
Material used is common graphite powder, remaining is identical as experimental example 2.
The test of composite property
It is prepared into button cell using experimental example 1-10 and comparative example as positive electrode and negative electrode lithium metal, prepared battery exists
After glove box is stood for 24 hours, at room temperature, charging/discharging voltage range is 0.005~2.000V, and discharge to it gram volume, 3C
High rate performance and 200 weeks circulation conservation rates are tested, and experimental data deck watch shown in table one and shown in FIG. 1 is obtained
Cycle life schematic diagram.
Table 1: embodiment 1-10 and comparative example buckle electricity experimental data contrast table
Comparative example 1-8 is implemented it can be found that sodium hydroxide solution plays key player in three-dimensional porous structure
The multiplying power discharging gram volume and conservation rate of example 1 are better than embodiment 7, and the present invention has found its reason master in carrying out research of the present invention
If the presence of porous structure can promote the lithium ion in electrolyte in the more quick intercalation/deintercalation of electrode interior.
By embodiment 1-8 and comparative example it was found that, with graphene oxide and common commercially available graphite powder with certain mass ratio
Electric discharge gram volume and high rate performance of the mixing by a series of negative electrode materials for handling obtained three-dimensional porous graphene coated carbon
All better than comparative example, the reason is that the specific surface area of the composite material is up to 1076.5m2/g, high specific surface area can be
The immersion of electrolyte provides more active sites.
Discovery is compared between embodiment 1-6, the performance that excessive or very few mass ratio is unfavorable for material plays, very few
The absorption for being unfavorable for electrolyte may be reduced relatively in hole accordingly, being easy to misplace if excessive, between material layer is possible to block
Duct has obtained graphene oxide shown in embodiment 3,4: the optimum quality ratio (0.11-0.16) of graphite: 1.
Discovery is compared between embodiment 1,9,10, sintering process has played significantly the effect of lithium ion battery negative material
Effect, the sintering process of inert atmosphere: rising to 850 DEG C with the speed of 2 DEG C/min, 850 DEG C of 3h is kept, then with 2 DEG C/min
Speed be cooled to room temperature, obtained mixing negative electrode material, to the electric discharge gram volume of lithium ion battery, the circulating ratio of battery
There can be significant beneficial effect.
Embodiments described above does not constitute the restriction to the technical solution protection scope.It is any in above-mentioned implementation
Made modifications, equivalent substitutions and improvements etc., should be included in the protection model of the technical solution within the spirit and principle of mode
Within enclosing.
Claims (10)
1. a kind of preparation method of lithium ion battery negative material, characterized in that include:
Graphene oxide is prepared,
The first solvent is dispersed by the graphene oxide, forms the first suspension；
The graphene oxide powder is isolated from first suspension, the graphene oxide powder surface is in three-dimensional pleat
Corrugation；
The graphene oxide powder and graphite powder are mixed and are scattered in the second solvent, forms the second suspension；
It is spray-dried second suspension, obtains dry solid powder；
Under an inert atmosphere, the solid powder is toasted, it is cooling to get lithium ion battery negative material.
2. the preparation method of lithium ion battery negative material according to claim 1, characterized in that
After isolating the graphene oxide powder in first suspension,
Before dispersing the second solvent in the graphene oxide powder and the graphite powder mixing of three-dimensional drape shape for surface,
Further include:
Surface is soaked in alkaline solution in the graphene oxide powder of three-dimensional drape shape, forms third suspension；
The graphene oxide powder, the three-dimensional porous pleat of the graphene oxide powder are isolated from the third suspension
A plurality of hole portions are also formed in wrinkle；
The graphene oxide powder and graphite powder are mixed and are scattered in the second solvent, specifically,
The graphene oxide powder that a plurality of hole portions are also formed on three-dimensional porous fold is mixed with the powdered graphite
It is scattered in second solvent.
3. the preparation method of lithium ion battery negative material according to claim 1, characterized in that
After isolating the graphene oxide powder in first suspension,
Before dispersing the second solvent in the graphene oxide powder and the graphite powder mixing of three-dimensional drape shape for surface,
Further include:
Surface will be mixed in the graphene oxide powder of three-dimensional drape shape with the powdered graphite, mixing is soaked in institute
Alkaline solution is stated to scheduled duration, the alkaline solution is filtered out, cleans, obtain hybrid solid powder；
The graphene oxide powder and graphite powder are mixed and are scattered in the second solvent, specifically,
The hybrid solid powder is mixed and is scattered in second solvent.
4. the preparation method of lithium ion battery negative material described according to claim 1 or 2 or 3 or 3, characterized in that
The graphite powder of mixing and the quality proportioning of the graphene oxide powder are as follows: 1: (0.01~0.28).
5. the preparation method of lithium ion battery negative material according to claim 4, characterized in that
The graphite powder of mixing and the quality proportioning of the graphene oxide powder are as follows: 1: (0.11~0.16).
6. the preparation method of lithium ion battery negative material according to claim 5, characterized in that
The graphite powder of mixing and the quality proportioning of the graphene oxide powder are as follows: 1: 0.11.
7. the preparation method of lithium ion battery negative material according to claim 5, characterized in that
The graphite powder of mixing and the quality proportioning of the graphene oxide powder are as follows: 1: 0.16.
8. the preparation method of lithium ion battery negative material according to claim 1 or 2 or 3, characterized in that
Specifically using Hummers method liquid phase oxidation, the graphene oxide is synthesized with graphite powder synthesis graphene oxide.
9. the preparation method of lithium ion battery negative material according to claim 1 or 2 or 3, characterized in that
First solvent is deionized water or ethyl alcohol.
10. the preparation method of lithium ion battery negative material according to claim 1 or 2 or 3, characterized in that
The first solvent is dispersed by the graphene oxide, forms the first suspension, comprising:
First solvent is added in the graphene oxide, ultrasonic wave disperses first solvent and suspends to get described first
Liquid.
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|---|---|---|---|---|
| CN113955747A (en) * | 2021-10-20 | 2022-01-21 | 北京化工大学常州先进材料研究院 | Preparation method of graphene-coated natural graphite negative electrode material |
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