CN106784747B - A kind of graphene-based lithium ion battery negative material - Google Patents
A kind of graphene-based lithium ion battery negative material Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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Abstract
The invention belongs to technical field of lithium ion, more particularly to a kind of graphene-based lithium ion battery negative material, negative electrode material is three-dimensional porous graphene-non-carbon material combination electrode material, it includes three-dimensional porous graphene and the non-carbon material that is carried on three-dimensional porous graphene, negative electrode material has pore structure abundant, and specific surface area is 170-400 m2/ g, Kong Rongwei 0.18-1.2 cm3/ g, block density are 0.6-3.0 g/cm3, and the sum of volume of negative electrode material mesoporous is 1.9 times -4 times of the sum of volume of non-carbon material.Compared with the existing technology, which solves the problems, such as the volume expansion of non-carbon active component in the material, optimizes the density of composite material, guarantees the ion transporting and electronic conductivity of composite material.The material has many advantages, such as that structure novel, good conductivity, electrochemical lithium storage content be big, good cycle, while preparation method is simple, and low cost is suitable for industrialization.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of graphene-based lithiums with suitable reserved space
Ion battery cathode material.
Background technique
Lithium ion battery is due to having the advantages that energy density height, good cycle, since its commercialization extensively
Applied to portable electronic products, electric vehicle and electrical network field.In particular with highlighting for energy and environment problem, lithium-ion electric
Pond has obtained more and more attention in the development of New Energy Industry.
The cathode of lithium ion battery is the important component of battery, its structure and performance directly affects lithium ion battery
Capacity, cycle performance and high rate performance.In current lithium ion battery negative material, realized extensive commercialization is graphite
Material.Graphite material is at low cost, from a wealth of sources, is suitable for commercialization, but its specific discharge capacity is low, Theoretical Mass specific capacity is only
372mAh/g；The density of graphite cathode is low simultaneously, and theoretical volumetric capacity is only 800mAh/cm3, limit in this way lithium from
Development of the sub- battery in terms of high quality specific capacity and high-volume and capacity ratio.
Non-carbon material such as silicon, metal oxide (such as SnO2、Fe2O3Deng) be used as negative electrode of lithium ion battery that there is very high matter
Specific capacity and high density are measured, to have very high volume and capacity ratio.Wherein SnO2Specific capacity is up to 782mAh/g, but SnO2
As electrode material, volume change is up to 260% in charge and discharge process, this can cause the crushing of electrode, cause active material with
The open circuit of collector.Si base negative electrode material is with the specific discharge capacity for being more than 3000mAh/g, but its volume expansion reaches 300%-
400%, the performance of its capacity is seriously affected in charge and discharge process.Therefore, non-carbon material is because of serious volume expansion problem
Limit its large-scale application in negative electrode of lithium ion battery.
Carbon material is introduced into for solving the problems, such as that volume expansion of the non-carbon negative material in cell operations is extremely closed
Key.The carbon skeleton of load non-carbon active material is designed, suitable space is reserved and meets non-carbon material in process of intercalation
Volume expansion, while designing reserved space, the density of composite material improved, to prepare novel carbon-non-carbon composite junction
Structure has very important significance for the specific discharge capacity and volume and capacity ratio tool that improve lithium ion battery.
Graphene has big specific surface and good electric conductivity as typical two-dimension flexible carbon material.Graphene with
Non-carbon active material combines, and has a good application prospect in lithium ion battery material.Open graphene skeleton structure, though
It so can sufficiently meet SnO2The volume expansion in process of intercalation, but the density of negative electrode material is reduced, to limit its volume
The raising of performance.Three-dimensional may be implemented using the method for the capillary evaporation of water during the removing of three-dimensional grapheme water-setting glue
The densification of graphene macroform.Non-carbon active material is carried in fine and close three-dimensional grapheme macroscopic body, it can significantly
Increase the density of composite material, but excessively fine and close graphene skeleton structure cannot fully meet non-carbon active material embedding
Volume expansion during lithium also results in the drop of negative electrode material volume performance to affect the capability and performance of the composite material
It is low.
In view of this, it is necessory to provide a kind of graphene-based negative electrode of lithium ion battery material with suitable reserved space
Material is loaded the non-carbon active material of high density, high capacity by design graphene skeleton, introduces and optimize reserved space,
The volume expansion for meeting non-carbon active material guarantees quick ion transmission channel and good electrical contact, is improving quality
While specific capacity, highdensity lithium ion battery negative material is obtained, to realize the raising of volume performance.
Summary of the invention
It is an object of the present invention to: in view of the deficiencies of the prior art, and provide a kind of with suitable reserved space
The preparation method of graphene-based lithium ion battery negative material loads high density, high capacity by design graphene skeleton
Non-carbon active material, introduce and optimize reserved space, meet the volume expansion of non-carbon active material, guarantee that quick ion passes
Defeated access and good electrical contact obtain highdensity lithium ion battery negative material while improving specific discharge capacity,
To realize the raising of volume performance.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of graphene-based lithium ion battery negative material, the negative electrode material are three-dimensional porous graphene-non-carbon material
Combination electrode material comprising three-dimensional porous graphene and the non-carbon material being carried on the three-dimensional porous graphene, it is described
Negative electrode material has pore structure abundant, specific surface area 170-400m2/ g, Kong Rongwei 0.18-1.2cm3/ g, block density
For 0.6-3.0g/cm3, and the sum of volume of the negative electrode material mesoporous be 1.9 times of the sum of volume of the non-carbon material-
4 times.
Compared with the existing technology, which solves the problems, such as the volume expansion of non-carbon active component in the material, excellent
The density for having changed composite material guarantees the ion transporting and electronic conductivity of composite material.The material has structure novel, leads
The advantages that electrical good, electrochemical lithium storage content is big, good cycle, while preparation method is simple, low cost is suitable for industrialization.
When the three-dimensional porous graphene-non-carbon material combination electrode material is as lithium ion battery negative material, quality capacity can be with
Reach 500-2000mAh/g, volume and capacity ratio can achieve 500-3000mAh/cm3, and with excellent cycle performance and again
Rate performance.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, the non-carbon material is titanium dioxide
At least one of tin, silicon and iron oxide.
It is three-dimensional more in the negative electrode material as a kind of improvement of the graphene-based lithium ion battery negative material of the present invention
Hole graphene and the mass ratio of non-carbon material are 1:(1.6-4).Certain carbon component can alleviate the volume expansion of non-carbon material,
Increase the electric conductivity of material simultaneously；Because the capacity of carbon component is limited, carbon component is controlled in lower content, can be improved material
Whole specific discharge capacity and density of material, and then realize higher volume and capacity ratio.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, the preparation method of the negative electrode material
It at least includes the following steps:
Sulphur-containing substance and acid is added in the first step in graphite alkenes dispersion liquid, and acid is sufficiently reacted with sulphur-containing substance generates sulphur
Dispersion liquid in an aqueous medium, and the presoma of non-carbon material is added, it is sufficiently stirred to obtain mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in hydrothermal reaction kettle and carries out hydro-thermal reaction, obtains graphite by second step
Alkene-compound the hydrogel of non-carbon material-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, remove impurity, it is laggard
Row moisture removal obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, obtain the non-carbon materials of three-dimensional porous graphene-
Expect combination electrode material.With other oxide templates (SiO2Deng) compare, sulphur can be realized closely altogether with non-carbon active particle
Raw relationship.After desulfurization, suitable expansion space can be reserved for non-carbon active particle.
This method is pre-filled as space by introducing sulphur in three-dimensional porous graphene and non-carbon material composite construction
Template, after sulphur is removed, space occupied by sulphur is that suitable sky has been reserved in volume expansion of the non-carbon material after embedding lithium
Between, so as to avoid the dusting of the rupture of negative electrode material and electrode in charge and discharge process, improve the cyclicity of negative electrode material
Can, finally realize excellent quality and volume performance.
This method has the advantages that
First, this method mild condition is easy to operate, preparation process green non-pollution, is acted on using the capillary evaporation of water
The fine and close of three-dimensional graphene framework may be implemented to shrink, and using sulphur as the pre-filled template in space, it can removed
Afterwards, be introduced into sufficient space to meet volume expansion of the non-carbon material in charge and discharge process, prevent non-carbon material dusting and
Reunite, make electrode cycle performance be improved significantly.
Second, accuracy controlling of the graphene skeleton to non-carbon material reserved space in a wide range of may be implemented in this method,
Specifically, the amount for the sulphur-containing substance being added by control, can regulate and control the size of reserved space, it is different swollen to be suitable for having
The regulation of the reserved space of the non-carbon material of swollen degree.
Third can be with by accurately controlling content of the sulphur in three-dimensional porous graphene-non-carbon material combination electrode material
Suitable space is obtained, in the case where meeting the requirement of non-carbon material volume expansion, excessively high porosity is avoided, obtains higher
Block density reach high volume and capacity ratio thus in the case where realizing excellent specific discharge capacity, resulting materials for
The raising of lithium ion battery quality and volume performance has a very important significance.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, in the first step, the dispersion of graphite alkenes
Liquid, sulphur-containing substance, acid and non-carbon material the mass ratio of presoma be 1:(0.6-18): (0.25-1.5): (1-4.5), it is described
The concentration of graphite alkenes dispersion liquid is 1-3mg/mL.The quality proportioning of the precursor species has fully considered each in material prepared
The content of component can regulate and control each component content in suitable range.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, in the first step, the graphene
Class dispersion liquid is at least one of graphene oxide dispersion, modified graphene dispersion liquid and porous graphene dispersion liquid；Institute
The sulphur-containing substance stated is at least one of distillation sulphur simple substance, sodium thiosulfate and vulcanized sodium；The acid is hydrochloric acid, nitric acid, sulphur
At least one of acid, sulfurous acid, carbonic acid and acetic acid；The presoma of the non-carbon material is tin tetrachloride, stannous chloride, two
At least one of artificial gold, silicon powder, ferric trichloride.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, in second step, the temperature of hydro-thermal reaction
Degree is 100 DEG C -250 DEG C, and hydro-thermal reaction duration is 3h-48h.At 100 DEG C -250 DEG C, sulphur is with mobility and centainly
Viscosity can either realize with non-carbon active particle and adequately combine, while can be avoided its group by the hydro-thermal of 3h-48h
It is poly-.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, in third step, the side of moisture removal
Method is drying, and drying temperature is 60 DEG C -90 DEG C, baking duration 6h-72h.In drying course, steamed using the capillary of water
Hair realizes the contraction to material.60 DEG C -90 DEG C may be implemented block and preferably shrink, while avoid fast under the conditions of higher temperature
Block caused by speed is shunk crushes；The abundant drying to material may be implemented in the drying time of 6h-72h.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, in the 4th step, desulfurization process is heat
Handle desulfurization, the method for being heat-treated desulfurization are as follows: under inert gas shielding atmosphere, be warming up to the heating rate of 3-20 DEG C/min
300 DEG C -500 DEG C, then constant temperature 3h-24h, sulphur is removed, and is cooled to room temperature.The fusing point and boiling point of sulphur are lower, heat treatment
The thorough removing to sulphur may be implemented in method.
As a kind of improvement of the graphene-based lithium ion battery negative material of the present invention, in the 4th step, desulfurization process is molten
Agent method desulfurization.Product to be processed grinding is placed in carbon disulfide, 6h-48h is persistently stirred, fills the sulphur in product to be processed
Divide and is dissolved in carbon disulfide.Sulphur is soluble in carbon disulfide, and the thorough removing to sulphur equally may be implemented in carbon disulfide desulfurization.
Detailed description of the invention
With reference to the accompanying drawings and detailed description, the present invention and its advantageous effects are described in detail.
Fig. 1 is three-dimensional porous graphene-stannic oxide macroscopic body material SEM figure prepared by the embodiment of the present invention 1.
Fig. 2 is that three-dimensional porous graphene-stannic oxide macroscopic body material nitrogen adsorption prepared by the embodiment of the present invention 1 is de-
Attached thermoisopleth (77K).
Fig. 3 is that three-dimensional porous graphene/stannic oxide macroscopic body material charge and discharge prepared by the embodiment of the present invention 1 are bent
Line.
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto.
Embodiment 1
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 191m2/ g, Kong Rongwei 0.25cm3/ g, block density are
2.18g/cm3, and the sum of volume of negative electrode material mesoporous is 2.59 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:2.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 2mg/mL graphene oxide dispersion 78.5mL to be placed in 100mL beaker, and 0.75g is added
Na2S2O3·5H2O, is then added 1M hydrochloric acid 6.5mL, and stirring 30min reacts it sufficiently, 350mg SnCl is then added4·
5H2O, stirring evenly dissolves it all, obtains mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 150 DEG C, and the hydro-thermal duration is 6h, obtains graphene-compound hydrogel of stannic oxide-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 48h hours is carried out at 70 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, specifically, under protection of argon gas, with
The heating rate of 10 DEG C/min is warming up to 400 DEG C, and then constant temperature 6 hours, sulphur is removed, and is cooled to room temperature, and obtains three-dimensional porous
Graphene-stannic oxide combination electrode material.
Three-dimensional porous graphene-stannic oxide macroscopic body material SEM that embodiment 1 provides schemes as shown in Figure 1, by Fig. 1
It can be seen that three-dimensional grapheme provides dense porous carbon skeleton as a result, not only contributing to lithium for stannic oxide active particle
The transmission of ion and electronics, while volume expansion of the stannic oxide particle in process of intercalation can be buffered.
Three-dimensional porous graphene-stannic oxide macroscopic body material nitrogen adsorption desorption isotherm that embodiment 1 provides
(77K) is as shown in Fig. 2, as seen from Figure 2: three-dimensional porous graphene has suitable pore structure and enough Kong Rong conducts
The reserved space of stannic oxide.
Embodiment 1 provide three-dimensional porous graphene/stannic oxide macroscopic body material charging and discharging curve as shown in figure 3,
As seen from Figure 3: three-dimensional porous graphene-stannic oxide macroscopic body material first circle coulombic efficiency with higher.
Embodiment 2
Unlike the first embodiment:
Three-dimensional porous graphene-stannic oxide combination electrode material specific surface area is 256m2/ g, Kong Rongwei 0.19cm3/
G, block density 2.46g/cm3, and the sum of volume of negative electrode material mesoporous is 1.98 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:2.
In the preparation method of the negative electrode material, the dosage of graphene oxide dispersion is adjusted to 83.5mL, Na2S2O3·
5H2The dosage of O is adjusted to 0.10g, and hydrochloric acid dosage is adjusted to 1.5mL, remaining is same as Example 1, and which is not described herein again.
Embodiment 3
Unlike the first embodiment:
Three-dimensional porous graphene-stannic oxide combination electrode material specific surface area is 228m2/ g, Kong Rongwei 0.21cm3/
G, block density 2.32g/cm3, and the sum of volume of negative electrode material mesoporous is 2.25 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:2.
In the preparation method of the negative electrode material, the dosage of graphene oxide dispersion is adjusted to 82.5mL, Na2S2O3·
5H2The dosage of O is adjusted to 0.21g, and hydrochloric acid dosage is adjusted to 2.5mL.Remaining is same as Example 1, and which is not described herein again.
Embodiment 4
Unlike the first embodiment:
Three-dimensional porous graphene-stannic oxide combination electrode material specific surface area is 182m2/ g, Kong Rongwei 0.26cm3/
G, block density 1.82g/cm3, and the sum of volume of negative electrode material mesoporous is 2.72 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:2.
In the preparation method of the negative electrode material, the dosage of graphene oxide dispersion is adjusted to 72mL, Na2S2O3·5H2O
Dosage be adjusted to 1.6g, hydrochloric acid dosage is adjusted to 13mL.Remaining is same as Example 1, and which is not described herein again.
Embodiment 5
Unlike the first embodiment:
Three-dimensional porous graphene-stannic oxide combination electrode material specific surface area is 170m2/ g, Kong Rongwei 0.27cm3/
G, block density 1.10g/cm3, and the sum of volume of negative electrode material mesoporous is 2.85 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:2.
In the preparation method of the negative electrode material, the dosage of graphene oxide dispersion is adjusted to 55mL, Na2S2O3·5H2O
Dosage be adjusted to 3.4g, hydrochloric acid dosage is adjusted to 28mL.Remaining is same as Example 1, and which is not described herein again.
Comparative example 1
Three-dimensional porous graphene-stannic oxide combination electrode material specific surface area is 277m2/ g, Kong Rongwei 0.18cm3/
G, block density 2.65g/cm3, and the sum of volume of negative electrode material mesoporous is 1.8 times of the sum of volume of non-carbon material.
In the preparation method of the negative electrode material, Na2S2O3·5H2The dosage of O is adjusted to 0g, and hydrochloric acid dosage is adjusted to 0mL.
Remaining is same as Example 1, and which is not described herein again.
By three-dimensional porous graphene-stannic oxide combination electrode material prepared by embodiment 1-5 and comparative example 1 and conduction
Additive (Super-P), binder (PVDF) carry out 8:1:1 (mass ratio) mixing, and negative electrode tab is made by collector of copper foil.
With LiPF6For electrolyte, lithium piece is that anode composition half-cell carries out electrochemical property test, tests the matter of the electrode composite material
It measures specific capacity and volume and capacity ratio, acquired results is as shown in table 1.
Table 1: the test result of embodiment 1 to 5 and comparative example 1.
As can be seen from Table 1: with the increase of desulfurization content, material reserved space is bigger, while density is smaller.It is accurate to adjust
Sulfur content is controlled, dense porous three-dimensional graphene framework can be obtained, meet the cubical expansivity of stannic oxide 250%, obtained
While obtaining high quality specific capacity (993mAh/g), high volume and capacity ratio (2167mAh/cm is obtained3)。
Embodiment 6
The specific surface area of three-dimensional porous graphene-stannic oxide combination electrode material provided in this embodiment is 224m2/ g,
Kong Rongwei 0.20cm3/ g, block density 2.34g/cm3, and the sum of volume of negative electrode material mesoporous is the volume of non-carbon material
The sum of 2.12 times.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:2.3.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 1.5mg/mL modified graphene dispersion liquid 78.5mL to be placed in 100mL beaker, and 0.76g distillation is added
Sulphur (is dissolved in 1mL carbon disulfide), and stirring 40min reacts it sufficiently, and 500mg SnCl is then added4·5H2O, stirring evenly makes
It is all dissolved, and obtains mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 180 DEG C, and the hydro-thermal duration is 12h, obtains graphene-compound hydrogel of stannic oxide-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 28h hours is carried out at 80 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, specifically, under nitrogen protection, with
The heating rate of 15 DEG C/min is warming up to 350 DEG C, then constant temperature 12h, and sulphur is removed, and is cooled to room temperature, and obtains three-dimensional porous stone
Black alkene-stannic oxide combination electrode material.
Embodiment 7
The specific surface area of three-dimensional porous graphene-stannic oxide combination electrode material provided in this embodiment is 187m2/ g,
Kong Rongwei 0.17cm3/ g, block density 2.51g/cm3, and the sum of volume of negative electrode material mesoporous is the volume of non-carbon material
The sum of 1.92 times.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:4.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 2.5mg/mL porous graphene dispersion liquid 78.5mL to be placed in 100mL beaker, and 0.75g vulcanization is added
Sodium, is then added 0.5M sulfurous acid 6.5mL, and stirring 50min reacts it sufficiently, 700mg SnCl is then added4·5H2O is stirred
Mixing dissolves it all, obtains mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 200 DEG C, and the hydro-thermal duration is 4h, obtains graphene-compound hydrogel of stannic oxide-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
12h is carried out at 85 DEG C adequately to dry, and by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, specifically, under nitrogen protection, with
The heating rate of 15 DEG C/min is warming up to 450 DEG C, then constant temperature 20h, and sulphur is removed, and is cooled to room temperature, and obtains three-dimensional porous stone
Black alkene-stannic oxide combination electrode material.
Embodiment 8
The specific surface area of three-dimensional porous graphene-stannic oxide combination electrode material provided in this embodiment is 257m2/ g,
Kong Rongwei 0.27cm3/ g, block density 1.62g/cm3, and the sum of volume of negative electrode material mesoporous is the volume of non-carbon material
The sum of 2.82 times.
Wherein, non-carbon material is stannic oxide, and the mass ratio of three-dimensional porous graphene and stannic oxide is 1:0.6.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 2.2mg/mL porous graphene dispersion liquid 78.5mL to be placed in 100mL beaker, and 0.75g vulcanization is added
Then 0.5M sulfurous acid 6.5mL is added in sodium, stirring 50min reacts it sufficiently, and 200mg stannous chloride is then added, and stirring is equal
It is even to dissolve it all, obtain mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 190 DEG C, and the hydro-thermal duration is 8h, obtains graphene-compound hydrogel of stannic oxide-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 16h hours is carried out at 75 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carries out desulfurization process, specifically, product to be processed is ground
It is placed in carbon disulfide, lasting stirring for 24 hours, is completely dissolved in the sulphur in product to be processed in carbon disulfide, obtains three-dimensional
Porous graphene-stannic oxide combination electrode material.
Comparative example 2
The specific surface area for the three-dimensional porous graphene that this comparative example provides is 262m2/ g, Kong Rongwei 0.47cm3/ g, block are close
Degree is 0.89g/cm3。
In preparation method, by SnCl in embodiment 64·5H2O dosage is adjusted to 0mg, remaining is same as Example 6, this
In repeat no more.
To there is three-dimensional porous graphene-stannic oxide combination electrode, three-dimensional prepared by embodiment 6-8 and comparative example 2
Porous graphene carries out 8:1:1 (mass ratio) with conductive additive (Super-P), binder (PVDF) and mixes, and is with copper foil
Negative electrode tab is made in collector.With LiPF6For electrolyte, lithium piece is that anode composition half-cell carries out electrochemical property test, the electricity
The specific discharge capacity and volume and capacity ratio of pole composite material, acquired results are as shown in table 2.
Table 2: the test result of embodiment 6 to 8 and comparative example 2.
As can be seen from Table 2: in the case where the load capacity of sulphur is certain, the content of stannic oxide active material is higher, close
Degree is higher, but reserved volume required for it is also higher.Size by adjusting stannic oxide content and reserved volume can be with
Obtain high-volume and capacity ratio.
Embodiment 9
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 342m2/ g, Kong Rongwei 1.03cm3/ g, block density are
0.68g/cm3, and the sum of volume of negative electrode material mesoporous is 3.56 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is silicon, and the mass ratio of three-dimensional porous graphene and silicon is 1:2.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 2mg/mL graphene oxide dispersion 78.5mL to be placed in 100mL beaker, and 0.75g is added
Na2S2O3·5H2Then 1M hydrochloric acid 6.5mL is added in O, stirring 30min reacts it sufficiently, 350mg nano silica fume is then added,
Stirring evenly dissolves it all, obtains mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 150 DEG C, and the hydro-thermal duration is 6h, obtains graphene-compound hydrogel of silicon-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 48h hours is carried out at 70 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, specifically, under protection of argon gas, with
The heating rate of 10 DEG C/min is warming up to 400 DEG C, then constant temperature 6h, and sulphur is removed, and is cooled to room temperature, and obtains three-dimensional porous graphite
Alkene-silicon combination electrode material.
Embodiment 10
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 305m2/ g, Kong Rongwei 0.90cm3/ g, block density are
0.75g/cm3, and the sum of volume of negative electrode material mesoporous is 3.12 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is silicon, and the mass ratio of three-dimensional porous graphene and silicon is 1:2.
In the preparation method of the negative electrode material, as different from Example 9: the dosage of graphene oxide dispersion is adjusted to
83.5mL,Na2S2O3·5H2The dosage of O is adjusted to 0.1g, and hydrochloric acid dosage is adjusted to 1.5mL.Remaining is same as Example 9, this
In repeat no more.
Embodiment 11
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 312m2/ g, Kong Rongwei 0.95cm3/ g, block density are
0.72g/cm3, and the sum of volume of negative electrode material mesoporous is 3.28 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is silicon, and the mass ratio of three-dimensional porous graphene and silicon is 1:2.
In the preparation method of the negative electrode material, in the preparation method of the negative electrode material, as different from Example 9: oxidation
Graphene dispersing solution replaces with modified graphene dispersion liquid, and the dosage of modified graphene dispersion liquid is 82.5mL, Na2S2O3·
5H2O is replaced with sublimed sulfur (being dissolved in 1mL carbon disulfide), and the dosage of sublimed sulfur is 0.21g, remaining is same as Example 9, this
In repeat no more.
Embodiment 12
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 355m2/ g, Kong Rongwei 1.06cm3/ g, block density are
0.67g/cm3, and the sum of volume of negative electrode material mesoporous is 3.65 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is silicon, and the mass ratio of three-dimensional porous graphene and silicon is 1:2.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 1.5mg/mL porous graphene dispersion liquid 72mL to be placed in 100mL beaker, and 1.6g vulcanized sodium is added,
Then 0.5M nitric acid 13mL is added, stirring 30min reacts it sufficiently, 350mg nano silica fume is then added, stirring evenly makes it
All dissolutions, obtain mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 170 DEG C, and the hydro-thermal duration is 15h, obtains graphene-compound hydrogel of silicon-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 12h hours is carried out at 85 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, specifically, under protection of argon gas, with 7
DEG C/heating rate of min is warming up to 420 DEG C, then constant temperature 9h, sulphur is removed, and is cooled to room temperature, and three-dimensional porous graphite is obtained
Alkene-silicon combination electrode material.
Embodiment 13
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 372m2/ g, Kong Rongwei 0.83cm3/ g, block density are
0.79g/cm3, and the sum of volume of negative electrode material mesoporous is 2.85 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is silicon, and the mass ratio of three-dimensional porous graphene and silicon is 1:2.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 2.5mg/mL porous graphene dispersion liquid 55mL to be placed in 100mL beaker, and 3.4g is added
Na2S2O3·5H2Then 1M sulfuric acid 28mL is added in O, stirring 30min reacts it sufficiently, 350mg nano silica fume is then added,
Stirring evenly dissolves it all, obtains mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 210 DEG C, and the hydro-thermal duration is 5h, obtains graphene-compound hydrogel of silicon-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 40h hours is carried out at 65 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carries out desulfurization process, specifically, product to be processed is ground
It is placed in carbon disulfide, persistently stirs 36h, be completely dissolved in the sulphur in product to be processed in carbon disulfide, obtain three-dimensional
Porous graphene-stannic oxide combination electrode material.
Comparative example 3
This comparative example provides a kind of graphene-based lithium ion battery negative material, and negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, specific surface area 298m2/ g, Kong Rongwei 0.35cm3/ g, block density 0.96g/
cm3, and the sum of volume of negative electrode material mesoporous is 3.56 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is silicon, and the mass ratio of three-dimensional porous graphene and silicon is 1:2.
In preparation method, and by unlike embodiment 9, Na2S2O3·5H2The dosage of O is adjusted to 0g, hydrochloric acid dosage
It is adjusted to 0mL.Remaining is same as Example 9, and which is not described herein again.
By three-dimensional porous graphene-silicon combination electrode material prepared by embodiment 10-13 and comparative example 3 and conductive addition
Agent (Super-P), binder (PVDF) carry out 8:1:1 (mass ratio) mixing, and negative electrode tab is made by collector of copper foil.With
LiPF6For electrolyte, lithium piece is that anode composition half-cell carries out electrochemical property test, the quality specific volume of the electrode composite material
Amount and volume and capacity ratio, as shown in table 3.
Table 3: the test result of embodiment 9 to 13 and comparative example 3.
As can be seen from Table 3: with the increase of desulfurization content, material reserved space is bigger, while density is smaller.It is accurate to adjust
Sulfur content is controlled, dense porous three-dimensional graphene framework can be obtained, meet the cubical expansivity of silicon 300%, it is high-quality obtaining
While measuring specific capacity (870mAh/g), high volume and capacity ratio (618mAh/cm is obtained3)。
Embodiment 14
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 323m2/ g, Kong Rongwei 0.30cm3/ g, block density are
1.70g/cm3, and the sum of volume of negative electrode material mesoporous is 2.25 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and the mass ratio of three-dimensional porous graphene and di-iron trioxide is 1:2.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 2mg/mL graphene oxide dispersion 78.5mL to be placed in 100mL beaker, and 0.75g is added
Na2S2O3·5H2O, is then added 1M hydrochloric acid 6.5mL, and stirring 30min reacts it sufficiently, 270mg FeCl is then added3·
6H2O, stirring evenly dissolves it all, obtains mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 150 DEG C, and the hydro-thermal duration is 6h, obtains graphene-compound hydrogel of di-iron trioxide-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 48h hours is carried out at 70 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, specifically, under protection of argon gas, with
The heating rate of 10 DEG C/min is warming up to 400 DEG C, then constant temperature 6h, and sulphur is removed, and is cooled to room temperature, and obtains three-dimensional porous graphite
Alkene-di-iron trioxide combination electrode material.
Embodiment 15
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 292m2/ g, Kong Rongwei 0.27cm3/ g, block density are
1.81g/cm3, and the sum of volume of negative electrode material mesoporous is 2.02 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and the mass ratio of three-dimensional porous graphene and di-iron trioxide is 1:2.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 1.5mg/mL porous graphene dispersion liquid 83.5mL to be placed in 100mL beaker, and 0.1g sublimed sulfur is added
(being dissolved in 1mL carbon disulfide), stirring 30min react it sufficiently, 270mg FeCl are then added3·6H2O, stirring evenly makes it
All dissolutions, obtain mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 220 DEG C, and the hydro-thermal duration is 8h, obtains graphene-compound hydrogel of di-iron trioxide-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Adequately drying in 40h hours is carried out at 80 DEG C, by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, specifically, under protection of argon gas, with 8
DEG C/heating rate of min is warming up to 450 DEG C, then constant temperature 10h, sulphur is removed, and is cooled to room temperature, and three-dimensional porous graphite is obtained
Alkene-di-iron trioxide combination electrode material.
Embodiment 16
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 305m2/ g, Kong Rongwei 0.29cm3/ g, block density are
1.75g/cm3, and the sum of volume of negative electrode material mesoporous is 2.15 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and the mass ratio of three-dimensional porous graphene and di-iron trioxide is 1:2.
In the preparation method of the negative electrode material as different from Example 14: by graphene oxide dispersion in embodiment 14
Dosage be adjusted to 82.5mL, Na2S2O3·5H2The dosage of O is adjusted to 0.21g, and hydrochloric acid dosage is adjusted to 2.5mL.Remaining and reality
Apply that example 1 is identical, and which is not described herein again.
Embodiment 17
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 328m2/ g, Kong Rongwei 0.31cm3/ g, block density are
1.68g/cm3, and the sum of volume of negative electrode material mesoporous is 2.36 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and the mass ratio of three-dimensional porous graphene and di-iron trioxide is 1:2.
In the preparation method of the negative electrode material as different from Example 14: by graphene oxide dispersion in embodiment 10
Dosage be adjusted to 72mL, Na2S2O3·5H2The dosage of O is adjusted to 1.6g, and hydrochloric acid dosage is adjusted to 13mL.Remaining and embodiment
1 is identical, and which is not described herein again.
Embodiment 18
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material comprising three-dimensional porous graphene and the non-carbon materials being carried on three-dimensional porous graphene
Material, negative electrode material have pore structure abundant, specific surface area 345m2/ g, Kong Rongwei 0.33cm3/ g, block density are
1.60g/cm3, and the sum of volume of negative electrode material mesoporous is 2.51 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and the mass ratio of three-dimensional porous graphene and di-iron trioxide is 1:2.
The preparation method of the negative electrode material at least includes the following steps:
The first step takes 1.5mg/mL modified graphene dispersion liquid 55mL to be placed in 100mL beaker, and 3.4g vulcanized sodium is added,
Then 0.5M sulfurous acid 28mL is added, stirring 30min reacts it sufficiently, 270mg FeCl is then added3·6H2O, stirring are equal
It is even to dissolve it all, obtain mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in the hydrothermal reaction kettle of 100mL and carries out hydro-thermal reaction, water by second step
Thermal response temperature is 140 DEG C, and the hydro-thermal duration is 15h, obtains graphene-compound hydrogel of di-iron trioxide-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, removes impurity, Zhi Hou
Carrying out hour for 24 hours at 85 DEG C adequately dries, and by moisture removal, obtains product to be processed；
4th step, the product to be processed that third step is obtained carries out desulfurization process, specifically, product to be processed is ground
It is placed in carbon disulfide, persistently stirs 40h, be completely dissolved in the sulphur in product to be processed in carbon disulfide, obtain three-dimensional
Porous graphene-stannic oxide combination electrode material.
Comparative example 4
This comparative example provides a kind of graphene-based lithium ion battery negative material, and negative electrode material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, specific surface area 275m2/ g, Kong Rongwei 0.24cm3/ g, block density 1.92g/
cm3, and the sum of volume of negative electrode material mesoporous is 1.85 times of the sum of volume of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and the mass ratio of three-dimensional porous graphene and di-iron trioxide is 1:2.
Preparation method is as different from Example 14: by Na in embodiment 142S2O3·5H2The dosage of O is adjusted to 0g,
Hydrochloric acid dosage is adjusted to 0mL.Remaining is identical as embodiment 14, and which is not described herein again.
By three-dimensional porous graphene-stannic oxide combination electrode material prepared by embodiment 11-18 and comparative example 4 with lead
Electric additive (Super-P), binder (PVDF) carry out 8:1:1 (mass ratio) mixing, and cathode is made by collector of copper foil
Piece.With LiPF6For electrolyte, lithium piece is that anode composition half-cell carries out electrochemical property test, the matter of the electrode composite material
It measures specific capacity and volume and capacity ratio, acquired results is as shown in table 4.
Table 4: the test result of embodiment 14 to 18 and comparative example 4.
As can be seen from Table 4: with the increase of desulfurization content, material reserved space is bigger, while density is smaller.It is accurate to adjust
Sulfur content is controlled, dense porous three-dimensional graphene framework can be obtained, meet the cubical expansivity of di-iron trioxide 200%,
While obtaining high quality specific capacity (589mAh/g), high volume and capacity ratio (677mAh/cm is obtained3)。
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (8)
1. a kind of preparation method of graphene-based lithium ion battery negative material, it is characterised in that: the negative electrode material is three-dimensional
Porous graphene-non-carbon material combination electrode material comprising three-dimensional porous graphene and be carried on the three-dimensional porous graphite
Non-carbon material on alkene, the negative electrode material have pore structure abundant, and specific surface area is 170-400 m2/ g, Kong Rongwei
0.18-1.2 cm3/ g, block density are 0.6-3.0 g/cm3, and the sum of volume of the negative electrode material mesoporous is described non-
1.9 times -4 times of the sum of the volume of carbon material；The non-carbon material is at least one of stannic oxide, silicon and iron oxide；
The preparation method of the negative electrode material at least includes the following steps:
Sulphur-containing substance and acid are added in graphite alkenes dispersion liquid, and the presoma of non-carbon material is added for the first step, sufficiently stir
It mixes to obtain mixed dispersion liquid；
The mixed dispersion liquid that the first step obtains is added in hydrothermal reaction kettle and carries out hydro-thermal reaction, it is non-to obtain graphene-by second step
The compound hydrogel of carbon material-sulphur；
Third step is adequately impregnated the hydrogel that second step obtains in deionized water, is removed impurity, is carried out water later
Divide removing, obtains product to be processed；
4th step, the product to be processed that third step is obtained carry out desulfurization process, it is multiple to obtain three-dimensional porous graphene-non-carbon material
Composite electrode material.
2. the preparation method of graphene-based lithium ion battery negative material according to claim 1, it is characterised in that: described
In negative electrode material, the mass ratio of three-dimensional porous graphene and non-carbon material is 1:(1.6-4).
3. the preparation method of graphene-based lithium ion battery negative material according to claim 1, which is characterized in that first
In step, graphite alkenes dispersion liquid, sulphur-containing substance, acid and non-carbon material the mass ratio of presoma be 1:(0.6-18): (0.25-
1.5): (1-4.5), the concentration of the graphite alkenes dispersion liquid are 1-3 mg/mL.
4. the preparation method of graphene-based lithium ion battery negative material according to claim 1, it is characterised in that: first
In step, the graphite alkenes dispersion liquid is graphene oxide dispersion, modified graphene dispersion liquid and porous graphene dispersion
At least one of liquid；The sulphur-containing substance is at least one of distillation sulphur simple substance, sodium thiosulfate and vulcanized sodium；It is described
Acid is at least one of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, carbonic acid and acetic acid；The presoma of the non-carbon material is tetrachloro
Change at least one of tin, stannous chloride, stannic disulfide, silicon powder, ferric trichloride.
5. the preparation method of graphene-based lithium ion battery negative material according to claim 1, it is characterised in that: second
In step, the temperature of hydro-thermal reaction is 100oC-250 oC, hydro-thermal reaction duration are 3 h-48 h.
6. the preparation method of graphene-based lithium ion battery negative material according to claim 1, it is characterised in that: third
In step, the method for moisture removal is drying, and drying temperature is 60oC-90 oC, baking duration are 6 h-72 h.
7. the preparation method of graphene-based lithium ion battery negative material according to claim 1, it is characterised in that: the 4th
In step, desulfurization process is heat treatment desulfurization, the method for being heat-treated desulfurization are as follows: under inert gas shielding atmosphere, with 3-20oC/
The heating rate of min is warming up to 300oC-500 oC, then 3 h-24 h of constant temperature, sulphur is removed, is cooled to room temperature.
8. the preparation method of graphene-based lithium ion battery negative material according to claim 1, it is characterised in that: the 4th
In step, desulfurization process is solvent method desulfurization: product to be processed grinding is placed in carbon disulfide, 6 h-48 h are persistently stirred,
It is completely dissolved in the sulphur in product to be processed in carbon disulfide.
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