CN114426301A - Tin oxide/sulfur-doped graphene composite material, preparation method thereof and battery - Google Patents

Tin oxide/sulfur-doped graphene composite material, preparation method thereof and battery Download PDF

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CN114426301A
CN114426301A CN202011182957.4A CN202011182957A CN114426301A CN 114426301 A CN114426301 A CN 114426301A CN 202011182957 A CN202011182957 A CN 202011182957A CN 114426301 A CN114426301 A CN 114426301A
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sulfur
intermediate product
composite material
tin oxide
tin
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李光胤
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Beijing Xiaomi Mobile Software Co Ltd
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Beijing Xiaomi Mobile Software Co Ltd
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
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    • C01—INORGANIC CHEMISTRY
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The disclosure provides a tin oxide/sulfur doped graphene composite material, a preparation method thereof and a battery. The preparation method of the tin oxide/sulfur doped graphene composite material comprises the following steps: carrying out hydrothermal reaction on a mixed solution of the graphene oxide dispersion liquid, the sulfur source, the tin source and the hydrochloric acid aqueous solution to obtain an intermediate product; washing and drying the intermediate product; and sintering the intermediate product after washing and drying to obtain the tin oxide/sulfur doped graphene composite material. The composite material has good conductivity, higher capacity, low volume expansion rate and stable structure, and is beneficial to improving the charge and discharge cycle stability of the battery.

Description

Tin oxide/sulfur-doped graphene composite material, preparation method thereof and battery
Technical Field
The disclosure relates to the technical field of batteries, in particular to a tin oxide/sulfur doped graphene composite material, a preparation method thereof and a battery.
Background
Graphite can be used as a negative electrode material of a lithium ion battery, but the capacity of the graphite is low, which is not beneficial to improving the energy density of the lithium ion battery. The capacity of the tin dioxide is high, the energy density of the lithium ion battery can be greatly improved, but the conductivity of the tin dioxide is poor, the volume expansion rate of the tin dioxide is high in the charging and discharging process of the lithium ion battery, the structure is unstable, and the cycling stability of the charging and discharging of the lithium ion battery is not facilitated.
Disclosure of Invention
The invention provides a tin oxide/sulfur doped graphene composite material, a preparation method thereof and a battery.
One aspect of the present disclosure provides a method for preparing a tin oxide/sulfur-doped graphene composite material, the method including:
carrying out hydrothermal reaction on a mixed solution of the graphene oxide dispersion liquid, the sulfur source, the tin source and the hydrochloric acid aqueous solution to obtain an intermediate product;
washing and drying the intermediate product;
and sintering the intermediate product after the washing treatment and the drying treatment to obtain the tin oxide/sulfur doped graphene composite material.
Optionally, before the hydrothermal reaction of the mixed solution of the graphene oxide dispersion liquid, the sulfur source, the tin source, and the aqueous hydrochloric acid solution, the method further includes:
and (3) uniformly mixing and stirring 1-100 ml of the graphene oxide dispersion liquid, 0.05-0.5 mmol of sulfur source, 0.01-0.1 mol of tin source and 1-10 ml of the hydrochloric acid aqueous solution to obtain the mixed solution, wherein the concentration of the graphene oxide dispersion liquid is 0.1-10 mg/ml.
Optionally, the sulfur source comprises C14H14S2、C12H12S2And C10H8S2At least one of (a).
Optionally, the tin source comprises SnCl2·2H2O。
Optionally, the hydrochloric acid aqueous solution comprises water and hydrochloric acid in a volume ratio of 5-10: 1, and the mass fraction of the hydrochloric acid is 35% -40%.
Optionally, the temperature of the hydrothermal reaction is 140-180 ℃, and the time of the hydrothermal reaction is 10-20 h.
Optionally, the washing treatment of the intermediate product comprises:
and (3) carrying out at least one washing treatment on the intermediate product by using deionized water and/or ethanol.
Optionally, the drying the intermediate product includes:
and carrying out freeze drying treatment on the intermediate product at the temperature of between 50 ℃ below zero and 40 ℃ below zero.
Optionally, the sintering treatment of the intermediate product after the washing treatment and the drying treatment includes:
and sintering the intermediate product subjected to the washing treatment and the drying treatment for 1-10 h in an inert gas atmosphere at the temperature of 200-500 ℃ to obtain the tin oxide/sulfur doped graphene composite material.
Another aspect of the present disclosure provides a tin oxide/sulfur-doped graphene composite material prepared by the method of any one of the above-mentioned methods.
Another aspect of the present disclosure provides a battery, the battery includes naked electric core, naked electric core includes the negative pole piece, the negative pole piece includes the above-mentioned tin oxide/sulphur doping graphite alkene combined material and negative current collector, tin oxide/sulphur doping graphite alkene combined material coat on the negative current collector.
The technical scheme provided by the disclosure at least has the following beneficial effects:
according to the tin oxide/sulfur doped graphene composite material, the preparation method and the battery provided by the embodiment of the disclosure, a hydrothermal reaction is performed on a mixed solution of a graphene oxide dispersion liquid, a sulfur source, a tin source and a hydrochloric acid aqueous solution to obtain an intermediate product, and then the intermediate product is subjected to washing treatment and drying treatment to remove impurities. And finally, sintering the intermediate product to form tin oxide in situ in the graphene and dope sulfur in the graphene to obtain the tin oxide/sulfur doped graphene composite material. The graphene is formed in the graphene in situ based on tin oxide, the graphene provides an expansion space for the tin oxide, the tin oxide occupies the inner space of the graphene when expanding, the volume expansion rate is reduced, the interfacial impedance is reduced, the structural stability of the composite material is good, the uniformity is good, and the cycling stability and the rate capability of a battery prepared from the composite material are improved. The tin dioxide endows the composite material with higher capacity, and is beneficial to improving the energy density of the battery. Based on the fact that sulfur is doped in graphene, defects are introduced into the graphene, and therefore the conductivity of the composite material is improved.
Drawings
Fig. 1 is a flow chart illustrating a method of preparing a tin oxide/sulfur doped graphene composite according to an exemplary embodiment of the present disclosure.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present disclosure, as detailed in the appended claims.
The terminology used in the present disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. Unless otherwise defined, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The use of "first," "second," and similar terms in the description and claims does not indicate any order, quantity, or importance, but rather is used to distinguish one element from another. Also, the use of the terms "a" or "an" and the like do not denote a limitation of quantity, but rather denote the presence of at least one. Unless otherwise indicated, the word "comprise" or "comprises", and the like, means that the element or item listed before "comprises" or "comprising" covers the element or item listed after "comprises" or "comprising" and its equivalents, and does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect.
As used in this disclosure and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
In the related art, a conductive agent, graphene, and tin dioxide are mixed by a physical mixing method to obtain a composite material. However, the interface resistance between the conductive agent and the tin dioxide is high, and the uniformity of the composite material is poor, so that the conductive performance of the material is poor, the volume expansion rate is high, the structure is unstable, and the cycle stability and the rate capability of battery charging and discharging are not facilitated.
In order to solve the above problems, embodiments of the present disclosure provide a tin oxide/sulfur-doped graphene composite material, a method for preparing the same, and a battery, which are described in detail below with reference to the accompanying drawings:
fig. 1 is a flow chart illustrating a method of preparing a tin oxide/sulfur doped graphene composite according to an exemplary embodiment of the present disclosure. Referring to fig. 1, a preparation method of a tin oxide/sulfur-doped graphene composite material provided by an embodiment of the present disclosure includes:
and 11, carrying out hydrothermal reaction on the mixed solution of the graphene oxide dispersion liquid, the sulfur source, the tin source and the hydrochloric acid aqueous solution to obtain an intermediate product.
Specifically, a mixed solution of the graphene oxide dispersion, the sulfur source, the tin source, and the hydrochloric acid aqueous solution may be placed in a hydrothermal reaction kettle to perform a hydrothermal reaction, thereby obtaining an intermediate product. The sulfur element and the tin element are infiltrated into the graphene layers and between the graphene layers through a hydrothermal reaction.
In some embodiments, the temperature of the hydrothermal reaction is 140 ℃ to 180 ℃, for example, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, and the time of the hydrothermal reaction is 10 to 20 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours, and the like. The temperature and the time of the hydrothermal reaction are set in such a way, so that the mixed solution can be ensured to fully carry out the hydrothermal reaction, the sulfur source, the tin source and the graphene oxide are uniformly reacted, and an intermediate product with uniform components is formed.
In some embodiments, prior to step 11, the method for preparing a tin oxide/sulfur-doped graphene composite material according to some embodiments of the present disclosure further includes: mixing and stirring uniformly 1-100 ml of graphene oxide dispersion liquid, 0.05-0.5 mmol of sulfur source, 0.01-0.1 mol of tin source and 1-10 ml of hydrochloric acid aqueous solution to obtain a mixed solution, wherein the concentration of the graphene oxide dispersion liquid is 0.1-10 mg/ml. The proportion of the graphene oxide, the sulfur source, the tin source and the hydrochloric acid aqueous solution is set, so that the proportion of each component is proper, and raw materials are saved. Illustratively, after the graphene oxide dispersion, the sulfur source, the tin source and the hydrochloric acid aqueous solution are mixed, the mixture may be stirred for 25-35 min, such as 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35min, so as to make the components of the mixed solution uniform.
Illustratively, the concentration of the graphene oxide dispersion may be 0.1mg/ml, 1mg/ml, 2mg/ml, 3mg/ml, 4mg/ml, 5mg/ml, 6mg/ml, 7mg/ml, 8mg/ml, 9mg/ml, or 10mg/ml, etc., and the volume of the graphene oxide dispersion may be 1ml, 10ml, 20ml, 30ml, 40ml, 50ml, 60ml, 70ml, 80ml, 90ml, or 100ml, etc.
Illustratively, the molar amount of the sulfur source may be 0.05mmol, 0.1mmol, 0.2mmol, 0.3mmol, 0.4mmol, 0.5mmol, or the like. The molar amount of the tin source may be 0.01mmol, 0.02mmol, 0.03mmol, 0.04mmol, 0.05mmol, 0.06mmol, 0.07mmol, 0.08mmol, 0.09mmol, 0.1mmol, or the like.
In some embodiments, the sulfur source comprises C14H14S2、C12H12S2And C10H8S2At least one of (a). C14H14S2Dibenzyl disulfide and other isomers may be included. C12H12S2May include 2, 7-bis- (methylthio) naphthalene, 2, 6-bis- (methylthio) naphthalene, [8- (thioalkylmethyl) naphthalen-1-yl]Methyl mercaptan or other isomers. C10H8S21, 5-dimercaptonaphthalene or other isomers may be included.
In some embodiments, the tin source comprises SnCl2·2H2And O. The tin source may also include other soluble tin compounds such as tin oxide.
In some embodiments, the hydrochloric acid aqueous solution includes water and hydrochloric acid at a volume ratio of 5-10: 1, for example, the volume ratio of water to hydrochloric acid may be 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, and the like, and the mass fraction of hydrochloric acid is 35% to 40%, for example, may be 35%, 36%, 37%, 38%, 39%, or 40%, and the like. By setting the content of the hydrochloric acid, the speed of the hydrothermal reaction can be adjusted by the hydrochloric acid, so that the graphene oxide, the sulfur source and the tin source can generate an intermediate product with uniform components.
And step 12, washing and drying the intermediate product.
In some embodiments, the intermediate product is subjected to a washing treatment comprising: and (3) carrying out at least one washing treatment on the intermediate product by using deionized water and/or ethanol to remove impurities in the intermediate product.
In some embodiments, the intermediate product is subjected to a drying process comprising: the intermediate product is subjected to freeze drying treatment at the temperature of between 50 ℃ below zero and 40 ℃ below zero. Illustratively, the temperature of the freeze-drying process may be-50 ℃, -47 ℃, -45 ℃, -42 ℃, or-40 ℃, etc. Illustratively, the drying process may further include a negative pressure process, and the evaporation of the solvent in the intermediate product is accelerated by the combination of the negative pressure process and the freeze-drying process. Compared with high-temperature drying treatment, the freeze drying treatment has small influence on the shape and structure of the intermediate product, and ensures that the tin dioxide can be generated in situ in the graphene at the later stage.
And step 13, sintering the intermediate product after washing and drying to obtain the tin oxide/sulfur doped graphene composite material.
In some embodiments, step 13 comprises:
and sintering the intermediate product subjected to washing treatment and drying treatment for 1-10 h in an inert gas atmosphere at the temperature of 200-500 ℃ to obtain the tin oxide/sulfur doped graphene composite material. The intermediate product may be sintered in a tube furnace. Illustratively, the inert gas comprises nitrogen. The sintering temperature can be 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃ and the like, and the sintering time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h and the like. Tin oxide is formed in situ in the gaps or between layers of graphene through sintering treatment, and sulfur is doped in the crystal lattice of graphene.
According to the preparation method of the tin oxide/sulfur doped graphene composite material provided by the embodiment of the disclosure, a mixed solution of a graphene oxide dispersion liquid, a sulfur source, a tin source and a hydrochloric acid aqueous solution is subjected to a hydrothermal reaction to obtain an intermediate product, and then the intermediate product is subjected to washing treatment and drying treatment to remove impurities. And finally, sintering the intermediate product to form tin oxide in situ in the graphene and dope sulfur in the graphene to obtain the tin oxide/sulfur doped graphene composite material. The graphene is formed in the graphene in situ based on tin oxide, the graphene provides an expansion space for the tin oxide, the tin oxide occupies the inner space of the graphene when expanding, the volume expansion rate is reduced, the interfacial impedance is reduced, the structural stability of the composite material is good, the uniformity is good, and the cycling stability and the rate capability of a battery prepared from the composite material are improved. The tin dioxide endows the composite material with higher capacity, and is beneficial to improving the energy density of the battery. Based on the fact that sulfur is doped in graphene, defects are introduced into the graphene, and therefore the conductivity of the composite material is improved.
Some embodiments of the present disclosure also provide a tin oxide/sulfur-doped graphene composite material, which is prepared by any one of the above-mentioned methods. In the tin oxide/sulfur-doped graphene composite material, tin oxide is formed in situ in graphene, and sulfur is doped in the graphene.
The tin oxide/sulfur-doped graphene composite material provided by the embodiment of the disclosure is formed in graphene in situ based on tin oxide, and the graphene provides an expansion space for the tin oxide, so that the tin oxide occupies the inner space of the graphene when expanding, the volume expansion rate is reduced, the interface impedance is reduced, the structural stability of the composite material is good, the uniformity is good, and the cycling stability and the rate capability of a battery prepared by adopting the composite material are improved. The tin dioxide endows the composite material with higher capacity, and is beneficial to improving the energy density of the battery. Based on the fact that sulfur is doped in graphene, defects are introduced into the graphene, and therefore the conductivity of the composite material is improved.
Some embodiments of this disclosure also provide a battery, the battery includes naked electric core, and naked electric core includes the negative pole piece, and the negative pole piece includes above-mentioned tin oxide/sulphur doping graphite alkene combined material and negative current collector, and tin oxide/sulphur doping graphite alkene combined material coats on the negative current collector. Specifically, the tin oxide/sulfur doped graphene composite material may be mixed with graphite and coated on a negative electrode current collector.
Exemplarily, the bare cell further comprises a positive plate, the positive plate comprises a positive material and a positive current collector, and the positive material is coated on the positive current collector. Exemplarily, the bare cell further comprises a positive tab and a negative tab, the positive tab is connected with the positive plate, and the negative tab is connected with the negative plate.
Illustratively, the battery comprises a lithium ion battery.
The battery provided by the embodiment of the disclosure, the negative plate based on the bare cell comprises the above mentioned tin oxide/sulfur doped graphene composite material, because the tin oxide is formed in the graphene in situ, the graphene provides an expansion space for the tin oxide, so that the tin oxide occupies the inner space of the graphene when expanding, the volume expansion rate is reduced, the interfacial impedance is reduced, the structural stability of the composite material is good, the uniformity is good, and the cycling stability and the rate capability of the battery are improved. The tin dioxide endows the composite material with higher capacity, and is beneficial to improving the energy density of the battery. Based on sulfur doping in graphene, defects are introduced to the graphene, so that the conductivity of the battery is improved.
In order to more clearly understand the effect of the tin oxide/sulfur doped graphene composite material provided by the embodiments of the present disclosure, the following description is made in conjunction with three embodiments:
example 1
This example provides a tin oxide/sulfur-doped graphene composite material, in which 0.15mmol C is added to 50ml graphene oxide dispersion liquid with a concentration of 1mg/ml14H14S2、0.04molSnCl2·2H2O and 5.5ml of hydrochloric acid aqueous solution (the volume ratio of water to hydrochloric acid is 5:1) are stirred for 30min to obtain a mixed solution. And then adding the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 16h at the temperature of 160 ℃ to obtain an intermediate product.
The intermediate product was washed repeatedly with deionized water and ethanol, and then freeze-dried at-45 ℃. And finally, sintering the intermediate product in a nitrogen atmosphere tubular furnace at 300 ℃ for 2h to obtain the tin oxide/sulfur doped graphene composite material provided in the embodiment 1.
Example 2
This example provides a tin oxide/sulfur-doped graphene composite material, in which 0.1mmol c is added to 30ml of graphene oxide dispersion liquid with a concentration of 0.5mg/ml12H12S2、0.02molSnCl2·2H2O and 2ml of hydrochloric acid aqueous solution (the volume ratio of water to hydrochloric acid is 7:1) are stirred for 30min to obtain a mixed solution. And then adding the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12h at the temperature of 140 ℃ to obtain an intermediate product.
The intermediate product was washed repeatedly with deionized water and ethanol, and then freeze-dried at-40 ℃. And finally, sintering the intermediate product in a nitrogen atmosphere tube furnace at 200 ℃ for 5h to obtain the tin oxide/sulfur doped graphene composite material provided by the embodiment 2.
Example 3
This example provides a tin oxide/sulfur-doped graphene composite material, in which 0.4mmol c is added to 70ml of graphene oxide dispersion liquid with a concentration of 4mg/ml10H8S2、0.08molSnCl2·2H2O and 8ml of hydrochloric acid aqueous solution (the volume ratio of water to hydrochloric acid is 6:1) are stirred for 30min to obtain a mixed solution. And then adding the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 16h at the temperature of 180 ℃ to obtain an intermediate product.
The intermediate product was washed repeatedly with deionized water and ethanol, and then freeze-dried at-50 ℃. And finally, sintering the intermediate product in a nitrogen atmosphere tubular furnace at 450 ℃ for 8h to obtain the tin oxide/sulfur doped graphene composite material provided by the embodiment 3.
Application example 1
Obtaining composite materials and tin dioxide with the same quality provided by the embodiments 1, 2 and 3, respectively, mixing the composite materials and the tin dioxide with the same quality with the graphene with the same quality to obtain negative electrode active materials, respectively manufacturing negative electrode sheets by using the negative electrode active materials by the same manufacturing process, and further manufacturing lithium ion batteries which are respectively numbered as a No. 1 lithium ion battery, a No. 2 lithium ion battery, a No. 3 lithium ion battery and a No. 4 lithium ion battery. And (2) respectively carrying out 800 charge-discharge cycles on the No. 1 lithium ion battery, the No. 2 lithium ion battery, the No. 3 lithium ion battery and the No. 4 lithium ion battery by adopting the same charge-discharge process, and detecting the volume expansion rate of each lithium ion battery relative to the lithium ion battery when the lithium ion battery is not charged or discharged. The full-charge time of the No. 1 lithium ion battery, the No. 2 lithium ion battery, the No. 3 lithium ion battery and the No. 4 lithium ion battery is respectively detected, the charging speed increasing rate of the No. 1 lithium ion battery, the No. 2 lithium ion battery and the No. 3 lithium ion battery respectively corresponding to the No. 4 lithium ion battery is calculated according to the full-charge time, and the specific parameters are detailed in the following table 1.
TABLE 1
Lithium ion battery numbering Volume ofSwelling rate/%) Charging rate increase/%)
Number 1 0.8％ 25％
Number 2 0.5％ 22％
No. 3 0.1％ 30％
Number 4 5％ ——
As can be seen from table 1, the volume expansion rate of the lithium ion battery nos. 1, 2 and 3 after 800 charge and discharge cycles is much smaller than that of the lithium ion battery No. 4 after 800 charge and discharge cycles. The lifting speed of the No. 1 lithium ion battery, the No. 2 lithium ion battery and the No. 3 lithium ion battery is respectively 25%, 22% and 30% when the batteries are fully charged, and the lifting speed is higher. Based on this, the lithium ion battery manufactured by using the tin oxide/sulfur doped graphene composite material provided by the embodiment of the disclosure has the advantages of high charging speed, good charging and discharging cycle stability and small volume expansion rate.
For the method embodiments, since they substantially correspond to the apparatus embodiments, reference may be made to the apparatus embodiments for relevant portions of the description. The method embodiment and the device embodiment are complementary.
The above embodiments of the present disclosure may be complementary to each other without conflict.
The above description is only exemplary of the present disclosure and should not be taken as limiting the disclosure, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims (11)

1. A preparation method of a tin oxide/sulfur doped graphene composite material is characterized by comprising the following steps:
carrying out hydrothermal reaction on a mixed solution of the graphene oxide dispersion liquid, the sulfur source, the tin source and the hydrochloric acid aqueous solution to obtain an intermediate product;
washing and drying the intermediate product;
and sintering the intermediate product after the washing treatment and the drying treatment to obtain the tin oxide/sulfur doped graphene composite material.
2. The method according to claim 1, wherein before the hydrothermal reaction of the mixed solution of the graphene oxide dispersion liquid, the sulfur source, the tin source, and the hydrochloric acid aqueous solution, the method further comprises:
and (3) uniformly mixing and stirring 1-100 ml of the graphene oxide dispersion liquid, 0.05-0.5 mmol of sulfur source, 0.01-0.1 mol of tin source and 1-10 ml of the hydrochloric acid aqueous solution to obtain the mixed solution, wherein the concentration of the graphene oxide dispersion liquid is 0.1-10 mg/ml.
3. The method of claim 2, wherein the sulfur source comprises C14H14S2、C12H12S2And C10H8S2At least one of (a).
4. The method of claim 2, wherein the tin source comprises SnCl2·2H2O。
5. The method according to claim 2, wherein the hydrochloric acid aqueous solution comprises water and hydrochloric acid in a volume ratio of 5-10: 1, and the mass fraction of the hydrochloric acid is 35-40%.
6. The method according to claim 2, wherein the temperature of the hydrothermal reaction is 140 ℃ to 180 ℃ and the time of the hydrothermal reaction is 10h to 20 h.
7. The method of claim 1, wherein the subjecting the intermediate product to a washing process comprises:
and (3) carrying out at least one washing treatment on the intermediate product by using deionized water and/or ethanol.
8. The method of claim 1, wherein the drying the intermediate product comprises:
and carrying out freeze drying treatment on the intermediate product at the temperature of between 50 ℃ below zero and 40 ℃ below zero.
9. The method according to claim 1, wherein the sintering process is performed on the intermediate product after the washing process and the drying process, and comprises:
and sintering the intermediate product subjected to the washing treatment and the drying treatment for 1-10 h in an inert gas atmosphere at the temperature of 200-500 ℃ to obtain the tin oxide/sulfur doped graphene composite material.
10. A tin oxide/sulfur-doped graphene composite material, which is prepared by the method of any one of claims 1 to 9.
11. A battery, characterized in that, the battery includes naked electric core, naked electric core includes the negative pole piece, the negative pole piece includes claim 10 tin oxide/sulphur doping graphite alkene combined material and negative current collector, tin oxide/sulphur doping graphite alkene combined material coat in on the negative current collector.
CN202011182957.4A 2020-10-29 2020-10-29 Tin oxide/sulfur-doped graphene composite material, preparation method thereof and battery Pending CN114426301A (en)

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