CN109449397B - A composite negative electrode material with excellent rate performance and preparation method thereof - Google Patents
A composite negative electrode material with excellent rate performance and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- 239000010405 anode material Substances 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 15
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- 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
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- 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
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Abstract
The invention belongs to the field of new energy materials and electrochemistry, and particularly relates to a composite anode material with excellent rate performance and a preparation method thereof. The preparation method comprises the steps of taking graphene oxide, tin salt and an organic sulfur source as raw materials, adopting a one-step solvothermal method to combine with heat treatment, and adding a surfactant to prepare the composite negative electrode material with excellent rate performance. The composite negative electrode material prepared by the method has excellent rate performance: at 1 A.g‑1The reversible specific capacity under the current density is 910 mAh.g‑1～1090mAh g‑1(ii) a At 10 A.g‑1The reversible specific capacity under the heavy current density is 725 mAh.g‑1～865mAh·g‑1。
Description
Technical Field
The invention belongs to the field of new energy materials and electrochemistry, and particularly relates to a composite anode material with excellent rate performance and a preparation method thereof.
Technical Field
In the 21 st century, although the economic and scientific technologies are rapidly developed, the main sources of energy are mainly fossil fuels such as petroleum, coal and natural gas which are limited on the earth. It is well known that gases derived from fossil fuel and biomass fuel emissions pollute the atmosphere, causing serious global problems. Furthermore, the increasing dependence on non-renewable energy sources abroad can also jeopardize national safety. Therefore, in the face of increasingly severe energy and environmental problems, the development of renewable clean energy has become a problem to be solved urgently in China.
Solar radiation energy, wind energy, ocean energy, geothermal energy and the like are renewable energy sources in the nature. However, these renewable energy sources are strongly dependent on time and space of change. But in the future they may be stored and converted by chemical energy forms. Chemical energy is the most convenient storage mode, which can bring convenience to power, illumination, communication and the like, and the battery provides a light and pollution-free chemical energy storage mode, and simultaneously can efficiently convert the chemical energy into electric energy. Compared with other rechargeable batteries (such as lead-acid batteries and nickel-metal hydride batteries), the lithium ion battery has the obvious advantages of high specific capacity, long cycle life, high voltage platform, no memory effect, quick charge and discharge, high safety performance, low self-discharge rate, small environmental pollution, small volume, light weight and the like, so the lithium ion battery has attracted attention. Currently, lithium ion batteries are increasingly widely used, and gradually move from small portable electric appliances such as mobile phones, notebook computers, digital cameras and the like to the field of electric vehicle power.
However, the energy density and the power density of the traditional lithium ion electrode material are lower, and at present, the theoretical specific capacity of the negative electrode material graphite of the commercial lithium ion battery is only 372mAh g-1And the step rate performance is poor, and the requirements of electric vehicles and hybrid vehicles on high energy density, long endurance life and rapid charging of power batteries cannot be met, so that the development of novel cathode materials with high specific capacity and excellent step rate performance is urgently needed. Wherein, SnS2The theoretical capacity is up to 1232 mAh.g-1The method has the characteristics of rich resources, low toxicity, low cost and the like, and is widely concerned by researchers in recent years. However, SnS2Electron conductivity and bulk lithium ion conductivity are betterPoor, resulting in poor step rate performance. This problem severely hinders SnS2The lithium ion battery cathode material is practically applied. To solve the above problems, the document is directed to SnS2The improvement method is to compound the composite anode material with a high-conductivity carbon matrix so as to improve the electronic conductance of the composite anode material and accelerate the kinetics of the electrochemical reaction of the electrode. Representative SnS2Research work on base electrode materials includes:
(1) the research group of the university of Wuhan WangTaihong professor uses a room temperature condensation reflux method, takes graphene oxide powder as a carbon source, stannic chloride as a tin source, thioacetamide as a sulfur source, reduces graphene oxide by hydrazine hydrate, and finally obtains SnS through heat treatment2the/rGO composite anode material. The electrochemical performance of the alloy is tested, and the result shows that: under the current density of 0.1C, the reversible specific capacity is 1034mAh g after the circulation for 200 times-1(J.Mater.chem.A., 2013,1, 8658-8664). However, the SnS obtained by the preparation process2The specific capacity of the/rGO composite negative electrode material is attenuated quickly along with the increase of current density, and the step rate performance needs to be further improved.
(2) The research group of DuNing professor of Zhejiang university adopts a room temperature wet chemical method, firstly modifies the carbon nano tube, and then synthesizes SnS through the electrostatic attraction between tin ions and the carbon nano tube2The nano-sheet/carbon nano-tube composite negative electrode material. The performance test of the obtained composite negative electrode material as a negative electrode material of a lithium ion battery shows that: at a current density of 100mA g-1The first discharge specific capacity is 1500mAh g-1(ii) a After 50 times of circulation, the reversible specific capacity is only 500mAh g-1(ACSAppl. Mater. interfaces,2011,3, 4067-. The specific capacity of the composite negative electrode material is lower, and needs to be further improved; and the step multiplying power performance is poor, the energy consumption in the preparation process is high, and the cost is high.
Currently, for the negative electrode material SnS of the lithium ion battery2Modification research of (2) to realize the modification of SnS2Improvement of material rate capability, but limited promotion effect, SnS2The step rate performance of (a) is still limited by some intrinsic characteristics. By introducing a highly electron-conductive matrix materialThe electronic conductance of the composite cathode material accelerates the electrode reaction kinetic process; however, the electrode reaction rate depends on the co-transport of electrons and ions, and the charge transfer process at the material interface. SnS2The ionic conductance of the base material is poor, the electronic conductance of the material is only improved, and the improvement of the rate capability of the electrode material has certain limitation. How to simultaneously improve the ion and electron transmission capability of the material is to realize high-rate SnS2The key technical bottleneck of the cathode material.
Disclosure of Invention
In order to solve the problems, the invention provides a composite negative electrode material with excellent rate performance, a preparation method and application, and the composite negative electrode material prepared by the method has excellent rate performance: at 1 A.g-1The reversible specific capacity under the current density is 910 mAh.g-1～1090mAh·g-1(ii) a At 10 A.g-1The reversible specific capacity under the heavy current density is 725 mAh.g-1～865mAh·g-1。
The invention is realized by the following technical scheme:
the composite negative electrode material with excellent rate performance is SnS2-SnS (n-p) junction/graphene composite anode material.
The invention also aims to provide a preparation method of the composite negative electrode material with excellent rate performance, wherein the preparation method comprises the steps of taking graphene oxide, tin salt and an organic sulfur source as raw materials, adopting a one-step solvothermal method to combine with heat treatment, and adding a surfactant to prepare the composite negative electrode material with excellent rate performance.
Further, the content of the preparation method is as follows:
Step 3, placing the precursor in a muffle furnace to react in an inert atmosphere, wherein during the reaction, the surfactant is cracked in situ into amorphous carbon, and the amorphous carbon further cracks the precursor SnS2Partial SnS in rGO2Reducing the reaction product into SnS, and finally obtaining the composite cathode material with excellent rate performance.
Further, the composite anode material with excellent rate capability is SnS2-SnS (n-p) junction/graphene composite anode material, i.e. SnS2-a SnS/rGO composite anode material.
Further, after the graphene oxide dispersion liquid is added with the solvent in the step 1, the concentration range of the graphene oxide is 0.01-20 g.L-1。
Further, the concentration range of the tin salt in the step 1 is 1 x 10 < -4 > to 1 x 10 < -1 > mol.L-1。
Further, the concentration range of the organic sulfur source in the step 1 is 4X 10-4～5×10-1mol·L-1。
Further, the surfactant concentration range in step 1 is 1 × 10-5～2×10-1mol·L-1。
Further, in the step 1, the tin salt is tin nitrate, tin chloride, tin sulfate, tin nitrate crystal hydrate, tin chloride crystal hydrate or tin sulfate crystal hydrate.
Further, the solvent in step 1 is one or more of deionized water, absolute ethyl alcohol, propyl alcohol and methanol.
Further, in the step 1, the organic sulfur source is ethanethiol, propenylthiol, thiourea or L-cysteine.
Further, the surfactant in step 1 is one or more of sodium carboxymethylcellulose, polyvinylidene fluoride, cetyl trimethyl ammonium bromide and sodium dodecyl sulfate.
Further, the temperature of the constant temperature box in the step 2 is 120-240 ℃; the reaction time is 10-40 h.
Further, the temperature of the muffle furnace in the step 3 is 300-600 ℃; the reaction time is 1-10 h.
Further, the inert atmosphere in step 3 is one or two of nitrogen and argon.
Another object of the present invention is to provide a lithium battery having excellent step rate performance, which is obtained by embedding lithium in the composite anode material having excellent rate performance.
The method of the invention improves SnS2Ion conduction in bulk phase, and considering SnS2The material has the characteristic of an n-type semiconductor, inorganic tin salt is used as a tin source, organic sulfide is used as a sulfur source, a surfactant is used as a carbon source, graphene oxide is used as a growth matrix, and SnS is obtained by a one-step solvothermal method2(ii)/rGO; in the subsequent heat treatment process, the surfactant is cracked into carbon in situ, and part of SnS is treated2Reducing into SnS with p-type conductivity, thereby obtaining closely combined SnS with n-p junction formed on interface2-SnS composite material grown on rGO matrix, i.e. said SnS2-SnS (n-p) junction/graphene composite anode material.
During insertion of lithium, SnS2N-p junction formed by an SnS interface, able to generate an n-p junction formed by SnS2Pointing to built-in electric field of SnS due to SnS2The lithium intercalation potential is higher than SnS, so that SnS in the lithium intercalation process can be accelerated2-lithium ion transport at the SnS interface, accelerating the electrode reaction kinetics; the three-dimensional conductive network graphene can improve the electronic conductivity of the composite material and ensure the full utilization of active substances; the flexible graphene is also beneficial to buffering the volume change generated by lithium desorption of active substances in the charging and discharging processes; cause SnS2the-SnS/rGO electrodes show excellent step rate performance and stable cycling performance.
The invention has the following beneficial technical effects:
SnS2the preparation method of the-SnS (n-p) junction/graphene composite anode material is simple and easy to implement, and can be applied to preparation of other heterostructure/graphene composite anode materials. SnS prepared by the method2-SnS (n-p) junction/grapheneThe composite anode material shows excellent rate performance: at 1 A.g-1The reversible specific capacity under the current density is 910 mAh.g-1～1090mAh·g-1(ii) a At 10 A.g-1The reversible specific capacity under the heavy current density is 725 mAh.g-1～865mAh·g-1The lithium ion battery cathode material is a potential high-performance lithium ion battery cathode material and is expected to be widely applied to the fields of various portable electronic devices, electric automobiles, aerospace and the like.
Drawings
FIG. 1 shows an embodiment of the present invention2Phase identification diagram of SnS (n-p) junction/graphene composite negative electrode material.
FIG. 2 shows an embodiment of the present invention2-surface topography of the SnS (n-p) junction/graphene composite anode material.
FIG. 3 shows an embodiment of the present invention2-high resolution of transmission of SnS (n-p) junction/graphene composite anode material.
FIG. 4 shows an embodiment of the invention2-rate performance diagram of SnS (n-p) junction/graphene composite anode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
Example 1
The embodiment provides a preparation method of a composite negative electrode material with excellent rate performance, which is characterized in that graphene oxide, tin salt and an organic sulfur source are used as raw materials, a one-step solvothermal method is adopted to combine with heat treatment, and a surfactant is added to prepare the composite negative electrode material with excellent rate performance.
The preparation method comprises the following steps:
Step 3, placing the precursor in a muffle furnace to react in an inert atmosphere, wherein during the reaction, the surfactant is cracked in situ into amorphous carbon, and the amorphous carbon further cracks the precursor SnS2Partial SnS in rGO2Reducing the reaction product into SnS, and finally obtaining the composite cathode material with excellent rate performance.
According to the preparation method, in this embodiment, the specific experimental contents are as follows:
4mL of the solution was measured and the concentration was 3 mg/mL-1Adding 60mL of deionized water into the graphene oxide dispersion liquid, then adding 0.1g of sodium carboxymethylcellulose, and uniformly stirring to completely dissolve the graphene oxide dispersion liquid; 0.6g of tin tetrachloride pentahydrate are subsequently added, stirred and dissolved completely, and 0.2g of thioacetamide are added and stirred homogeneously. Pouring the obtained mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 120 ℃ in a constant temperature box, and centrifugally drying to obtain a precursor; finally, the precursor is put in a muffle furnace to react for 0.5h at 500 ℃ in Ar atmosphere to finally obtain SnS2-SnS (n-p) junction/graphene composite anode material.
Uniformly mixing 80 wt.% of composite negative electrode material, 10 wt.% of acetylene black and 10 wt.% of sodium carboxymethylcellulose to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum, stamping to obtain a circular electrode piece, taking metal lithium as a counter electrode, and 1 mol.L-1LiPF6The volume ratio of/EC + DEC + DMC (1: 1:1) is the electrolyte, Celgard2400 is the diaphragm,and assembling the button cell. The battery is subjected to a step rate performance test, the charging and discharging voltage range is 0.01-2.5V, and the result shows that: at 1 A.g-1The reversible specific capacity is 1090 mAh.g under the current density-1(ii) a Even at 10A g-1Under the condition of large current density, the reversible specific capacity still has 865 mAh.g-1。
Example 2
A method for preparing a composite anode material having excellent rate characteristics according to this example is substantially the same as in example 1. According to the preparation method, in this embodiment, the specific experimental contents are as follows:
6mL of the solution was measured and the concentration was 5 mg/mL-1Adding 74mL of ethanol into the graphene oxide dispersion liquid, then adding 0.5g of hexadecyl trimethyl ammonium bromide, and uniformly stirring to completely dissolve the graphene oxide dispersion liquid; 0.5g of tin tetrachloride pentahydrate was then added, stirred and dissolved completely, and 0.4g L-cysteine was added and stirred well. Pouring the obtained mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, reacting for 10 hours at 200 ℃ in a constant temperature box, and centrifugally drying to obtain a precursor; finally, the precursor is placed in a muffle furnace, N2Reacting for 3 hours at 400 ℃ under the atmosphere to finally obtain SnS2-SnS (n-p) junction/graphene composite anode material.
Uniformly mixing 80 wt.% of composite negative electrode material, 10 wt.% of acetylene black and 10 wt.% of sodium carboxymethyl cellulose to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum, stamping to form a circular electrode plate, taking metal lithium as a counter electrode, and 1 mol.L-1LiPF6And the button cell is assembled by using/EC + DEC + DMC (volume ratio of 1:1:1) as an electrolyte and Celgard2400 as a diaphragm. The battery is subjected to a step rate performance test, the charging and discharging voltage range is 0.01-2.5V, and the result shows that: at 1 A.g-1The reversible specific capacity is 910 mAh.g under the current density-1(ii) a Even at 10A g-1Under high current density, the reversible specific capacity is only 725mAh g-1。
Example 3
A method for preparing a composite anode material having excellent rate characteristics according to this example is substantially the same as in example 1. According to the preparation method, in this embodiment, the specific experimental contents are as follows:
the amount of 12mL of the solution was 1 mg/mL-1Adding 48mL of methanol into the graphene oxide dispersion liquid, then adding 0.1g of polyvinylidene fluoride, and uniformly stirring to completely dissolve the graphene oxide dispersion liquid; 0.5g of tin tetrachloride pentahydrate was then added, stirred and dissolved completely, and 1.2g of thiourea was added and stirred uniformly. Pouring the obtained mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, reacting for 12 hours at 180 ℃ in a constant temperature box, and centrifugally drying to obtain a precursor; finally, the precursor is placed in a muffle furnace, and the gas flow ratio is 3:1 Ar/N2Reacting for 8 hours at 300 ℃ in mixed atmosphere to finally obtain SnS2-SnS (n-p) junction/graphene composite anode material.
Uniformly mixing 80 wt.% of composite negative electrode material, 10 wt.% of acetylene black and 10 wt.% of sodium carboxymethyl cellulose to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum, stamping to form a circular electrode plate, taking metal lithium as a counter electrode, and 1 mol.L-1LiPF6And the button cell is assembled by using/EC + DEC + DMC (volume ratio of 1:1:1) as an electrolyte and Celgard2400 as a diaphragm. The battery is subjected to a step rate performance test, the charging and discharging voltage range is 0.01-2.5V, and the result shows that: at 1 A.g-1The reversible specific capacity is 970mAh g under the current density-1(ii) a Even at 10A g-1Under high current density, the reversible specific capacity is only 820mAh g-1。
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