CN114242982A - Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof - Google Patents
Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
The invention discloses a graphene-coated two-dimensional metal compound electrode material and a preparation method and application thereof2Calcining in a gas mixed atmosphere, and cooling in a furnace after calcining to obtain the catalyst, wherein X is selected from one or more of S, Se and Te. The invention utilizes metal simple substance and CX2The metal thermal reaction of the compound in the form of the compound synthesizes a carbon-coated two-dimensional metal sulfide electrode in situ, the carbon layer exists in the form of graphene, and the structural stability of the material is effectively improvedThe property and the conductivity are improved, thereby improving the cycle stability of the cathode material. The synthesis method provided by the invention is completed in only one step, is convenient and fast, has low cost and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium ion battery material preparation, in particular to a graphene-coated two-dimensional metal compound electrode material and a preparation method and application thereof.
Background
The lithium ion battery is used as a secondary energy storage device, is widely applied to small-sized portable electronic products and electric vehicles, and has extremely high application prospect. The lithium ion battery is composed of four main raw materials, namely a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode material is one of key factors influencing the capacity, the cycle performance and the rate performance of the lithium ion battery. The theoretical capacity of a commercial graphite negative electrode which is mainly applied in the current market is only 372mAh/g, and the research and development of a negative electrode material with higher specific capacity are important tasks in the field of secondary batteries. Wherein the two-dimensional metal compound MX2The unique layered structure and lithium storage characteristics (M ═ Mo/W/Sn, etc., and X ═ S/Se/Te, etc.) make it possible to provide theoretical specific capacity over 600mAh/g, and thus it is a new type of negative electrode material with development prospect. The problems of volume expansion, byproduct dissolution and the like of an independent two-dimensional metal compound generally exist in the battery circulation process, so that the circulation performance is poor, and the problems can be effectively relieved by compounding the metal compound and a carbon material. At present, it has been reported that a hydrothermal method, a chemical vapor deposition method and the like are adopted to successfully synthesize a related two-dimensional metal compound/carbon material composite negative electrode material (such as MoS) with higher specific capacity and more stable cycling performance2、WS2、MoSe2Etc.), however, most of the methods reported at present have the defects of complicated preparation process, low yield, high cost and the like, and are in the laboratory stage.
Chinese patent CN 109671937a discloses an in-situ synthesis method of a transition metal oxide/graphene composite material, which has a process that is approximately: dissolving and mixing soluble ferric salt, soluble transition metal salt and soluble cerium salt in deionized water to obtain a uniform solution, dropwise adding a precipitator into the uniform solution, aging, filtering, washing and drying to obtain a transition metal hydroxide compound precipitate; weighing graphite and potassium permanganate, mixing, adding concentrated sulfuric acid and phosphoric acid mixed acid solution, reacting to obtain a gray green solution, carrying out ice bath treatment, adding a transition metal hydroxide compound for precipitation, then slowly adding hydrogen peroxide, stirring and dispersing to obtain a suspension of transition metal hydroxide/graphene oxide which is coated and grown mutually, and washing, centrifuging, drying and roasting the suspension to obtain the transition metal oxide/graphene composite material. In the patent technology, in the process of in-situ synthesis of graphene oxide, a transition metal hydroxide compound is directly added to obtain a transition metal oxide/graphene composite material with a porous structure, and the specific surface area reaches 100-200 m-2In each case, CeO2The addition of the graphene is beneficial to the generation of the nano-rods, the graphene is uniformly dispersed among gaps of product particles, the structure can buffer the volume expansion effect of the metal oxide in the charge-discharge cycle process, and the electrode reaction dynamic performance is improved. However, the patent technology still has the defects of complicated preparation process, low yield, high cost and the like, and cannot be industrially applied.
Disclosure of Invention
The invention aims to: aiming at the problems, the invention provides a graphene-coated two-dimensional metal compound electrode material and a preparation method and application thereof2The synthesis method provided by the invention is completed in one step, is convenient and fast, has low cost, is suitable for industrial large-scale production and use, and overcomes the defect that the conventional synthesis method for the compound has the defects that the carbon-coated two-dimensional metal sulfide electrode is synthesized in situ, the carbon layer exists in the form of graphene, and the structural stability and the electrical conductivity of the material are effectively improved, so that the cycle stability of the cathode material is improvedThe technology has the defects.
The technical scheme adopted by the invention is as follows: the in-situ synthesis method of the graphene-coated two-dimensional metal compound electrode material comprises the steps of placing metal simple substance powder in a vacuum tube furnace, and then placing inert gas and CX2Calcining in a gas mixed atmosphere, and cooling in a furnace after calcining to obtain the catalyst, wherein X is selected from one or more of S, Se and Te.
Further, the metal simple substance is one or more of Mo, W, Sn, and the like, and is not limited to the first three metal simple substances.
Furthermore, the calcination temperature is 600-1000 ℃, and the calcination time is 4-6 h.
Furthermore, the heating rate is 2-6 ℃/min during the calcination.
Further, the inert gas is argon, argon and CX2Is 100: 1-10. the volume ratio is preferably in this range if CX2If the volume fraction of (A) is too low, the reaction time is longer and the conversion is incomplete, whereas if CX is too low2Too high volume fraction of (C), CS2More waste, high cost and environmental pollution.
Preferably, the metal simple substance is Mo, and the CX is2Is CS2。
The invention further discloses a graphene-coated two-dimensional metal compound electrode material, which is prepared by the method.
Further, the inner layer of the electrode material is a layered metal compound, and the outer layer of the electrode material is graphene.
The invention also comprises a lithium ion battery which comprises a negative electrode material, wherein the negative electrode material is the graphene-coated two-dimensional metal compound electrode material.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the carbon-coated two-dimensional metal compound electrode material, the inner layer is a layered metal compound, the outer layer is graphene, the carbon-coated two-dimensional metal compound electrode material has good structural stability and conductivity, and can provide high specific capacity and good cycling stability when being used as a negative electrode of a secondary ion battery;
2. the invention utilizes metal simple substance and CX2The synthesis method provided by the invention is completed in one step, is convenient and fast, has low cost, is suitable for industrial large-scale production and use, and overcomes the defects in the prior art.
Drawings
FIG. 1 is an SEM image of the original molybdenum powder before reaction in example 1 of the present invention;
FIG. 2 shows the MoS synthesized after the reaction in example 1 of the present invention2SEM topography of @ graphene;
FIG. 3 shows MoS in example 1 of the present invention2TEM images of @ graphene;
FIG. 4 shows MoS in example 1 of the present invention2XRD pattern of @ graphene;
FIG. 5 shows MoS of example 1 of the present invention2@ graphene and comparative example 1 MoS2A cyclic graph of (a);
FIG. 6 is a cycle plot of example 2 SnS @ graphene of the present invention versus comparative example 1 SnS;
FIG. 7 shows WS according to embodiment 3 of the present invention2@ graphene and comparative example 1 WS2The cycle graph of (a).
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
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 and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Test main detection equipment
X-ray diffraction (XRD) test: x-ray diffractometer, instrument model: rigaku UltimaIV-185, Japan.
Scanning Electron Microscope (SEM) testing: scanning electron microscope, instrument model: FEIQuanta, the netherlands.
Assembling method of CR2025 button battery
The electrode materials (example 1, example 2, example 3), acetylene black, and polyvinylidene fluoride (PVDF) were mixed in a ratio of 7: 2: 1, preparing slurry, coating the slurry on a copper foil, drying, cutting the dried copper foil into small round pieces with the diameter of about 1cm by using a cutting machine, using a metal lithium piece as a counter electrode, using Celgard2500 as a diaphragm, and using EC/DMC/EMC 1: 1: 1(W/W) +1M LiPF6A CR2025 button cell was assembled in an argon atmosphere glove box as an electrolyte.
And (3) electrochemical performance testing:
an LANDCT 2001A tester (blue electronic, Inc., Wuhan city) is adopted to carry out electrochemical performance test on the assembled battery, the test temperature is 30 ℃, the test voltage range is 0.01-3V, and charging and discharging are carried out at 100mAh/g in the test process.
Example 1
Preparation of graphene coated MoS2A method of (M ═ Mo, X ═ S) electrode material, comprising the steps of:
s1, weighing 1g of nano-scale molybdenum powder, placing the nano-scale molybdenum powder in a tube furnace, and then introducing argon and CS2Wherein CS is2The volume ratio of (A) is 8%;
s2, calcining molybdenum powder at a heating speed of 4 ℃ min, heating to 900 ℃, preserving heat for 5 hours, and cooling along with the furnace to obtain graphene-coated MoS2An electrode material.
Coating the obtained graphene-coated MoS2The electrode material is made into a negative pole piece and a button cell is made for performance comparison. Wherein, the negative pole is composed of: composite anode material: conductive additive: binder 70: 20: 10, adopting a Celgard2500 type diaphragm, adopting a lithium metal counter electrode, and adopting an EC/DMC/EMC 1: 1: 1(W/W) +1M LiPF6 is an electrolyte.
Example 2
A method for preparing a graphene coated SnS electrode material comprises the following steps:
s1, weighing 1g of nano-scale tin powder, placing the nano-scale tin powder in a tube furnace, and then introducing argon and CS2Wherein CS is2The volume percentage of (A) is 2%;
s2, calcining tin powder at a heating speed of 5 ℃ min by setting a heating program, heating to 800 ℃, preserving heat for 5 hours, and then cooling along with a furnace to obtain graphene-coated SnS2An electrode material.
SnS obtained in the above embodiment2An electrode sheet was prepared as a negative electrode using a lithium metal sheet as a counter electrode, Celgard2500 as a separator, and a 1M carbonate solution as an electrolyte (wherein the solvent was a mixed solution of ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 1, and the solute was LiPF6) The CR2025 button cell was assembled in a glove box under argon atmosphere. At 100mA · g－1And testing the performance of the battery under the charge and discharge current density.
Example 3
Preparation of graphene coated WS2A method of (M-W, X-S) electrode material, comprising the steps of:
s1, weighing 1g of nano-grade tungsten powder, placing the powder in a tube furnace, and then introducing argon and CS2Wherein CS is2The volume ratio of (A) is 5%;
s2, setting a heating program to be a heating speed of 6 ℃ min, calcining tungsten powder, heating to 700 ℃, preserving heat for 5 hours, and cooling along with a furnace to obtain the graphene coated WS2An electrode material.
WS obtained in the above example2An electrode sheet was prepared as a negative electrode using a lithium metal sheet as a counter electrode, Celgard2500 as a separator, and a 1M carbonate solution as an electrolyte (wherein the solvent was a mixed solution of ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 1, and the solute was LiPF6) The CR2025 button cell was assembled in a glove box under argon atmosphere. At 100mA · g－1And testing the performance of the battery under the charge and discharge current density.
Comparative example 1
For commercial MoS2A sample (Mecline, 99.5% or more and 100nm) is prepared into a negative electrode plate according to the method of the embodiment 1, a button cell is assembled, and the cell test is carried out under the same test conditions as the embodiment 1.
Comparative example 2
A commercially available SnS sample (with a melting material, 99.99%, 325 mesh) was fabricated into a negative electrode tab according to the method described in example 1, assembled into a button cell, and subjected to a battery test under the same test conditions as in example 1.
Comparative example 3
For commercially available WS2Samples (alatin, 99.9%, 2 μm) were fabricated into negative electrode sheets as described in example 1, assembled into coin cells, and subjected to cell testing under the same test conditions as in example 1.
The material obtained in example 1 has a lamellar morphology as shown by SEM tests. TEM tests show that the surface of the sheet of the material obtained in example 1 is coated with the graphene layer. XRD tests show that the main component of the material obtained in example 1 is molybdenum disulfide. The result of the constant-current charge and discharge test of the battery shows that the MoS described in the embodiment 1 is adopted under the condition of 100mA/g current density2The initial specific discharge capacity of the @ graphene negative electrode material is 746.6mAh/g, and the capacity retention rate reaches 77% after 100 times of circulation. SnS as described in example 22The initial discharge specific capacity of the @ graphene negative electrode material is 1194mAh/g, and the capacity retention rate is 42% after 20 times of circulation. WS as described in example 32The initial discharge specific capacity of the @ graphene negative electrode material is 707mAh/g, and the capacity retention rate reaches 88% after 20 times of circulation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. An in-situ synthesis method of a graphene-coated two-dimensional metal compound electrode material is characterized by comprising the following steps: placing the metal simple substance powder in a vacuum tube furnace, and then adding CX into inert gas2Calcining in a gas mixed atmosphere, and cooling in a furnace after calcining to obtain the catalyst, wherein X is selected from one or more of S, Se and Te.
2. The in-situ synthesis method of the graphene-coated two-dimensional metal compound electrode material according to claim 1, wherein the metal simple substance is one or more of Mo, W and Sn.
3. The in-situ synthesis method of the graphene-coated two-dimensional metal compound electrode material as claimed in claim 2, wherein the calcination temperature is 600-1000 ℃ and the calcination time is 4-6 h.
4. The in-situ synthesis method of the graphene-coated two-dimensional metal compound electrode material as claimed in claim 3, wherein the temperature rise rate is 2-6 ℃/min during calcination.
5. The in-situ synthesis method of graphene-coated two-dimensional metal compound electrode material according to claim 1, wherein the inert gas is argon, and the argon and the CX are2Is 100: 1-10.
6. the in-situ synthesis method of graphene-coated two-dimensional metal compound electrode material according to claim 1, wherein the metal simple substance is Mo, and CX is2Is CS2。
7. A graphene-coated two-dimensional metal compound electrode material, which is prepared by the in-situ synthesis method of any one of claims 1 to 6.
8. The graphene-coated two-dimensional metal compound electrode material according to claim 7, wherein an inner layer of the electrode material is a layered metal compound, and an outer layer is graphene.
9. A lithium ion battery, comprising a negative electrode material, wherein the negative electrode material is the graphene-coated two-dimensional metal compound electrode material according to claim 8.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003173775A (en) * | 2001-12-05 | 2003-06-20 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| US20060239882A1 (en) * | 2003-01-31 | 2006-10-26 | Seo Dong-Kyun | Preparation of metal chalcogenides from reactions of metal compounds and chalcogen |
| US20120121973A1 (en) * | 2010-11-15 | 2012-05-17 | Samsung Electro-Mechanics Co., Ltd. | Negative active material and lithium secondary battery with the same, and method for manufacturing the lithium secondary battery |
| CN102522543A (en) * | 2011-12-15 | 2012-06-27 | 清华大学 | Method for preparing nanometer compound of tin disulfide-graphene |
| US8303926B1 (en) * | 2009-01-22 | 2012-11-06 | Stc.Unm | Synthetic methods for generating WS2 nanostructured materials |
| US20140110635A1 (en) * | 2011-06-14 | 2014-04-24 | Ulrich Wietelmann | Method for producing a carbon-coated lithium sulfide and use thereof |
| CN105621355A (en) * | 2016-03-08 | 2016-06-01 | 上海大学 | Composite material with hollow graphene spheres loaded with nanometer tin disulfide and method for preparing composite material |
| WO2018024183A1 (en) * | 2016-08-01 | 2018-02-08 | 福建新峰二维材料科技有限公司 | Method for preparing three-dimensional graphene/mos2 composite material |
| CN107959005A (en) * | 2017-10-25 | 2018-04-24 | 温州大学 | A kind of composite material of transient metal sulfide and graphene and preparation method and application |
| CN108346783A (en) * | 2018-01-11 | 2018-07-31 | 三峡大学 | A kind of layered structure MoSxSe2-x/ graphene negative material and preparation method thereof |
| WO2018148518A1 (en) * | 2017-02-10 | 2018-08-16 | University Of North Texas | Passivation of lithium metal by two-dimensional materials for rechargeable batteries |
| CN111530491A (en) * | 2020-06-11 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of three-dimensional molybdenum sulfide/nitrogen doped graphene electrocatalyst and hydrogen evolution application thereof |
-
2021
- 2021-12-20 CN CN202111560111.4A patent/CN114242982B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003173775A (en) * | 2001-12-05 | 2003-06-20 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| US20060239882A1 (en) * | 2003-01-31 | 2006-10-26 | Seo Dong-Kyun | Preparation of metal chalcogenides from reactions of metal compounds and chalcogen |
| US8303926B1 (en) * | 2009-01-22 | 2012-11-06 | Stc.Unm | Synthetic methods for generating WS2 nanostructured materials |
| US20120121973A1 (en) * | 2010-11-15 | 2012-05-17 | Samsung Electro-Mechanics Co., Ltd. | Negative active material and lithium secondary battery with the same, and method for manufacturing the lithium secondary battery |
| US20140110635A1 (en) * | 2011-06-14 | 2014-04-24 | Ulrich Wietelmann | Method for producing a carbon-coated lithium sulfide and use thereof |
| CN102522543A (en) * | 2011-12-15 | 2012-06-27 | 清华大学 | Method for preparing nanometer compound of tin disulfide-graphene |
| CN105621355A (en) * | 2016-03-08 | 2016-06-01 | 上海大学 | Composite material with hollow graphene spheres loaded with nanometer tin disulfide and method for preparing composite material |
| WO2018024183A1 (en) * | 2016-08-01 | 2018-02-08 | 福建新峰二维材料科技有限公司 | Method for preparing three-dimensional graphene/mos2 composite material |
| WO2018148518A1 (en) * | 2017-02-10 | 2018-08-16 | University Of North Texas | Passivation of lithium metal by two-dimensional materials for rechargeable batteries |
| CN107959005A (en) * | 2017-10-25 | 2018-04-24 | 温州大学 | A kind of composite material of transient metal sulfide and graphene and preparation method and application |
| CN108346783A (en) * | 2018-01-11 | 2018-07-31 | 三峡大学 | A kind of layered structure MoSxSe2-x/ graphene negative material and preparation method thereof |
| CN111530491A (en) * | 2020-06-11 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of three-dimensional molybdenum sulfide/nitrogen doped graphene electrocatalyst and hydrogen evolution application thereof |
Non-Patent Citations (5)
| Title |
|---|
| ANWER, S等: ""Nature-Inspired, Graphene-Wrapped 3D MoS2 Ultrathin Microflower Architecture as a High-Performance Anode Material for Sodium-Ion Batteries"", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 11, no. 25, pages 22323 - 22331 * |
| TAN, G等: ""Burning lithium in CS2 for high-performing compact Li2S–graphene nanocapsules for Li–S batteries"", 《NATURE ENERGY》, vol. 2, pages 1 - 10 * |
| 白金曼: "过渡金属硫属化合物结构的设计合成及电化学性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 07, pages 016 - 424 * |
| 陈俊杰等: ""二硫化钼/石墨烯复合电极的制备及其储锂性能"", 《武汉大学学报(理学版)》, vol. 62, no. 1, pages 19 - 24 * |
| 韩大伟;江素华;: "WSe_2负载掺氮三维石墨烯的制备及储锂性能", 复旦学报(自然科学版), no. 05 * |
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