CN113675391A - Heterogeneous layered composite material for lithium ion battery cathode and preparation method thereof - Google Patents
Heterogeneous layered composite material for lithium ion battery cathode and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 73
- 238000000498 ball milling Methods 0.000 claims abstract description 65
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 23
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 16
- 239000011324 bead Substances 0.000 claims description 14
- 229910052961 molybdenite Inorganic materials 0.000 claims description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910015667 MoO4 Inorganic materials 0.000 claims description 3
- 101100502609 Caenorhabditis elegans fem-1 gene Proteins 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 229910016002 MoS2a Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 30
- 229910052799 carbon Inorganic materials 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 7
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000003860 storage Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- -1 transition metal sulfide Chemical class 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a heterogeneous layered composite material for a lithium ion battery cathode and a preparation method thereof, and the preparation method comprises the following steps: uniformly mixing a precursor of the first two-dimensional material and the second two-dimensional material; ball milling the mixture; roasting the ball-milled compound in nitrogen atmosphere to obtain heterogeneous layered MoS2a/C composite material. After roasting, the first stepThe precursor of one two-dimensional material is decomposed to generate the corresponding two-dimensional material, and the two-dimensional material also has the characteristics of small size and thin layer, so that the two-dimensional material and the second two-dimensional material are stacked in a staggered mode, and aggregation is prevented from happening. Few-layer MoS prepared by the invention2the/C composite material is used as the negative electrode material of the lithium ion battery at a larger current of 500 mA.g‑1At a current density of 532 mAh g, the capacity remained substantially unchanged after 150 cycles‑1。
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a negative electrode material for a lithium ion battery.
Background
A large number of sites for charge insertion are arranged between the two-dimensional layered metal oxysulfide layers, and the two-dimensional layered metal oxysulfide has huge energy storage potential, thereby arousing wide interest of electrochemical researchers. And the central metal atom has rich oxidation states, so that in the charging and discharging processes, 1 mol of electrode material can capture a plurality of mol of electrons, and the theoretical specific capacity is high. However, its specific capacity is limited due to the inability to fully utilize interlayer sites, low conductivity, and unstable structure. The interlayer spacing of the two-dimensional material is fully improved, the stacking layer number is reduced, the two-dimensional material is small in size, the utilization rate of reaction sites between layers of the two-dimensional material can be improved, and the defects are effectively overcome. Professor Huangfuqiang, Shanghai silicate institute, and the like, and MoS is adopted2Method for preparing MoS by ball milling with worm graphite2The graphene composite material is used for researching the negative performance of the lithium ion battery. The initial specific capacity of the product is higher, however, the cycling stability of the two-dimensional material laminate participating in compounding needs to be improved because the laminate is thicker. Therefore, the efficiency of charge diffusion and migration in the charge and discharge process can be effectively improved by regulating and controlling the structure of the negative electrode material, so that the electricity storage performance of the material is improved. According to the application requirements, the structural design and preparation of the two-dimensional material also arouse the wide interest of researchers.
The existing method for compounding two-dimensional materials (if one of the two-dimensional materials is a carbon material, the other is two-dimensional oxysulfide) generally comprises the steps of directly growing two-dimensional oxysulfide on the surface of graphene oxide (method one) and liquid-phase stripping and layer-by-layer assembly (method two). The thickness size and distribution randomness of the metal oxysulfide nanosheets and the graphene oxide in the mixed hybrid structure obtained by the first method are large, so that reaction sites of the metal oxysulfide nanosheets and the graphene oxide cannot be fully utilized. The second method needs to strip the metal oxysulfide in advance, and has harsh reaction conditions, difficult control and lower stripping efficiency. Both of them generally adopt graphene oxide as a carrier for compounding, and then reduce the graphene oxide into graphene (rGO) through post-treatment, and the preparation process is complex and is not easy for mass production.
The researchers also produced the transition metal sulfide/transition metal sulfide heterojunction material by means of transfer or CVD growthNature Materials, 13, 1096-1101(2014)]. Researchers at Manchester university also used water as a main solvent to prepare stable and high-concentration water-based two-dimensional material ink and jet-printed heterostructures of various two-dimensional materialsNature Nanotechnology 12, 343-350(2017)]. It has also been reported that a complex of a two-dimensional transition metal oxide and a sulfide is obtained by using the two-dimensional transition metal oxide and a sulfur source as a precursor and controlling the reaction conditionsJournal of Electronic Materials 47, 6767-6773(2018)，ACS Sustainable Chemistry&Engineering 5, 8025-8034(2017)]. The resulting composite generally has a high degree of surface sulfidation and a predominantly oxide material interior. Two different metals can also be used for preparing the two metal sulfides, and then the two metals are reacted with a sulfur source. The method can obtain the compound of the metal oxide and the metal oxide or the metal sulfide and the metal sulfide, the microstructure is random, and the regulation and control are difficultChemistrySelect 3, 11020-11026(2018)]。
Disclosure of Invention
The invention aims to provide a negative electrode material for a lithium ion battery and a preparation method thereof, the method is simple, convenient and controllable, can be used for large-scale production, and can realize the assembly and uniform and ordered compounding of two-dimensional materials.
In order to solve the technical problems, the invention provides a technical scheme that a method for efficiently preparing a heterogeneous layered composite material by using a ball milling method comprises the following steps:
(1) weighing a precursor of a first two-dimensional material and a second two-dimensional material in a certain mass ratio, and uniformly mixing;
(2) ball-milling the mixture to obtain a precursor compound with small size and ordered stacking;
(3) and roasting the precursor composite with small size and ordered stacking in nitrogen atmosphere to obtain the heterogeneous layered compound composite material.
In a preferred embodiment of the present invention, the molar ratio of the precursor of the first two-dimensional material to the second two-dimensional material isx1, wherein 1/5 is less than or equal toxLess than or equal to 5; the precursor of the first two-dimensional material is ammonium thiomolybdate (NH)4)2MoS4Ammonium molybdate (NH)4)2MoO4A salt of a plasma crystal and a second two-dimensional material of MoS2，MoO3Or any of expanded graphite.
In the preferred technical scheme of the invention, the mass ratio of the grinding ball to the raw materials isy：(x + 1), wherein 3 is less than or equal toyLess than or equal to 30; the ball milling time is 5-15 h; the ball milling speed is 200-500 r.min-1。
In the preferred technical scheme of the invention, the ball milling medium is beads with the diameter of 2 mm or 5 mm.
In the preferred technical scheme of the invention, the ball milling medium is mixed beads with the diameter of 2 mm and 5 mm, and the mass ratio of the two beads isz:1, wherein 1/8 is less than or equal toz≤8。
In the preferred technical scheme of the invention, the heating rate of roasting is 2 ℃/min, the roasting temperature is 400-700 ℃, and the roasting time is 2-6 h.
The invention also provides the application of the heterogeneous layered composite material as a lithium ion battery cathode material.
Compared with the prior art, the invention has the following advantages:
(1) the nano-sheets of the two-dimensional materials in the heterogeneous two-dimensional material compound prepared by the invention are both in a small-size and few-layer structure, and the material has high specific capacity and excellent cycle performance as a lithium ion battery cathode material.
(2) The few-layer MoS prepared by the invention2The composite material with less carbon layer is used as the negative electrode material of the lithium ion battery at a larger current of 500 mA.g-1At a current density of 532 mAh g, the capacity remained substantially unchanged after 150 cycles-1。
Drawings
FIG. 1 is a diagram showing a ball milling composite mechanism of ammonium thiomolybdate and expanded graphite.
FIG. 2 is a few layer MoS prepared in example 12Transmission electron microscopy of the/C complex.
FIG. 3 is a few layer MoS prepared in example 12composite/C and pure MoS20.5A · g as the negative electrode material of the lithium ion battery–1Cycling stability at current density.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
The present invention is illustrated by way of example and not by way of limitation. It should be noted that references to "an" or "one" embodiment in this disclosure are not necessarily to the same embodiment, but to at least one.
Various aspects of the invention are described below. It will be apparent, however, to one skilled in the art that the present invention may be practiced according to only some or all aspects of the present invention. For purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without specific details. In other instances, well-known features are omitted or simplified in order not to obscure the present invention.
Various operations will be described as multiple discrete steps in turn, and in a manner that is most helpful in understanding the present invention; however, the description in order should not be construed as to imply that these operations are necessarily order dependent.
Various embodiments will be described in terms of typical classes of reactants. It will be apparent to those skilled in the art that the present invention may be practiced using any number of different types of reactants, not just those provided herein for purposes of illustration. Furthermore, it will also be apparent that the invention is not limited to any particular hybrid example.
The invention provides a simple, convenient and controllable method for realizing ordered composite assembly of two-dimensional materials, which can be produced in a large scale. The nano-sheets of the two-dimensional materials in the prepared hybrid compound are both of a structure with few layers and small size. The ordered hybrid structure shows ideal lithium storage performance and has application potential even in other related energy light aspects.
Referring to fig. 1, in the ball milling process for preparing the heterogeneous layered composite material, a salt precursor of a two-dimensional material is adopted, the salt substance is generally an ionic crystal, and the ionic crystal has a crystal configuration with high hardness and regularity. The high-hardness and sharp crystal edge can transfer impact force and shearing force generated by ball milling, so that the pressure applied to the other two-dimensional material is locally increased. Thus, the other two-dimensional material can be efficiently chopped and peeled apart. And the ion crystal is ground and uniformly distributed on the surface of another two-dimensional material. After further calcination treatment in a certain atmosphere, the dispersed ionic crystals are decomposed into corresponding two-dimensional materials, which are also characterized by small size and thin layer. The heterogeneous compound has small two-dimensional size, enlarged interlayer spacing and accelerated ion and electron transmission rate, thereby increasing the specific capacity of active reaction sites and materials. The ball milling process generates certain impact force to ensure that the two substances are in close contact, and the transmission capability of the charges in the two media is improved, so that the multiplying power performance of the electrode material is improved. The corresponding two-dimensional material has a thin-layer structure, so that the flexibility of the material is increased, and the capacity of the material for resisting the volume effect in the charging and discharging process is improved, thereby improving the cycling stability of the electrode material.
The invention relates to a method for efficiently preparing a heterogeneous layered composite material for a lithium ion battery cathode material by using a ball milling method, which comprises the following steps of:
(1) according to a certain mass ratiox:1 weighing a precursor of the first two-dimensional material and the second two-dimensional material, placing the two-dimensional material and the precursor into a ball milling tank, wherein the mass ratio of 1/5 is less than or equal toxLess than or equal to 5; wherein the precursor of the first two-dimensional material is ammonium thiomolybdate (NH)4)2MoS4Or ammonium molybdate (NH)4)2MoO4The second two-dimensional material is MoS2，MoO3Or expanded graphite.
(2) According to the mass ratio of ball materials ofy：（x+ 1) putting ball grinding ball, y is more than or equal to 3 and less than or equal to 30.
(3) The ball milling beads have two sizes of 2 mm and 5 mm respectively, and the mass ratio of the two beads isz:1, wherein 1/8 is less than or equal toz≤8。
(4) Packaging the ball milling tank, and carrying out ball milling in a planetary ball mill at the rotating speed of 200-500 r.min-1The ball milling time is 5-15 h.
(5) And opening the ball milling tank after the ball milling is finished, and separating the ball milling tank from the ball milling beads to obtain the precursor compound with small size and ordered stacking.
(6) Roasting the precursor composite with small size and ordered stacking in nitrogen atmosphere to obtain heterogeneous layered compound composite material, decomposing the precursor of the first two-dimensional material after roasting to generate corresponding two-dimensional material, namely the first two-dimensional material, wherein the first two-dimensional material also has the characteristics of small size and thin layer, realizing staggered stacking with the second two-dimensional material and mutually preventing aggregation.
Example 1:
respectively weighing 1.25 g of ammonium thiomolybdate and 0.25 g of expanded graphite powder, and adding the weighed materials into a ball-milling tank; and additionally weighing 90 g of 2 mm and 5 mm agate balls, wherein the mass ratio of the two balls is 3: 1; the ball milling can is packaged and ball milling is carried out on a planetary ball mill; setting the rotating speed of the ball mill to 400 r.min-1Separating agate balls after ball milling for 14 h to obtain a compound assembled by ammonium thiomolybdate and few layers of carbon, roasting in nitrogen for 4 h, and decomposing the ammonium thiomolybdate into MoS2Obtaining the small-size and few-layer MoS2Composites with few layers of carbon. FIG. 2 is a transmission electron micrograph of the resulting composite showing the composition of the ball milled layered material, showing the smaller size MoS of the few layers visible2The lamina and the few layers of carbon are effectively assembled, so that the expanded graphite is effectively stripped in the ball milling process, and the ammonium thiomolybdate is also small-sized and uniformly distributed on the carbon layer.
The obtained few-layer MoS2the/C compound is used as an electrode material, and is mixed with acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to the mass ratio of 8: 1: 1, mixing, uniformly stirring in a solution of methyl dipyrrolidone (NMP), coating on a copper foil or a carbon paper, and drying in vacuum to prepare the electrode plate. Lithium sheet is used as an electrode, Celgard 2502 membrane is used as a diaphragm, Ethylene Carbonate (EC), dimethyl carbonate (DMC) and lithium hexafluorophosphate (LiPF)6) As an electrolyte, a CR2016 button cell was assembled. Constant current charge and discharge tests are carried out at room temperature within the voltage range of 0.05-3.0V. FIG. 3 shows the battery at 0.5 A.g–1Cycling stability at higher current densities. The specific capacity of the battery reaches 800 mAh.g-1And the specific capacity is still 532 mAh g after circulating for 150 circles-1This compares favorably with the reported data. While pure MoS was ball milled by the same method2The specific capacity attenuation of the obtained product is extremely obvious, and the composite structure of the heterogeneous two-dimensional material obtained by the method has positive significance for improving the lithium storage performance.
Example 2:
respectively weighing 1.25 g of ammonium thiomolybdate and 0.25 g of expanded graphite powder, and adding the weighed materials into a ball-milling tank; 90 g of 5 mm agate balls are weighed and added into a ball milling tank; the ball milling can is packaged and ball milling is carried out on a planetary ball mill; setting the rotating speed of the ball mill to 400 r.min-1Separating agate balls after ball milling for 14 h to obtain a compound assembled by ammonium thiomolybdate and few layers of carbon, roasting in nitrogen for 4 h, and decomposing the ammonium thiomolybdate into MoS2Obtaining MoS2A carbon/carbon composite. MoS in the samples obtained under these conditions2Larger size of (a) than example 1, and larger thickness of the carbon layer, indicating that the pure 5 mm ball milling beads could not be stripped and crushed to a certain size limit.
The test as the electrode material of the lithium ion battery shows that: at 0.5 A.g–1The specific capacity of the battery reaches 720 mAh.g under the current density of the battery-1But the attenuation is more pronounced.
Example 3:
1.25 g of ammonium thiomolybdate and 0.25 g of expanded graphite powder were weighed out and addedIn a ball milling tank; and additionally weighing 90 g of 2 mm and 5 mm agate balls, wherein the mass ratio of the two agate balls is controlled to be 6: 1, adding the mixture into a ball milling tank; the ball milling can is packaged and ball milling is carried out on a planetary ball mill; setting the rotating speed of the ball mill to 400 r.min-1Separating agate balls after ball milling for 14 h to obtain a compound assembled by ammonium thiomolybdate and few layers of carbon, roasting in nitrogen for 4 h, and decomposing the ammonium thiomolybdate into MoS2Obtaining MoS2A carbon/carbon composite. MoS in the samples obtained under these conditions2The size of the carbon is small, the thickness is thin, carbon is effectively stripped, and the carbon are compounded uniformly.
The test as the electrode material of the lithium ion battery shows that: at 0.5 A.g–1The specific capacity of the battery reaches 820 mAh g under the current density of-1The specific capacity of the battery is 490 mAh g after 150 circles-1And about 80% of the specific discharge capacity at the second time.
Example 4:
respectively weighing 1.25 g of ammonium thiomolybdate and 0.69 g of molybdenum trioxide powder, and adding the mixture into a ball milling tank; 58.2 g of 2 mm agate balls are weighed and added into a ball milling tank; the ball milling can is packaged and ball milling is carried out on a planetary ball mill; setting the rotating speed of the ball mill to 400 r.min-1Separating agate balls after ball milling for 14 h to obtain a compound assembled by ammonium thiomolybdate and few layers of carbon, roasting in nitrogen for 4 h, and decomposing the ammonium thiomolybdate into MoS2Obtaining the few-layer MoS2And few layers of MoO3The complex of (1). MoS in the samples obtained under these conditions2Has a small size and a thin thickness of MoO3Is effectively stripped, and the two are uniformly compounded.
The test as the electrode material of the lithium ion battery shows that: at 0.2 A.g–1The specific capacity of the battery reaches 924 mAh.g under the current density of (A)-1The specific capacity of the battery is 700 mAh g after 100 circles-1And has higher capacity retention rate.
Example 5:
respectively weighing 0.84 g of ammonium molybdate and 0.77 g of molybdenum disulfide powder, and adding the ammonium molybdate and the molybdenum disulfide powder into a ball milling tank; weighing 48.6 g of 2 mm agate balls, and adding the agate balls into a ball milling tank; the ball milling can is packaged and ball milling is carried out on a planetary ball mill; is provided with a ball millThe rotating speed is 400 r.min-1Separating agate balls after ball milling for 14 h to obtain a compound assembled by ammonium thiomolybdate and few layers of carbon, roasting in oxygen for 4 h, and decomposing ammonium molybdate into MoO3Obtaining the few-layer MoS2And few layers of MoO3The complex of (1). MoS in the samples obtained under these conditions2Has small size, thin thickness, small amount of oxidation at the edge, and MoO3Is effectively stripped, and the two are uniformly compounded.
The test as the electrode material of the lithium ion battery shows that: calcination of MoS in oxygen2Is partially oxidized and is reacted with MoO3Few layers are orderly compounded, so that the product has special structure and composition. When used as the negative electrode material of the lithium ion battery, the lithium ion battery has particularly high initial specific capacity of 0.2 A.g–1The initial specific capacity of the battery is up to 1800 mAh.g at the current density of (A)-1Followed by some attenuation.
In the above embodiment, the impact force and the shearing force generated in the ball milling process are used to crush and strip the precursor, the first two-dimensional material in the ball milling process is added in the form of salt, and the salt is an ionic crystal, which can be converted into a corresponding two-dimensional material in the subsequent roasting treatment process, and has the characteristics of high hardness, sharp edges and corners and the like. Therefore, in the ball milling process, the ball milling device can be used as a ball milling medium to transfer ball milling impact force and shearing force, so that the local pressure born by the second two-dimensional material is increased, and the second two-dimensional material is crushed and stripped. In the ball milling process, the proportion of two ball milling beads with different sizes is controlled, so that the primary chopping and stripping functions of the large beads are fully exerted, the small beads fill the ball milling gaps of the large beads, the material is further finely ground and thinned, and the primary compounding of two-dimensional materials is efficiently realized. And (3) performing further roasting treatment in an inert atmosphere to obtain the lithium ion battery cathode material with two heterogeneous layered compounds orderly compounded. The composite material has a loose structure, reaction sites are fully exposed, and the transmission capability of charges in two mediums can be improved, so that the rate capability of the electrode material is improved. The two-dimensional material exists in a thin layer or small-size form, so that the flexibility of the material is improved, and the capacity of the material for resisting the volume effect in the charging and discharging processes is improved, so that the cycling stability of the electrode material is improved. The ball milling process used in the invention has the advantages of simple preparation conditions, high yield, low cost and easy scale-up production.
The above-described specific embodiments are merely preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, various modifications or substitutions can be made without departing from the principle of the present invention, and these modifications or substitutions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing heterogeneous layered composite material by using a ball milling method is characterized by comprising the following steps:
(1) weighing a precursor of a first two-dimensional material and a second two-dimensional material in a certain mass ratio, and uniformly mixing;
(2) ball-milling the mixture to obtain a precursor compound with small size and ordered stacking;
(3) and roasting the precursor composite in a nitrogen atmosphere to obtain the heterogeneous layered compound composite material.
2. The method of claim 1, wherein the molar ratio of the precursor of the first two-dimensional material to the second two-dimensional material isx1, wherein 1/5 is less than or equal tox≤5。
3. The method of claim 1, wherein the precursor of the first two-dimensional material is ammonium thiomolybdate (NH)4)2MoS4Or ammonium molybdate (NH)4)2MoO4。
4. The method of claim 1, wherein the second two-dimensional material is MoS2、MoO3Or expanded graphite.
5. The method of claim 1, wherein the ball-to-material ratio is at ball millingy：(x + 1), wherein 3 is less than or equal toyLess than or equal to 30; the ball milling time is5-15 h; the ball milling speed is 200-500 r.min-1。
6. The method of claim 1, wherein the ball milling media are 2 mm or 5 mm beads.
7. The method of claim 1, wherein the ball milling media is 2 mm and 5 mm mixed beads, and the mass ratio of the two beads isz:1, wherein 1/8 is less than or equal toz≤8。
8. The method of claim 1, wherein the temperature rise rate of the roasting is 2 ℃/min, the roasting temperature is 400 ℃ to 700 ℃, and the roasting time is 2 h to 6 h.
9. A heterogeneous layered composite prepared according to the method of any one of claims 1 to 8.
10. Use of the heterogeneous layered composite prepared according to the method of any one of claims 1 to 8 as a negative electrode material for lithium ion batteries.
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