CN113659141A - SiO @ Mg/C composite material and preparation method and application thereof - Google Patents
SiO @ Mg/C composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- -1 aryl carboxylic acid Chemical class 0.000 claims abstract description 13
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims 2
- 239000012046 mixed solvent Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 210000001787 dendrite Anatomy 0.000 abstract 1
- 239000012917 MOF crystal Substances 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006138 lithiation reaction Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003756 stirring Methods 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a SiO @ Mg/C composite material and a preparation method and application thereof. Adjusting the pH value of a mixed solution containing polybasic aryl carboxylic acid and magnesium salt to acidity, transferring the mixed solution into a high-pressure reaction kettle, and carrying out solvothermal reaction to obtain a Mg-MOF metal organic framework material; mixing the Mg-MOF metal organic framework material with SiO by ball milling to obtain a Mg-MOF/SiO mixture; and (3) placing the Mg-MOF/SiO mixture in a protective atmosphere, and calcining to obtain the SiO @ Mg/C composite material. The SiO @ Mg/C composite material can effectively inhibit SiO volume expansion, reduce lithium ion consumption and lithium dendrite generation, and therefore effectively improve the first coulombic efficiency and cycle performance of the lithium ion battery.
Description
Technical Field
The invention relates to a lithium ion battery cathode material. In particular to a SiO @ Mg/C composite negative electrode material, a preparation method of the SiO @ Mg/C composite material and application of the SiO @ Mg/C composite material as a negative electrode material of a lithium ion battery, belonging to the technical field of lithium batteries.
Background
With the rapid development of portable electronic devices, unmanned aerial vehicles, electric tools, and electric vehicles, rechargeable batteries with high energy density, high power density, high safety, and long life span have received much attention. Although lithium ion batteries based on conventional graphite negative electrode materials have achieved widespread use, their relatively low theoretical energy density has limited their further development. Finding alternative materials for graphite anodes is becoming the key to current secondary battery research.
Silicon is the lithium ion battery anode material with the highest known specific capacity (4200mAh), but the electrochemical performance is sharply deteriorated due to the huge volume effect (> 300%). Therefore, silicon oxide having a small volume effect is a more desirable choice. Among them, the volume effect (150%) of the silicon oxide (SiO) is small, and at the same time, the silicon oxide (SiO) has a high theoretical capacity (>1500mAh), and becomes a hot spot for the research of the negative electrode material of the lithium ion battery in recent years.
Although the volume effect of the silicon oxide (SiO) is smaller than that of silicon, the cycling performance and the first coulombic efficiency of the silicon oxide (SiO) are poorer, and in order to improve the cycling performance and the first coulombic efficiency of the silicon oxide (SiO), researches show that the carbon material is coated on the surface of the silicon oxide (SiO) to be used as an expansion buffer layer, and the pre-lithiation treatment on the silicon oxide (SiO) material can greatly improve the cycling performance and the first coulombic efficiency of the silicon oxide (SiO).
Such as: chinese patent (CN 112820863A) provides a method for modified carbon-coated prelithiation, and the first coulombic efficiency of the method reaches 88 percent. Chinese patent (CN201710838388.6) provides an electrochemical pre-lithium technology, a semi-cell model is assembled by prefabricating a silica material cathode plate and a metal lithium plate, pre-lithiation is carried out in a mode of discharging the cell to the outside, and the first cycle efficiency of the pre-lithiated silica material can reach more than 90%. In the method of "Enabling SiOx/C anode with high initial catalytic reaction for high energy of a chemical pre-lithiation reaction-on bases" published by Ming-Yan Yan Yan, et al, the pre-lithiation reaction is carried out by dissolving a lithium sheet in an organic solvent in advance, then adding a silica material to carry out the pre-lithiation reaction, and finally calcining to obtain the pre-lithiated silica material, wherein the first efficiency can reach 90%. However, these methods have problems that they are expensive and difficult to industrialize.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a SiO @ Mg/C composite material, the composite material is formed by uniformly coating a Mg/C composite on the surface of a silicon monoxide particle, and the Mg/C composite is formed by a porous carbon framework and a simple substance magnesium uniformly distributed in the porous carbon framework, so that the expansion of the silicon monoxide particle (SiO) in the charging process can be effectively inhibited, the consumption of a lithium source by an SEI film can be continuously and effectively reduced, the generation of lithium crystal branches is reduced, and the service life of a battery material is prolonged.
The second purpose of the invention is to provide a preparation method of the SiO @ Mg/C composite material, which is simple to operate, low in cost and beneficial to large-scale production.
The third purpose of the invention is to provide an application of the SiO @ Mg/C composite material as a lithium ion battery cathode material, and the application of the SiO @ Mg/C composite material in a lithium ion battery can effectively improve the first coulombic efficiency and the cycle performance of the lithium ion battery.
In order to achieve the technical purpose, the invention provides a preparation method of a SiO @ Mg/C composite material, which comprises the following steps:
1) adjusting the pH value of a mixed solution containing polybasic aryl carboxylic acid and magnesium salt to acidity, transferring the mixed solution into a high-pressure reaction kettle, and carrying out solvothermal reaction to obtain a Mg-MOF metal organic framework material;
2) mixing the Mg-MOF metal organic framework material with SiO by ball milling to obtain a Mg-MOF/SiO mixture;
3) and placing the Mg-MOF/SiO mixture in a protective atmosphere, and calcining to obtain the Mg-MOF/SiO composite material.
According to the technical scheme, firstly, polybasic aryl carboxylic acid and magnesium salt are used as raw materials, a solvent thermal method is used for forming a Mg-MOF metal organic framework material, in the solvent thermal method process, the polybasic aryl carboxylic acid and divalent magnesium ions form the Mg-MOF metal organic framework material which is regular in appearance and has a three-dimensional porous structure in a special coordination mode, the Mg-MOF metal organic framework material and SiO are uniformly mixed and then calcined, the Mg-MOF metal organic framework material forms a uniform coating layer on the surface of the SiO, meanwhile, the Mg-MOF metal organic framework material is pyrolyzed at high temperature to form a regular porous carbon framework, and metal magnesium is uniformly distributed in the porous carbon framework in an atomic state. The porous carbon frame can effectively inhibit the volume change of SiO during charging and discharging, and the stability of the negative electrode SEI film is improved. The characteristic defect of the silicon monoxide material as the battery cathode material is mainly caused by the oxygen component in the material, and a large amount of Li source is consumed by the SEI film and the lithium silicate material during the formation process, so that the initial coulombic efficiency of the material is low. Magnesium uniformly distributed in the porous carbon skeleton can react preferentially to form an SEI film and a magnesium silicate substance, so that the consumption of a lithium source is reduced, and the first coulombic efficiency of the material is improved.
Preferably, the molar ratio of the polybasic aryl carboxylic acid to the magnesium salt is 2: 8-4: 6, and the magnesium salt can be common water-soluble magnesium salt, and can be common magnesium nitrate and the like. The molar ratio of the polybasic aryl carboxylic acid to the magnesium salt is more preferably 3: 7.
As a preferred scheme, the polybasic aryl carboxylic acid comprises at least one of benzene dicarboxylic acid, biphenyl dicarboxylic acid, benzene hexacarboxylic acid, 2, 5-dihydroxy terephthalic acid, benzene tricarboxylic acid and benzene tetracarboxylic acid. Most preferably 2, 5-dihydroxyterephthalic acid. All of the polyaryl carboxylic acids can form Mg-MOF metal organic framework materials with magnesium ions, and the preferably adopted 2, 5-dihydroxyterephthalic acid is relatively common and cheap, and the prepared Mg-MOF metal organic framework materials have stable three-dimensional honeycomb structures.
Preferably, the pH of the mixed solution containing the polybasic aryl carboxylic acid and the magnesium salt is adjusted to 2-5. The pH value mainly influences the growth speed of the crystal and the appearance of the crystal, the crystal growth is inhibited when the pH value is too low, the crystal growth speed is too slow, and the crystal is difficult to form when the pH value is too high. The pH value is adjusted by adopting a common alkali reagent, such as at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide and triethylamine. The addition of the alkali reagent can neutralize the acidity of the reaction system, the pH value of the reaction system is adjusted to 2-5, the growth speed of Mg-MOF crystals can be accelerated, and the appearance of the crystals can be controlled. The balance point of the growth speed and the crystal morphology within the pH range of 2-5 is optimal within the pH range; further preferably, the pH value is adjusted to 2.5 to 4.5.
As a preferred embodiment, the solvothermal reaction conditions are: the temperature is 100-200 ℃, and the time is 12-72 h. The temperature of the solvothermal reaction is further preferably 125-200 ℃; the time is more preferably 14 to 20 hours.
As a preferable scheme, the mass percentage of the Mg-MOF metal organic framework material to the SiO is 5-20% to 80-95%. Further preferably, the proportion of the Mg-MOF metal organic framework material is 5-10%; the ratio of the SiO material is 90-95%.
As a preferred embodiment, the calcination conditions are: the temperature is 500-1200 ℃ and the time is 1-4 h. If the calcination temperature is too low, carbonization of the Mg-MOF metal-organic framework material is incomplete, and if the temperature is too high, disproportionation reaction of SiO occurs. The heating rate in the calcining process is 3-8 ℃, and the control of the lower heating rate is beneficial to keeping the skeleton morphology of the Mg-MOF metal organic framework material in the carbonizing process. The more preferable calcination temperature is 600 to 900 ℃. The more preferable calcination time is 2 to 3 hours.
Preferably, the ball milling and mixing time is 1 to 6 hours.
The invention also provides a SiO @ Mg/C composite material which is prepared by the preparation method.
As a preferable scheme, the SiO @ Mg/C composite material is formed by uniformly coating a Mg/C composite material on the surface of a silicon oxide; the Mg/C composite material is formed by uniformly distributing metal magnesium in a porous carbon framework.
The invention also provides an application of the SiO @ Mg/C composite material, which is applied as a lithium ion battery cathode material.
The SiO @ Mg/C composite material is used for a lithium ion battery: the SiO @ Mg/C composite material comprises the following components in percentage by mass: mixing the SiO @ Mg/C composite material (80-95%), the conductive agent SP (2-10%), the binder SBR (2-5.5%), the thickening agent CMC (1-4.5%), adding deionized water, uniformly stirring to prepare slurry with the viscosity of 2500-3500 CPS, and then assembling the slurry and lithium sheets in a glove box to form the button cell.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the SiO @ Mg/C composite material provided by the invention can effectively inhibit the expansion of the silicon monoxide particles in the charging process, can continuously and effectively slow down the consumption of an SEI film on a lithium source, and simultaneously reduces the generation of lithium crystal branches and prolongs the service life of a battery material.
The preparation method of the SiO @ Mg/C composite material provided by the invention is simple to operate, low in cost and beneficial to large-scale production.
The SiO @ Mg/C composite material provided by the invention is applied as a lithium ion battery cathode material, and can effectively improve the first coulombic efficiency and the cycle performance of the lithium ion battery.
Drawings
FIG. 1 is a scanning electron micrograph of the SiO @ Mg/C composite prepared in example 1;
fig. 2 to 5 are charge and discharge curves of button cells made of the SiO @ Mg/C composite material according to examples 1 to 4, respectively.
Detailed description of the preferred embodiments
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
All the raw materials and reagents in the following examples are commercially available conventional raw materials and reagents unless otherwise specified.
Example 1
The embodiment provides a preparation method of a composite silicon oxide (SiO @ Mg/C) anode material, which comprises the following steps:
1)0.111g of 2, 5-dihydroxyterephthalic acid and 0.456g of Mg (NO)3)2·6H2O was dissolved in 100mL of a mixed solution of N, N-dimethyldiamide, ethanol and water (15:1:1), and 0.12mL of triethylamine was added. Packaging the mixed solution into a hydrothermal reaction kettle, and reacting for 20 hours at 125 ℃. And naturally cooling to room temperature after reaction, washing the obtained product with DMF for three times, then washing the product with deionized water for three times, and drying the product in an oven at 100 ℃ overnight to obtain the Mg-MOF crystal.
2) Grinding and crushing the Mg-MOF crystals, and mixing the Mg-MOF crystals with the following raw materials in mass ratio: and weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the proportion of 1:9, uniformly mixing, and mechanically milling for 1h to obtain the Mg-MOF/SiO mixed material.
3) And (3) putting the Mg-MOF/SiO mixed material into a crucible, carbonizing at the high temperature of 600 ℃ for 2h in a tubular furnace under the protection of nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain the product composite silicon monoxide (SiO @ Mg/C) negative electrode material.
Example 2
1)0.111g of 2, 5-dihydroxyterephthalic acid and 0.456g of Mg (NO)3)2·6H2O was dissolved in 100mL of a mixed solution of N, N-dimethyldiamide, ethanol and water (15:1:1), and 0.12mL of triethylamine was added. Packaging the mixed solution into a hydrothermal reaction kettle, and reacting for 20 hours at the temperature of 150 ℃. And naturally cooling to room temperature after reaction, washing the obtained product with DMF (dimethyl formamide), washing with deionized water, and drying in an oven at 100 ℃ overnight to obtain the Mg-MOF crystal.
2) Grinding and crushing the Mg-MOF crystals, and mixing the Mg-MOF crystals with the following raw materials in mass ratio: and weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the proportion of 1:9, uniformly mixing, and mechanically milling for 2h to obtain the Mg-MOF/SiO mixed material.
3) And (3) putting the Mg-MOF/SiO mixed material into a crucible, carbonizing at the high temperature of 900 ℃ for 1h in a tubular furnace under the protection of nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain the product composite silicon monoxide (SiO @ Mg/C) negative electrode material.
Example 3
1)0.111g of 2, 5-dihydroxyterephthalic acid and 0.456g of Mg (NO)3)2·6H2O was dissolved in 100mL of a mixed solution of N, N-dimethyldiamide, ethanol and water (15:1:1), and 0.12mL of triethylamine was added. Packaging the mixed solution into a hydrothermal reaction kettle, and reacting for 20 hours at the temperature of 200 ℃. And naturally cooling to room temperature after reaction, washing the obtained product with DMF (dimethyl formamide), washing with deionized water, and drying in an oven at 100 ℃ overnight to obtain the Mg-MOF crystal.
2) Grinding and crushing the Mg-MOF crystals, and mixing the Mg-MOF crystals with the following raw materials in mass ratio: and weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the proportion of 1:9, uniformly mixing, and mechanically milling for 3h to obtain the Mg-MOF/SiO mixed material.
3) And (3) putting the synthesized Mg-MOF/SiO mixed material into a crucible, carbonizing at the high temperature of 900 ℃ for 4h in a tubular furnace under the protection of nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and naturally cooling to the room temperature to obtain the product composite silicon monoxide (SiO @ Mg/C) negative electrode material.
Example 4
1)0.111g of 2, 5-dihydroxyterephthalic acid and 0.456g of Mg (NO)3)2·6H2O was dissolved in 100mL of a mixed solution of N, N-dimethyldiamide, ethanol and water (15:1:1), and 0.12mL of triethylamine was added. Packaging the mixed solution into a hydrothermal reaction kettle, and reacting for 20 hours at the temperature of 200 ℃. And naturally cooling to room temperature after reaction, washing the obtained product with DMF (dimethyl formamide), washing with deionized water, and drying in an oven at 100 ℃ overnight to obtain the Mg-MOF crystal.
2) Grinding and crushing the Mg-MOF crystals, and mixing the Mg-MOF crystals with the following raw materials in mass ratio: and weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the proportion of 1:9, uniformly mixing, and mechanically milling for 3h to obtain the Mg-MOF/SiO mixed material.
3) And (3) putting the synthesized Mg-MOF/SiO mixed material into a crucible, carbonizing at 1200 ℃ for 2h in a tubular furnace under the protection of nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain the product composite silicon monoxide (SiO @ Mg/C) negative electrode material.
The materials obtained in the four embodiments are respectively made into button cells, and electrochemical performance tests are carried out: the materials obtained in the above examples 1, 2 and 3 were mixed in proportion of SiO @ Mg/C (85%), conductive agent SP (10%), binder SBR (3.5%), thickener CMC (1.5%), coated, sliced, and assembled into a 2025 button-type lithium ion battery in a glove box. The electrolyte is 1mol/L LiPF6/(EC + DMC), and the diaphragm is Celgard2400 membrane.
The assembled battery was subjected to a constant current charge-discharge experiment using a chanhe battery program-controlled tester of wuhan blue-electron company LANHE.
FIG. 1 is an SEM representation of SiO @ Mg/C material. Fig. 2 to 5 are charge and discharge curves of the button cell made of the SiO @ Mg/C composite material prepared in examples 1 to 4 at a magnification of 0.1C at 25 ℃.
The first discharge specific capacity of the button cell made of the SiO @ Mg/C composite material in the embodiment 1 can reach 1666.7mAh/g, the reversible specific capacity is also up to 1525.5mAh/g, and the first coulombic efficiency is 91.5%.
The first discharge specific capacity of the button cell made of the SiO @ Mg/C composite material in the embodiment 2 can reach 1888.1mAh/g, the reversible specific capacity is also 1717.4mAh/g, and the first coulombic efficiency is 90.95%.
The first discharge specific capacity of the button cell made of the SiO @ Mg/C composite material in the embodiment 3 can reach 1734.9mAh/g, the reversible specific capacity is also up to 1544.5mAh/g, and the first coulombic efficiency is 89.02%.
The first discharge specific capacity of the button cell made of the SiO @ Mg/C composite material in the embodiment 4 is 1655.9mAh/g, the reversible specific capacity is 1236.6mAh/g, and the first coulombic efficiency is 74.68%. In example 4, when the calcination temperature was too high, a part of the active material, silica, was lost, resulting in a decrease in electrochemical performance.
Table 1 shows the capacity retention data of 200 cycles of the foregoing three examples of the button cell made of SiO @ Mg/C material at a current density of 0.5C and a temperature of 25 ℃, and it can be seen from table 1 that the capacity attenuation of the battery made of SiO @ Mg/C material in examples 1 to 3 is small. The SiO @ Mg/C material lithium battery cathode material provided by the invention can be applied to a battery, so that the cycling stability of the battery can be improved, and the service life of the battery can be prolonged.
TABLE 1
Claims (10)
1. A preparation method of a SiO @ Mg/C composite material is characterized by comprising the following steps: the method comprises the following steps:
1) adjusting the pH value of a mixed solution containing polybasic aryl carboxylic acid and magnesium salt to acidity, transferring the mixed solution into a high-pressure reaction kettle, and carrying out solvothermal reaction to obtain a Mg-MOF metal organic framework material;
2) mixing the Mg-MOF metal organic framework material with SiO by ball milling to obtain a Mg-MOF/SiO mixture;
3) and placing the Mg-MOF/SiO mixture in a protective atmosphere, and calcining to obtain the Mg-MOF/SiO composite material.
2. The method for preparing the SiO @ Mg/C composite material according to claim 1, wherein the method comprises the following steps: the molar ratio of the polybasic aryl carboxylic acid to the magnesium salt is 2: 8-4: 6;
the magnesium salt is magnesium nitrate;
the polybasic aryl carboxylic acid comprises at least one of benzene dicarboxylic acid, biphenyl dicarboxylic acid, mellitic acid, 2, 5-dihydroxyterephthalic acid, trimesic acid and benzene tetracarboxylic acid.
3. The method for preparing the SiO @ Mg/C composite material according to claim 1, wherein the method comprises the following steps: the solvent in the mixed solution containing the polybasic aryl carboxylic acid and the magnesium salt is a mixed solvent of N, N-dimethylformamide, ethanol and water; wherein the volume ratio of the N, N-dimethylformamide to the ethanol to the water is 10-20: 1: 1.
4. The method for preparing the SiO @ Mg/C composite material according to claim 1, wherein the method comprises the following steps: the pH value of the mixed solution containing the polybasic aryl carboxylic acid and the magnesium salt is adjusted to 2-5.
5. The method for preparing the SiO @ Mg/C composite material according to claim 1, wherein the method comprises the following steps: the conditions of the solvothermal reaction are as follows: the temperature is 100-200 ℃, and the time is 12-72 h.
6. The method for preparing the SiO @ Mg/C composite material according to claim 1, wherein the method comprises the following steps: the mass percentage of the Mg-MOF metal organic framework material to the SiO is 5-20 percent and 80-95 percent.
7. The method for preparing the SiO @ Mg/C composite material according to claim 1, wherein the method comprises the following steps: the calcining conditions are as follows: the temperature is 500-1200 ℃ and the time is 1-4 h.
8. A SiO @ Mg/C composite material is characterized in that: the preparation method of any one of claims 1 to 7.
9. A SiO @ Mg/C composite material according to claim 8, wherein: the coating is formed by uniformly coating a Mg/C composite material on the surface of the silicon oxide; the Mg/C composite material is formed by uniformly distributing metal magnesium in a porous carbon framework.
10. Use of a SiO @ Mg/C composite material according to claim 8 or 9, characterized in that: the material is applied as a negative electrode material of a lithium ion battery.
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| WO2023001213A1 (en) * | 2021-07-23 | 2023-01-26 | 湖南金硅科技有限公司 | Sio@mg/c composite material, and preparation method therefor and application thereof |
| WO2023202189A1 (en) * | 2022-04-22 | 2023-10-26 | 贝特瑞新材料集团股份有限公司 | Negative electrode material and preparation method therefor, and lithium-ion battery |
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