CN113659141B - 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 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- -1 poly-aryl carboxylic acid Chemical class 0.000 claims abstract description 13
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 79
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 73
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 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
- 238000000034 method Methods 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 239000007773 negative electrode material Substances 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
- 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
- 238000004519 manufacturing process Methods 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
- 239000003054 catalyst Substances 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
- 239000002904 solvent Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 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
- 239000010405 anode material Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000006138 lithiation reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 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
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 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
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising 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
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 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
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase 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
- 238000001000 micrograph Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a SiO@Mg/C composite material and a preparation method and application thereof. The pH value of the mixed solution containing the poly-aryl carboxylic acid and the magnesium salt is regulated to be acidic, and then the mixed solution is transferred into a high-pressure reaction kettle to carry out solvothermal reaction to obtain the Mg-MOF metal organic frame material; mixing the Mg-MOF metal organic framework material with SiO through 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 the volume expansion of SiO, reduce the consumption of lithium ions and the generation of lithium dendrites, and further effectively improve the first coulomb efficiency and the 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, and belongs 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 having high energy density, high power density, high safety, and long life are attracting attention. Although lithium ion batteries based on conventional graphite negative electrode materials have found wide application, their relatively low theoretical energy density has limited their further development. Searching for alternative materials for graphite negative electrodes is a key to current secondary battery research.
Silicon is the lithium ion battery anode material with the highest specific capacity (4200 mAh) currently known, but the electrochemical performance is drastically deteriorated due to its huge volume effect (> 300%). Therefore, silicon oxide with smaller volume effect is a desirable choice. The silicon oxide (SiO) has small volume effect (150%) and high theoretical capacity (> 1500 mAh), and becomes a hot spot for researching lithium ion battery cathode materials in recent years.
Although the volume effect of the silicon oxide (SiO) is smaller than that of silicon, the cycle performance and the first coulombic efficiency are poorer, and in order to improve the cycle performance and the first coulombic efficiency, the research finds that the carbon material is coated on the surface of the silicon oxide (SiO) as an expansion buffer layer, and the cycle performance and the first coulombic efficiency can be greatly improved by carrying out the pre-lithiation treatment on the silicon oxide (SiO) material.
Such as: chinese patent (CN 112820863 a) provides a modified carbon-coated prelithiation method with a first coulombic efficiency up to 88%. Chinese patent (CN 201710838388.6) provides an electrochemical pre-lithium technology, wherein a half-battery model is assembled by prefabricating a silicon-oxygen material negative electrode plate and a metal lithium plate, pre-lithiation is carried out in a mode of discharging the battery, and the first-week efficiency of the pre-lithiated silicon-oxygen material can reach more than 90%. The lithium is pre-lithiated in a liquid phase mode in the Enabled SiOx/C anode with high initial coulombic efficiency through a chemical pre-lithiation strategy for high energy dDensity lithium-ion batteries published by Ming-Yan et al, the lithium sheet is dissolved in an organic solvent in advance, then a silica material is added for the pre-lithiation reaction, and finally the pre-lithiated silica material is obtained by calcination, wherein the first efficiency can reach 90%. However, these methods have problems of high cost and difficult industrialization.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a SiO@Mg/C composite material, which is formed by uniformly coating Mg/C composite on the surfaces of silicon oxide particles, wherein the Mg/C composite is formed by a porous carbon frame and elemental magnesium uniformly distributed in the porous carbon frame, so that the expansion of the silicon oxide particles (SiO) in the charging process can be effectively inhibited, the consumption of a lithium source by an SEI film can be continuously and effectively slowed down, the generation of lithium crystal branches is reduced, and the service life of a battery material is prolonged.
The second aim 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 mass production.
The third purpose of the invention is to provide an application of the SiO@Mg/C composite material as a negative electrode material of a lithium ion battery, and the application of the SiO@Mg/C composite material in the 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 aim, the invention provides a preparation method of a SiO@Mg/C composite material, which comprises the following steps:
1) The pH value of the mixed solution containing the poly-aryl carboxylic acid and the magnesium salt is regulated to be acidic, and then the mixed solution is transferred into a high-pressure reaction kettle to carry out solvothermal reaction to obtain the Mg-MOF metal organic frame material;
2) Mixing the Mg-MOF metal organic framework material with SiO through ball milling to obtain a Mg-MOF/SiO mixture;
3) And (3) placing the Mg-MOF/SiO mixture in a protective atmosphere, and calcining to obtain the catalyst.
According to the technical scheme, the Mg-MOF metal organic frame material is formed by taking the poly-aryl carboxylic acid and the magnesium salt as raw materials through a solvothermal method, the poly-aryl carboxylic acid and the divalent magnesium ions form the Mg-MOF metal organic frame material which is regular in appearance and has a three-dimensional porous structure through a special coordination mode in the solvothermal method, the Mg-MOF metal organic frame material and SiO are uniformly mixed and then calcined, the Mg-MOF metal organic frame material forms a uniform coating layer on the surface of the SiO, meanwhile, the Mg-MOF metal organic frame material is pyrolyzed at a high temperature to form a regular porous carbon frame, and the metal magnesium is uniformly distributed in the porous carbon frame in an atomic state. The porous carbon frame can effectively inhibit the volume change of SiO during charge and discharge, and the stability of the negative electrode SEI film is improved. The silicon oxide material also has intrinsic defects as a battery anode material, mainly due to the existence of oxygen components in the material, and a large amount of Li sources are consumed in the formation process due to the formation of SEI films and lithium silicate substances, so that the initial coulombic efficiency of the material is low. Magnesium uniformly distributed in the porous carbon skeleton can react preferentially to form SEI film and magnesium silicate substance, so that consumption of lithium source is reduced, and first coulombic efficiency of the material is improved.
As a preferable scheme, 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 magnesium nitrate and the like. The molar ratio of the polybasic aryl carboxylic acid to magnesium salt is more preferably 3:7.
As a preferred embodiment, the polybasic aryl carboxylic acid includes at least one of benzene dicarboxylic acid, biphenyl dicarboxylic acid, benzene hexacarboxylic acid, 2, 5-dihydroxyterephthalic acid, benzene tricarboxylic acid, benzene tetracarboxylic acid. Most preferred is 2, 5-dihydroxyterephthalic acid. These poly aryl carboxylic acids can form Mg-MOF metal organic frame materials with magnesium ions, and the 2, 5-dihydroxyterephthalic acid which is preferably adopted is more common and has low price, and the prepared Mg-MOF metal organic frame materials have stable three-dimensional honeycomb structures.
As a preferred embodiment, the pH of the mixed solution containing the polybasic aryl carboxylic acid and the magnesium salt is adjusted to 2 to 5. The pH value mainly influences the growth speed of the crystal, and also the morphology of the crystal, when the pH value is too low, the crystal growth is inhibited, and when the pH value is too high, the crystal is difficult to form. The pH is regulated by adopting at least one of common alkaline reagents such as sodium hydroxide, potassium hydroxide, lithium hydroxide and triethylamine. The addition of the alkali reagent can neutralize the acidity of the reaction system, adjust the pH value of the reaction system to 2-5, accelerate the growth speed of Mg-MOF crystal and control the morphology of the crystal. The equilibrium point of growth speed and crystal morphology within the ph=2 to 5 range is optimal at this pH range; further preferably, the pH 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 composition of the Mg-MOF metal organic framework material and the SiO is 5% -20%, 80% -95%. Further preferably, the Mg-MOF metal organic framework material accounts for 5% -10%; the SiO material accounts for 90-95 percent.
As a preferred embodiment, the conditions for the calcination 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 may be incomplete, and if the temperature is too high, disproportionation of SiO may occur. The temperature rising rate in the calcining process is 3-8 ℃, and the control of the lower temperature rising rate is favorable for maintaining the skeleton morphology of the Mg-MOF metal organic frame material in the carbonization process. Further preferred calcination temperatures are 600 to 900 ℃. Further preferably, the calcination time is 2 to 3 hours.
As a preferred embodiment, the ball milling mixing time is 1 to 6 hours.
The invention also provides a SiO@Mg/C composite material which is obtained by the preparation method.
As a preferable scheme, the SiO@Mg/C composite material is formed by uniformly coating the Mg/C composite material on the surface of silicon oxide; the Mg/C composite material is formed by uniformly distributing metal magnesium in a porous carbon frame.
The invention also provides application of the SiO@Mg/C composite material, which is applied as a lithium ion battery anode material.
The SiO@Mg/C composite material disclosed by the invention is used for a lithium ion battery: the SiO@Mg/C composite material comprises the following components in percentage by mass: siO@Mg/C composite material (80-95%):conductive agent SP (2-10%):binder SBR (2-5.5%):thickener CMC (1-4.5%) is mixed in proportion, deionized water is added and stirred uniformly to prepare slurry with the viscosity of 2500-3500 CPS, and then the slurry and lithium sheets are assembled into the button cell in a glove box.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the SiO@Mg/C composite material provided by the invention not only can effectively inhibit the expansion of the silicon oxide particles in the charging process, but also can continuously and effectively slow down the consumption of the SEI film on a lithium source, simultaneously reduce the generation of lithium crystal branches and prolong the service life of battery materials.
The preparation method of the SiO@Mg/C composite material provided by the invention is simple to operate, low in cost and beneficial to mass production.
The SiO@Mg/C composite material provided by the invention can be applied to a lithium ion battery cathode material, so that the first coulombic efficiency and the cycle performance of the lithium ion battery can be effectively improved.
Drawings
FIG. 1 is a scanning electron microscope image of the SiO@Mg/C composite material prepared in example 1;
FIGS. 2 to 5 are charge and discharge curves of button cells made of the SiO@Mg/C composite materials of examples 1 to 4, respectively.
Embodiments of the invention
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Unless otherwise indicated, all starting materials and reagents in the examples below were as usual as commercially available.
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 ·6H 2 O was dissolved in 100mL of a mixed solution of N, N-dimethylformamide, ethanol and water (15:1:1), and 0.12mL of triethylamine was added. The mixed solution is packaged into a hydrothermal reaction kettle and reacted for 20 hours at 125 ℃. After the reaction, naturally cooling to room temperature, washing the obtained product with DMF three times, washing with deionized water three times, and drying in a 100 ℃ oven for one night to obtain Mg-MOF crystals.
2) Grinding and crushing the Mg-MOF crystal, and mixing the Mg-MOF crystal with the following components in percentage by mass: and (3) weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the ratio of SiO=1:9, uniformly mixing, and mechanically ball-milling for 1h to obtain the Mg-MOF/SiO mixed material.
3) And (3) loading the Mg-MOF/SiO mixed material into a crucible, carbonizing for 2 hours at a high temperature of 600 ℃ in a tube furnace under the protection of nitrogen atmosphere, heating at a rate of 5 ℃/min, and naturally cooling to room temperature to obtain the composite silicon oxide (SiO@Mg/C) anode material.
Example 2
1) 0.111g of 2, 5-dihydroxyterephthalic acid and 0.456g of Mg (NO 3 ) 2 ·6H 2 O was dissolved in 100mL of a mixed solution of N, N-dimethylformamide, ethanol and water (15:1:1), and 0.12mL of triethylamine was added. Packaging the mixed solution into a hydrothermal reaction kettle, and forming strips at 150 DEG CThe reaction was carried out under the reaction piece for 20 hours. After the reaction, naturally cooling to room temperature, washing the obtained product with DMF, washing with deionized water, and drying in a 100 ℃ oven for one night to obtain Mg-MOF crystals.
2) Grinding and crushing the Mg-MOF crystal, and mixing the Mg-MOF crystal with the following components in percentage by mass: and (3) weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the ratio of SiO=1:9, uniformly mixing, and mechanically ball-milling for 2 hours to obtain the Mg-MOF/SiO mixed material.
3) And (3) loading the Mg-MOF/SiO mixed material into a crucible, carbonizing for 1h at a high temperature of 900 ℃ in a tube furnace under the protection of nitrogen atmosphere, heating at a rate of 5 ℃/min, and naturally cooling to room temperature to obtain the composite silicon oxide (SiO@Mg/C) anode material.
Example 3
1) 0.111g of 2, 5-dihydroxyterephthalic acid and 0.456g of Mg (NO 3 ) 2 ·6H 2 O was dissolved in 100mL of a mixed solution of N, N-dimethylformamide, 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 200 ℃. After the reaction, naturally cooling to room temperature, washing the obtained product with DMF, washing with deionized water, and drying in a 100 ℃ oven for one night to obtain Mg-MOF crystals.
2) Grinding and crushing the Mg-MOF crystal, and mixing the Mg-MOF crystal with the following components in percentage by mass: and (3) weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the ratio of SiO=1:9, uniformly mixing, and mechanically ball-milling for 3 hours to obtain the Mg-MOF/SiO mixed material.
3) And (3) loading the synthesized Mg-MOF/SiO mixed material into a crucible, carbonizing for 4 hours at a high temperature of 900 ℃ in a tube furnace under the protection of nitrogen atmosphere, heating at a rate of 5 ℃/min, and naturally cooling to room temperature to obtain the composite silicon oxide (SiO@Mg/C) anode material.
Example 4
1) 0.111g of 2, 5-dihydroxyterephthalic acid and 0.456g of Mg (NO 3 ) 2 ·6H 2 O was dissolved in 100mL of a mixed solution of N, N-dimethylformamide, 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 200 ℃. Naturally cooling to room temperature after the reaction, washing the obtained product with DMF and then with deionized waterWashing and drying in an oven at 100 ℃ for one night to obtain Mg-MOF crystals.
2) Grinding and crushing the Mg-MOF crystal, and mixing the Mg-MOF crystal with the following components in percentage by mass: and (3) weighing 0.1g of Mg-MOF crystal and 0.9g of SiO respectively according to the ratio of SiO=1:9, uniformly mixing, and mechanically ball-milling for 3 hours to obtain the Mg-MOF/SiO mixed material.
3) And (3) loading the synthesized Mg-MOF/SiO mixed material into a crucible, carbonizing for 2 hours at a high temperature of 1200 ℃ in a tube furnace under the protection of nitrogen atmosphere, heating at a rate of 5 ℃/min, and naturally cooling to room temperature to obtain the composite silicon oxide (SiO@Mg/C) anode material.
The materials obtained in the four embodiments are respectively made into button cells for electrochemical performance test: the materials obtained in example 1, example 2 and example 3 are respectively mixed according to the ratio of SiO@Mg/C (85%):conductive agent SP (10%):binder SBR (3.5%):thickener CMC (1.5%), coated, sliced and assembled into 2025 button type lithium ion battery in a glove box. The electrolyte is LiPF 6/(EC+DMC) with the concentration of 1mol/L, and the diaphragm is Celgard2400 membrane.
And adopting a LANHE battery program control tester of the Wuhan blue electric company to carry out constant current charge and discharge experiments on the assembled battery.
FIG. 1 is an SEM characterization of SiO@Mg/C material. FIGS. 2 to 5 are charge and discharge curves of button cells made of the SiO@Mg/C composite materials prepared in examples 1 to 4 at 25℃and 0.1C magnification, respectively.
The SiO@Mg/C composite material of the embodiment 1 is prepared into a button cell, the first discharge specific capacity can reach 1666.7mAh/g, the reversible specific capacity can reach 1525.5mAh/g, and the first coulomb efficiency is 91.5%.
The SiO@Mg/C composite material of the embodiment 2 can reach a first discharge specific capacity of 1888.1mAh/g, a reversible specific capacity of 1717.4mAh/g and a first coulomb efficiency of 90.95%.
The SiO@Mg/C composite material of the embodiment 3 is prepared into a button cell, the first discharge specific capacity can reach 1734.9mAh/g, the reversible specific capacity can reach 1544.5mAh/g, and the first coulomb efficiency is 89.02%.
The SiO@Mg/C composite material of example 4 is prepared into a button cell with a first discharge specific capacity of 1655.9mAh/g, a reversible specific capacity of 1236.6mAh/g and a first coulomb efficiency of 74.68%. The active material silica fraction at too high a calcination temperature in example 4 is lost, resulting in a decrease in electrochemical performance.
Table 1 shows capacity retention data of 200 cycles of the first three examples at 25℃and 0.5C current density for the SiO@Mg/C button cell, and it can be seen from Table 1 that the capacity fading of the cells made of the SiO@Mg/C material in examples 1 to 3 is small. Namely, 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 (8)
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) The pH value of the mixed solution containing the poly aryl carboxylic acid and the magnesium salt is adjusted to 2-5, and then the mixed solution is transferred into a high-pressure reaction kettle for solvothermal reaction to obtain the Mg-MOF metal organic frame material; the solvothermal reaction conditions are as follows: the temperature is 100-200 ℃ and the time is 12-72 h;
2) Mixing the Mg-MOF metal organic framework material with SiO through ball milling to obtain a Mg-MOF/SiO mixture;
3) And (3) placing the Mg-MOF/SiO mixture in a protective atmosphere, and calcining to obtain the catalyst.
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 poly 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 mass percentage composition of the Mg-MOF metal organic framework material and the SiO is 5% -20%, 80% -95%.
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 calcination are as follows: the temperature is 500-1200 ℃ and the time is 1-4 h.
6. A SiO@Mg/C composite material is characterized in that: obtained by the production process according to any one of claims 1 to 5.
7. The sio@mg/C composite material according to claim 6, wherein: the Mg/C composite material is uniformly coated on the surface of the silicon oxide; the Mg/C composite material is formed by uniformly distributing metal magnesium in a porous carbon frame.
8. Use of a sio@mg/C composite material according to claim 6 or 7, characterized in that: the material is applied as a negative electrode material of a lithium ion battery.
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| CN116083927B (en) * | 2023-02-10 | 2023-08-29 | 江西理工大学 | Uniform pre-magnesia method for silicon oxide anode material and application of uniform pre-magnesia method in lithium ion battery |
| CN117174836A (en) * | 2023-11-03 | 2023-12-05 | 陕西晶泰新能源科技有限公司 | Pre-magnesium intermediate buffer layer of lithium ion battery silicon oxide cathode |
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