CN116364873A - Hard carbon composite material with uniformly dispersed nano silicon dioxide, and preparation method and application thereof - Google Patents
Hard carbon composite material with uniformly dispersed nano silicon dioxide, and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 51
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002210 silicon-based material Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 239000004111 Potassium silicate Substances 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 13
- 235000019353 potassium silicate Nutrition 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- 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
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a hard carbon composite material with evenly dispersed nano silicon dioxide, a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving a soluble silicon-containing compound in water to prepare a solution with the mass concentration of 1-30%; adding a high polymer containing an exchange group into the solution, fully stirring at a rotating speed of 100 rpm-900 rpm until ion exchange is completed, filtering and cleaning the solution, and drying a filtered product to obtain the high polymer containing the silicon group; and heating the high molecular polymer with the silicon-containing group to 800-1200 ℃ at the heating rate of 0.5-5 ℃/min under the environment of protective atmosphere, and preserving the heat for 5-20 hours to obtain the hard carbon composite material containing the nano silicon dioxide.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a hard carbon composite material with uniformly dispersed nano silicon dioxide, a preparation method and application thereof.
Background
With the development of lithium batteries, currently commonly used carbon negative electrode materials mainly comprise various carbon materials such as artificial graphite, natural graphite, carbon nanotubes, hard carbon and the like. The hard carbon material is used as amorphous carbon, has higher reversible capacity, and theoretically reaches 700 mAh/g-1000 mAh/g, and exceeds the theoretical capacity 372mAh/g of graphitized carbon. Meanwhile, as the hard carbon has an irregular structure, the structural stability in the charge and discharge process can be ensured, so that the lithium battery can have longer cycle life and better multiplying power performance. And the silicon dioxide with wide source is used as a negative electrode material, has the theoretical capacity of 1965mAh/g, and can also be used as a potential negative electrode material of a lithium battery.
However, at present, the reversible capacity of the commercial hard carbon material is still low (200 mAh/g-400 mAh/g), and the silicon dioxide needs to be in an amorphous state to be active, for example, won-Seok Chang et al in literature (Quartz SiO2a new energy storage anode material for Li-ion batteries) adopts a ball milling method to prepare nano silicon dioxide, so that the active cathode material is obtained. There are therefore many limitations to the current commercial hard carbon materials.
Although some materials have been able to possess the properties of higher capacity and higher capacity retention, the industry is actively seeking better commercially applicable hard carbon materials with higher capacity and capacity retention that can be obtained by simpler manufacturing methods.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a hard carbon composite material with evenly dispersed nano silicon dioxide, a preparation method and application thereof. The preparation equipment of the hard carbon composite material with uniformly dispersed nano silicon dioxide is simple, the raw material cost is low, the repeatability is good, and the operation is easy. The prepared hard carbon composite material has uniform dispersion of nano silicon dioxide particles, amorphous state and activity. The material can be used for negative electrode materials of lithium batteries or other fields.
In view of the above, the embodiment of the invention provides a method for preparing a hard carbon composite material with uniformly dispersed nano silicon dioxide, which comprises the following steps:
dissolving a soluble silicon-containing compound in water to prepare a solution with the mass concentration of 1-30%;
adding a high polymer containing an exchange group into the solution, fully stirring at a rotating speed of 100 rpm-900 rpm until ion exchange is completed, filtering and cleaning the solution, and drying a filtered product to obtain the high polymer containing the silicon group;
and heating the high molecular polymer with the silicon-containing group to 800-1200 ℃ at the heating rate of 0.5-5 ℃/min under the environment of protective atmosphere, and preserving the heat for 5-20 hours to obtain the hard carbon composite material containing the nano silicon dioxide.
Preferably, the exchange group comprises a sulfonic acid group (-SO) 3 H) Carboxyl (-COOH), quaternary amino (-NR) 3 OH) is provided.
Preferably, the molar ratio of silicon in the soluble silicon-containing compound to the exchange groups in the high molecular polymer containing exchange groups is 0.1:1 to 1:1.
Preferably, the time from the complete stirring to the completion of the ion exchange is 24 to 48 hours.
Preferably, the high molecular polymer includes: one or a combination of several of polystyrene, epoxy resin, urea resin, acrylic resin and polyoxyethylene;
the soluble silicon-containing compound includes: sodium silicate and/or potassium silicate.
Preferably, the protective atmosphere is a nitrogen atmosphere or an argon atmosphere, and the second protective atmosphere is an argon atmosphere.
In a second aspect, an embodiment of the present invention provides a hard carbon composite material prepared by the preparation method of the first aspect, where nano silica particles are uniformly dispersed in the hard carbon composite material;
the particle size of the hard carbon composite material ranges from 0.1nm to 100nm, and the mass content of the nano silicon dioxide in the hard carbon composite material is 1-80%.
Preferably, the hard carbon composite material is formed by ion exchange of a high molecular polymer containing exchange groups and a soluble silicon-containing compoundCarbonizing the high molecular polymer containing silicon groups; the exchange group comprises a sulfonic acid group (-SO) 3 H) Carboxyl (-COOH), quaternary amino (-NR) 3 OH) is provided.
In a third aspect, an embodiment of the present invention provides a negative electrode, where the negative electrode includes the hard carbon composite material described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium battery, where the lithium battery includes the negative electrode described in the third aspect.
The preparation method of the hard carbon composite material with uniformly dispersed nano silicon dioxide has the advantages of simple preparation equipment, low raw material cost, good repeatability and easy operation. The prepared hard carbon composite material has uniform dispersion of nano silicon dioxide particles, amorphous state and activity. The material can be used for negative electrode materials of lithium batteries or other fields.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a flowchart of a method for preparing a hard carbon composite material with uniformly dispersed nano-silica provided by an embodiment of the invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a hard carbon composite material with uniformly dispersed nano-silica provided in example 1 of the present invention;
FIG. 3 is a graph of the dispersion spectrum (EDS) of a hard carbon composite with uniformly dispersed nanosilica provided in example 1 of the present invention;
FIG. 4 is an X-ray diffraction (XRD) pattern of a hard carbon composite with uniformly dispersed nanosilica provided in example 1 of the invention;
fig. 5 is a comparative graph of the charge-discharge curves of the present invention in examples 1 and 2.
Detailed Description
The technical scheme of the invention is further described in detail through the drawings and the embodiments. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.
Fig. 1 is a schematic diagram of a hard carbon composite material with uniformly dispersed nano silica, which is prepared by a preparation process shown in fig. 1. The preparation method comprises the following steps:
specifically, the soluble silicon-containing compound includes: sodium silicate and/or potassium silicate.
specifically, the exchange group includes a sulfonic acid group (-SO) 3 H) Carboxyl (-COOH), quaternary amino (-NR) 3 OH) is provided. The high molecular polymer includes: one or a combination of several of polystyrene, epoxy resin, urea-formaldehyde resin, acrylic resin and polyoxyethylene.
The addition amount of the high molecular polymer containing the exchange group is 0.1:1-1:1 according to the mole ratio of silicate groups in the soluble silicon-containing compound to the exchange groups in the high molecular polymer containing the exchange group.
The time from the complete stirring to the completion of the ion exchange is 24 to 48 hours.
The silicon-containing group in the high molecular polymer of the silicon-containing group includes a silicate in this embodiment. Of course, other silicon-containing groups capable of forming nanosilica after high temperature processing, as known to those skilled in the art from common general knowledge, are also within the scope of the present invention.
And 130, heating the high molecular polymer with the silicon-containing group to 800-1200 ℃ at a heating rate of 0.5-5 ℃/min in a protective atmosphere environment, and preserving the heat for 5-20 hours to obtain the hard carbon composite material containing the nano silicon dioxide.
The protective atmosphere is nitrogen atmosphere or argon atmosphere; the reaction apparatus may be a conventional apparatus such as a high temperature furnace, and is not particularly limited herein.
The hard carbon composite material prepared by the invention is internally and uniformly dispersed with nano silicon dioxide particles; the particle size range of the hard carbon composite material is 0.1 nm-100 nm, and the mass content of the nano silicon dioxide in the hard carbon composite material is 1-80%.
The hard carbon composite material with uniformly dispersed nano silicon dioxide prepared by the invention can be used as a negative electrode material of a lithium ion battery.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the hard carbon composite material containing nano silicon dioxide by applying the method provided by the embodiment of the invention, and the method and the battery characteristics for applying the hard carbon composite material to the lithium ion secondary battery are respectively described in a plurality of specific examples.
Example 1
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 20g of potassium silicate is taken, 1980ml of water is added into the mixture to prepare a solution with the mass concentration of about 1%, 289g of polystyrene containing carboxyl (-COOH) exchange groups (the exchange capacity is about 4.5 mmol/g) is added into the mixture according to the mol ratio of silicon to exchange groups in the high polymer of about 1:1, the mixture is fully stirred for 24 hours at the rotating speed of 100r/min until the ion exchange is completed, the high polymer is filtered and washed for 3 times, and the high polymer containing silicon groups is obtained after drying.
Step 2: and (3) placing the dried sample into a reaction device, heating to 1200 ℃ at a speed of 0.5 ℃/min, and preserving heat for 6 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
SEM and EDS tests are carried out on the hard carbon composite material containing nano silicon dioxide obtained in the embodiment, and FIG. 2 is an SEM diagram of the hard carbon composite material containing nano silicon dioxide provided in the embodiment 1 of the invention, and FIG. 3 is an EDS diagram, wherein the hard carbon particles contain silicon element and are uniformly distributed; fig. 4 is an XRD pattern of the hard carbon composite material containing nano silica provided in example 1 of the present invention, which does not show characteristic peaks of silica, and illustrates that the silica distributed inside the hard carbon composite material reaches a nano level and is in an amorphous state.
Example 2
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of potassium silicate is taken, 6500ml of water is added into the potassium silicate to be dissolved and prepared into a solution with the mass concentration of about 3%, 2890g (about 4.5 mmol/g) of polystyrene containing carboxyl (-COOH) exchange groups is added according to the molar ratio of 0.1:1 of the exchange groups in the silicon to the high polymer, the mixture is fully stirred for 24 hours at the rotating speed of 100r/min until the ion exchange is completed, the high polymer is filtered and washed for 3 times, and the high polymer containing the silicon groups is obtained after drying.
Step 2: and (3) placing the dried sample into a reaction device, heating to 800 ℃ at a speed of 5 ℃/min, and preserving heat for 20 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 3
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of potassium silicate is taken, 800ml of water is added into the potassium silicate to be dissolved and prepared into a solution with the mass concentration of about 20%, 1445g (the exchange capacity is about 4.5 mmol/g) of polystyrene containing carboxyl (-COOH) exchange groups is added according to the molar ratio of 0.5:1 of the exchange groups in the silicon to the high polymer, the mixture is fully stirred for 24 hours at the rotating speed of 100r/min until the ion exchange is completed, the high polymer is filtered and washed for 3 times, and the high polymer containing the silicon groups is obtained after drying.
Step 2: and (3) placing the dried sample into a reaction device, heating to 1000 ℃ at a speed of 2 ℃/min, and preserving heat for 10 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 4
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of potassium silicate is taken, 1800ml of water is added into the potassium silicate to be dissolved and prepared into a solution with the mass concentration of about 10%, 2890g (about 4.5 mmol/g) of polystyrene containing carboxyl (-COOH) exchange groups is added according to the mol ratio of 0.1:1 of the exchange groups in the silicon to the high polymer, the mixture is fully stirred for 24 hours at the rotating speed of 100r/min until the ion exchange is completed, the high polymer is filtered and washed for 3 times, and the high polymer containing the silicon groups is obtained after drying.
Step 2: and (3) placing the dried sample into a reaction device, heating to 1100 ℃ at a speed of 0.5 ℃/min, and preserving heat for 10 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 5
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of sodium silicate is taken, 1800ml of water is added into the sodium silicate to be dissolved and prepared into a solution with the mass concentration of about 10%, 364g (the exchange capacity is about 4.5 mmol/g) of polystyrene containing carboxyl (-COOH) exchange groups is added according to the mol ratio of 1:1 of the exchange groups in the silicon to the high polymer, the mixture is fully stirred for 24 hours at the rotating speed of 100r/min until the ion exchange is completed, the high polymer is filtered and washed for 3 times, and the high polymer containing the silicon groups is obtained after drying.
Step 2: and (3) placing the dried sample into a reaction device, heating to 1100 ℃ at a speed of 5 ℃/min, and preserving heat for 15 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 6
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of sodium silicate is taken and added with 1800ml of water to be dissolved to prepare a solution with the mass concentration of about 10 percent, and quaternary amine groups (-NR) are added according to the mole ratio of 0.5:1 of the silicon to the exchange groups in the high polymer 3 OH) 936g of polystyrene with exchange groups (exchange capacity about 3.5 mmol/g), and stirring for 24 hours at a speed of 100r/min, filtering and washing the high molecular polymer for 3 times after ion exchangeAnd drying to obtain the silicon-containing group high molecular polymer.
Step 2: and (3) placing the dried sample into a reaction device, heating to 1100 ℃ at a speed of 1 ℃/min, and preserving heat for 20 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 7
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of sodium silicate is taken and added with 1800ml of water to be dissolved to prepare a solution with the mass concentration of about 10 percent, and quaternary amine groups (-NR) are added according to the mole ratio of 0.7:1 of the silicon to the exchange groups in the high polymer 3 OH) exchange group of polystyrene 1311g (exchange capacity about 3.5 mmol/g), stirring for 24 hours at a speed of 100r/min, filtering and cleaning the high molecular polymer for 3 times after ion exchange, and drying to obtain the high molecular polymer containing silicon groups.
Step 2: and (3) placing the dried sample into a reaction device, heating to 1050 ℃ at a speed of 5 ℃/min, and preserving heat for 10 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 8
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of potassium silicate is taken and added with 1800ml of water to be dissolved to prepare a solution with the mass concentration of about 10 percent, and quaternary amine groups (-NR) are added according to the mole ratio of 0.1:1 of the silicon to the exchange groups in the high polymer 3 OH) 3715g (exchange capacity about 3.5 mmol/g) of polystyrene with exchange groups, stirring for 24 hours at a rotating speed of 100r/min, filtering and cleaning the high molecular polymer for 3 times after the ion exchange is completed, and drying to obtain the high molecular polymer with silicon groups.
Step 2: and (3) placing the dried sample into a reaction device, heating to 950 ℃ at a speed of 5 ℃/min, and preserving heat for 10 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 9
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of potassium silicate is taken and added with 1800ml of water to be dissolved to prepare a solution with the mass concentration of about 10 percent, and quaternary amine groups (-NR) are added according to the mol ratio of 1:1 of exchange groups in silicon and high polymer 3 372g (exchange capacity about 3.5 mmol/g) of OH) exchange group polystyrene, and fully stirring for 30h at a rotating speed of 200r/min until ion exchange is completed, filtering and cleaning the high molecular polymer for 3 times, and drying to obtain the high molecular polymer containing silicon groups.
Step 2: and (3) placing the dried sample into a reaction device, heating to 900 ℃ at a speed of 5 ℃/min, and preserving heat for 15 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
Example 10
The embodiment provides a preparation method of a hard carbon composite material containing nano silicon dioxide, which comprises the following steps:
step 1: 200g of potassium silicate is taken and added with 1800ml of water to be dissolved to prepare a solution with the mass concentration of about 10 percent, and quaternary amine groups (-NR) are added according to the mole ratio of 0.5:1 of the silicon to the exchange groups in the high polymer 3 OH) 743g (exchange capacity about 3.5 mmol/g) of high molecular polymer of exchange group, stirring for 28h at a rotation speed of 100r/min, filtering and cleaning the high molecular polymer for 3 times after ion exchange is completed, and drying to obtain the high molecular polymer of silicon-containing group.
Step 2: and (3) placing the dried sample into a reaction device, heating to 950 ℃ at a speed of 5 ℃/min, and preserving heat for 20 hours under nitrogen atmosphere for carbonization to obtain the hard carbon composite material containing nano silicon dioxide.
To test the electrochemical properties of the materials prepared in each example, the obtained hard carbon composite material containing nano silicon dioxide was used as a negative electrode material, and was uniformly mixed with carbon black 2% of the total mass (excluding solvent), sodium cellulose 2% and styrene-butadiene rubber 3% in a polyvinylidene fluoride (PVDF) solvent to form a battery slurry, which was coated on a copper foil, dried and cut into wafers having a diameter of 14mm, and vacuum-dried at 100℃for 12 hours and then subjected to a process comprising high-purity Ar gasLiPF with metallic lithium as counter electrode, 1 mol in glove box of atmosphere 6 The solution of (ethylene carbonate (EC)/dimethyl carbonate (DMC) v: v=1:1) was used as an electrolyte to assemble a button cell, and the structure and electrochemical properties thereof were evaluated by the test.
The constant current charge and discharge mode test was used, the discharge cut-off voltage was 0.005V, the charge cut-off voltage was 1.5V, and the charge and discharge test was performed at a C/10 current density. The results are recorded in table 1. Fig. 5 is a comparative graph of the charge-discharge curves of the present invention in the embodiment 1 and the embodiment 2.
TABLE 1
As can be seen from Table 1 and charge-discharge curves, the hard carbon composite material with uniformly dispersed nano silicon dioxide inside has higher first-week charge specific capacity and first-week cycle efficiency. The reversible specific capacity of the material is improved compared with that of the existing commercial hard carbon material by uniformly dispersing the nano silicon dioxide particles inside. The preparation method provided by the invention has the characteristics of simple equipment, low raw material cost, good repeatability, easiness in operation and the like, and the prepared hard carbon-based composite material has uniform dispersion of nano silicon dioxide particles, so that the specific capacity of the hard carbon negative electrode material can be effectively improved.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A method for preparing a hard carbon composite material with evenly dispersed nano silicon dioxide, which is characterized by comprising the following steps:
dissolving a soluble silicon-containing compound in water to prepare a solution with the mass concentration of 1-30%;
adding a high polymer containing an exchange group into the solution, fully stirring at a rotating speed of 100 rpm-900 rpm until ion exchange is completed, filtering and cleaning the solution, and drying a filtered product to obtain the high polymer containing the silicon group;
and heating the high molecular polymer with the silicon-containing group to 800-1200 ℃ at the heating rate of 0.5-5 ℃/min under the environment of protective atmosphere, and preserving the heat for 5-20 hours to obtain the hard carbon composite material containing the nano silicon dioxide.
2. The method for producing a hard carbon composite material according to claim 1, wherein the exchange group includes a sulfonic acid group (-SO) 3 H) Carboxyl (-COOH), quaternary amino (-NR) 3 OH) is provided.
3. The method for producing a hard carbon composite material according to claim 1, wherein a molar ratio of silicon in the soluble silicon-containing compound to the exchange group in the high molecular polymer containing the exchange group is 0.1:1 to 1:1.
4. The method of producing a hard carbon composite material according to claim 1, wherein the time from the completion of the sufficient agitation to the completion of the ion exchange is 24 hours to 48 hours.
5. The method for producing a hard carbon composite material according to claim 1, wherein the high molecular polymer comprises: one or a combination of several of polystyrene, epoxy resin, urea resin, acrylic resin and polyoxyethylene;
the soluble silicon-containing compound includes: sodium silicate and/or potassium silicate.
6. The method for producing a hard carbon composite material according to claim 1, wherein the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
7. A hard carbon composite material prepared by the preparation method according to any one of claims 1 to 6, wherein nano silica particles are uniformly dispersed inside the hard carbon composite material;
the particle size of the hard carbon composite material ranges from 0.1nm to 100nm, and the mass content of the nano silicon dioxide in the hard carbon composite material is 1-80%.
8. The hard carbon composite material according to claim 7, wherein,
the hard carbon composite material is formed by carbonizing a high molecular polymer containing a silicon group, wherein the high molecular polymer contains an exchange group, and the high molecular polymer contains the silicon group formed by ion exchange of a soluble silicon-containing compound; the exchange group comprises a sulfonic acid group (-SO) 3 H) Carboxyl (-COOH), quaternary amino (-NR) 3 OH) is provided.
9. A negative electrode comprising the hard carbon composite material according to any one of claims 1 to 6.
10. A lithium battery comprising the negative electrode of claim 7.
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