CN116979045A - Composite silicon oxide negative electrode material and preparation method and application thereof - Google Patents
Composite silicon oxide negative electrode material 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 58
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 title claims description 28
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000011149 active material Substances 0.000 claims abstract description 32
- 239000010405 anode material Substances 0.000 claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021383 artificial graphite Inorganic materials 0.000 claims abstract description 12
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 36
- 238000000227 grinding Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 16
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 16
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 16
- 239000004570 mortar (masonry) Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 abstract description 8
- 239000010439 graphite Substances 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
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- 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
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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
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- H01M4/04—Processes of manufacture in general
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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
- H01M4/48—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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a composite silicon oxide anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing a binder; (2) Preparing conductive carbon black, and auxiliary materials obtained by mixing aqueous single-wall carbon nanotube slurry with a binder; (3) Preparing an active material obtained by mixing SiO and artificial graphite; (4) And compounding the active material, auxiliary materials and piezoelectric material lead titanate to finally obtain the composite silicon oxide anode material. The method adopts the combination of graphite and silicon oxide, slows down the volume expansion of a silicon-based material through the piezoelectric effect of doped lead titanate, reduces the charge diffusion resistance and accelerates the lithium ion migration rate, thereby preparing the composite silicon oxide anode material with high specific capacity and high circularity.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a composite silicon oxide negative electrode material, a preparation method and application thereof.
Background
The lithium ion battery is widely applied to the fields of electric automobiles, information technology, aerospace and the like, is a mainstream technology of a new generation energy storage power supply at present, but with the continuous development of portable electronic equipment and new energy automobiles, higher requirements are put on specific energy and cycle performance of the power battery. The negative electrode material is taken as one of important components of the lithium ion battery, and the performance of the negative electrode material directly influences the energy density of the whole battery. The cathode material of the current commercial lithium ion battery is mainly graphite, the theoretical specific capacity of the graphite is lower and is only 372mAh/g, and the development requirement of the lithium ion battery with high specific energy and high circularity in the current market is difficult to meet. Compared with graphite, silicon oxide (SiO) is used as a cathode material, has high specific capacity (theoretical specific capacity is 2100 mAh/g), is rich in reserve and easy to process, is considered as an ideal cathode material for lithium ion batteries with high power for replacing graphite materials, however, siO is large in volume expansion in the circulating process, and is easy to cause pulverization and capacity attenuation of the materials, so that the circulating performance of the lithium ion batteries is poor, and the intrinsic conductivity of the SiO is low, so that the practical application of the lithium ion batteries in a large range is restricted.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a composite silicon oxide negative electrode material, a preparation method and application thereof, wherein the method adopts graphite and silicon oxide to be compounded, improves the specific capacity of the composite material, reduces the volume expansion of a silicon-based material by the piezoelectric effect of doped lead titanate, reduces the charge diffusion resistance and accelerates the lithium ion migration rate, thereby preparing the lithium ion battery negative electrode material with high specific capacity and high circularity.
In order to achieve the above purpose, the invention discloses a preparation method of a composite silicon oxide anode material, which comprises the following steps:
(1) Preparing a binder: adding sodium carboxymethylcellulose into deionized water, and stirring at room temperature for a certain time until the sodium carboxymethylcellulose is completely dissolved to obtain a binder;
(2) Preparing auxiliary materials: drying conductive carbon black (Super P) for a certain time, then putting the dried conductive carbon black into a mortar for grinding to be uniform, then adding aqueous single-walled carbon nanotube slurry into the uniformly ground conductive carbon black, continuously grinding the two raw materials to be fully mixed to obtain a mixture A, adding the mixture A into the binder obtained in the step (1), and grinding the mixture A to be uniform to obtain auxiliary materials;
(3) Preparing an active material: drying SiO and artificial graphite, and then putting into a mortar for grinding until the SiO and the artificial graphite are uniform, thus obtaining an active material;
(4) Preparing a composite anode material: adding the active material obtained in the step (3) into the auxiliary material obtained in the step (2), grinding uniformly to obtain a mixture B, adding the piezoelectric material into the mixture B, continuously grinding uniformly, transferring the mixture into a beaker, and stirring and mixing to obtain the composite silicon oxide anode material;
in the step (1), the stirring time is 2-3 h, and the mass fraction of the sodium carboxymethyl cellulose in the binder is 1.5%.
In the step (2), the drying temperature is 60-80 ℃ and the drying time is 12 hours; the grinding time is 0.5 h-1.0 h each time; the solid content of the aqueous single-walled carbon nanotube slurry is 0.4%.
The mass ratio of the conductive carbon black to the single-walled carbon nano tube in the step (2) to the sodium carboxymethyl cellulose in the step (1) is 8.5:1.5:10;
in the step (3), the mass ratio of SiO to artificial graphite is 1:3, the drying temperature is 60-80 ℃, and the drying time is 12 hours; the grinding time is 0.5 h-1.0 h.
In the step (4), the mass ratio of the active material to the auxiliary material is 16:1-16:4, the mass ratio of the active material to the piezoelectric material is 16:1-16:3, the two mass ratios do not contain the mass of water and other solvents, and the piezoelectric material is lead titanate; grinding time is 0.5-1.0 h, and stirring time is 3-4 h.
The theoretical specific capacity of graphite is lower, the intrinsic conductivity of SiO is low, and the volume expansion is large in the circulation process, so that the pulverization and capacity attenuation of the material are easy to cause, and if the graphite and the silicon oxide are compounded, the good conductivity and the higher specific capacity of the material can be realized. Adding conductive carbon black into the material to improve the conductivity of the material; the single-wall carbon nano tube has a flexible network and strong van der Waals acting force, and can be used as a negative electrode material to improve the cycle performance of the composite material; the lead titanate piezoelectric material can generate a local micro-electric field under the action of mechanical stress, so that the migration speed of lithium ions can be increased, meanwhile, the volume expansion of silicon oxide in the charge and discharge process can be restrained, the cyclicity of the composite material is improved, and the lithium storage performance of the negative electrode material can be improved.
Based on the above, the preparation method provided by the invention utilizes the piezoelectric effect of lead titanate, and prepares the composite silicon oxide anode material by compounding with graphite, silicon oxide, single-wall carbon nano tubes and the like.
The invention also aims to provide the composite silicon oxide anode material prepared by the preparation method and application of the material as the anode material of the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method has the advantages of simple process, short preparation period, strong repeatability, low equipment requirement and great application potential.
(2) The diffusion distance of lithium ions and electrons is shortened, the lithium storage performance of the material is improved, the volume change of the material in the circulation process is restrained, the circulation stability is improved, and the electrochemical performance of the material, including conductivity, specific capacity of a lithium ion battery and circulation stability, is further effectively improved.
(3) When the prepared composite silicon oxide anode material is used as an anode material of a lithium ion battery, the initial discharge specific capacity can reach 1264.13mAh/g, the initial coulomb efficiency can reach 83.45%, the composite silicon oxide anode material has higher specific capacity, the discharge specific capacity after 50 times of circulation still reaches 1323.6mAh/g, the capacity retention rate is good, the coulomb efficiency after 50 times of circulation is as high as 99.09%, and the excellent circulation performance is shown. The test result shows that the composite silicon oxide negative electrode material has excellent high capacity and high cycle performance, and is expected to meet the commercial requirement of the current high-energy-density lithium ion battery.
Drawings
FIG. 1 is a cycle performance curve of the composite silica negative electrode material prepared in example 1;
FIG. 2 is a cycle performance curve of the composite silica negative electrode material prepared in example 2;
fig. 3 is a cycle performance curve of the composite silicon oxide negative electrode material prepared in comparative example 1.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings. The following examples are based on the technology of the present invention and give detailed embodiments and operation steps, but the scope of the present invention is not limited to the following examples.
Wherein, the aqueous single-walled carbon nanotube slurry in the embodiment is outsourced, and the solid content of the aqueous single-walled carbon nanotube slurry is 0.4%;
example 1:
(1) Preparing a binder: adding 0.025g of sodium carboxymethyl cellulose into 1.642g of deionized water, and stirring at room temperature for 2 hours until the sodium carboxymethyl cellulose is completely dissolved to obtain a binder with the mass fraction of 1.5%;
(2) Preparing auxiliary materials: drying 0.0213g of conductive carbon black (Super P) at 80 ℃ for 12 hours, then putting into a mortar for grinding for 0.5 hour until uniformity, adding 0.938g of aqueous single-wall carbon nanotube slurry (solid content is 0.4%) into the uniformly ground conductive carbon black, continuously grinding for 0.5 hour until the two raw materials are fully mixed to obtain a mixture A, adding the mixture A into the binder obtained in the step (1), and grinding for 1.0 hour in the mortar until uniformity is achieved, thus obtaining auxiliary materials;
(3) Preparing an active material: drying 0.1g of SiO and 0.3g of artificial graphite at 80 ℃ for 12 hours, and then putting the dried materials into a mortar for grinding for 1.0 hour until the materials are uniformly mixed to obtain an active material;
(4) Preparing a composite anode material: adding the active material obtained in the step (3) into the auxiliary material obtained in the step (2), grinding for 0.5h until the mixture is uniformly mixed to obtain a mixture B, adding 0.05g of piezoelectric material lead titanate into the mixture B, continuously grinding for 0.5h until the mixture is uniformly mixed, transferring the mixture into a beaker, and stirring and mixing the mixture for 3h by adopting an electromagnetic stirring device to finally obtain the composite silicon oxide anode material;
in this embodiment, the mass ratio of the active material (SiO to artificial graphite) to the auxiliary material (conductive carbon black, single-walled carbon nanotube, sodium carboxymethyl cellulose) is 8:1, and the mass ratio of the active material to the piezoelectric material (lead titanate) is also 8:1, i.e., the two mass ratios do not include deionized water and other solvents used, and the mass fraction of the active material is 80% of the total mass of the obtained composite anode material (the mass excluding water and other solvents).
Electrochemical performance test: the prepared composite silicon oxide negative electrode material was coated on a copper foil, dried at 80 ℃ for 12 hours, cut into a round electrode sheet with a diameter of 12mm as a working electrode, assembled a battery in a glove box using a Cellgard 2300 microporous polypropylene member membrane and a Li wafer counter electrode, and measured for battery performance of a lithium ion battery negative electrode using a CR2025 coin-type battery test material. Battery charge/discharge tests were performed on an LANHE battery test system (CT 2001A, chinese armed) at a voltage window of 0.01-3V (vs li+/Li).
Fig. 1 is a cycle performance curve of the composite silicon oxide anode material prepared in the embodiment, and fig. 1 shows that the composite silicon oxide anode material is tested as a lithium ion battery anode material under the current density of 0.1C, the first discharge specific capacity can reach 1264.1mAh/g, the first charge specific capacity can reach 1055mAh/g, the first coulomb efficiency can reach 83.45%, the composite silicon oxide anode material has higher specific capacity, the discharge specific capacity after 50 cycles still reaches 1323.6mAh/g, the charge specific capacity can reach 1311.6mAh/g, the coulomb efficiency is 99.09%, the capacity retention rate is good, and the excellent cycle performance is shown.
Example 2:
(1) Preparing a binder: adding 0.0125g of sodium carboxymethyl cellulose into 0.82g of deionized water, and stirring at room temperature for 2h until the sodium carboxymethyl cellulose is completely dissolved to obtain a binder with a mass fraction of 1.5%;
(2) Preparing auxiliary materials: drying 0.0107g of conductive carbon black (Super P) at 80 ℃ for 12 hours, then putting the dried conductive carbon black into a mortar for grinding for 0.5 hour until the mixture is uniform, adding 0.469g of aqueous single-wall carbon nanotube slurry (the solid content is 0.4%) into the uniformly ground conductive carbon black, continuously grinding for 0.5 hour until the two raw materials are fully mixed to obtain a mixture A, adding the mixture A into the binder obtained in the step (1), and grinding the mixture A in the mortar for 1.0 hour until the mixture is uniform to obtain auxiliary materials;
(3) Preparing an active material: drying 0.1g of SiO and 0.3g of artificial graphite at 80 ℃ for 12 hours, and then putting the dried materials into a mortar for grinding for 1.0 hour until the materials are uniformly mixed to obtain an active material;
(4) Preparing a composite anode material: adding the active material obtained in the step (3) into the auxiliary material obtained in the step (2), grinding for 0.5h until the mixture is uniformly mixed to obtain a mixture B, adding 0.075g of piezoelectric material lead titanate into the mixture B, continuously grinding for 1.0h until the mixture is uniformly mixed, transferring the mixture into a beaker, and stirring and mixing the mixture for 3h by adopting an electromagnetic stirring device to finally obtain the composite silicon oxide anode material.
In this embodiment, the mass ratio of the active material to the auxiliary material is 16:1, and the mass ratio of the active material to the piezoelectric material is 16:3, i.e., the two mass ratios do not include deionized water and other solvents used, and the mass of the active material accounts for 80% of the total mass of the obtained composite anode material (the mass excluding water and other solvents).
The composite silicon oxide negative electrode material obtained in this example was tested by the same electrochemical performance test method as in example 1, and fig. 2 is a cycle performance curve of the composite silicon oxide negative electrode material prepared in this example, and fig. 2 shows that when the composite silicon oxide negative electrode material is tested as a lithium ion battery negative electrode material at a current density of 0.1C, the first discharge specific capacity can reach 914mAh/g, the first charge specific capacity can reach 777mAh/g, the first coulomb efficiency can reach 85.00%, the discharge specific capacity after 30 cycles is 742.9mAh/g, the charge specific capacity can reach 739.3mAh/g, and the coulomb efficiency can reach 99.53%.
Comparative example 1:
(1) Preparing a binder: adding 0.05g of sodium carboxymethyl cellulose into 3.28g of deionized water, and stirring at room temperature for 3 hours until the sodium carboxymethyl cellulose is completely dissolved to obtain a binder with the mass fraction of 1.5%;
(2) Preparing auxiliary materials: drying 0.0425g of conductive carbon black (Super P) at 80 ℃ for 12 hours, then putting into a mortar for grinding for 0.5 hour until uniformity, adding 1.875g of aqueous single-wall carbon nanotube slurry (solid content is 0.4%) into the uniformly ground conductive carbon black, continuously grinding for 0.5 hour until the two raw materials are fully mixed to obtain a mixture A, adding the mixture A into the binder obtained in the step (1), and grinding for 1.0 hour in the mortar until uniformity is achieved to obtain auxiliary materials;
(3) Preparing an active material: drying 0.1g of SiO and 0.3g of artificial graphite at 80 ℃ for 12 hours, and then putting the dried materials into a mortar for grinding for 1.0 hour until the materials are uniformly mixed to obtain an active material;
(4) Preparing a composite anode material: adding the active material obtained in the step (3) into the auxiliary material obtained in the step (2), grinding for 1.0h until the active material is uniformly mixed, transferring the active material into a beaker, and stirring and mixing the active material for 3h by adopting an electromagnetic stirring device to finally obtain the composite silicon oxide negative electrode material.
In the comparative example, the mass ratio of the active material (SiO to artificial graphite) to the auxiliary material (conductive carbon black, single-walled carbon nanotube, sodium carboxymethyl cellulose) was 4:1, i.e., the two mass ratios do not contain deionized water and other solvents used, and the mass fraction of the active material in the total mass of the obtained composite anode material (excluding the mass of water and other solvents) was 80%.
The composite silicon oxide negative electrode material obtained in this comparative example was tested by the same electrochemical performance test method as in example 1, and fig. 3 is a cycle performance curve of the composite silicon oxide negative electrode material of the undoped lead titanate piezoelectric material prepared in this comparative example, and fig. 3 shows that when the composite silicon oxide negative electrode material is tested as a lithium ion battery negative electrode material at a current density of 0.1C, the first discharge specific capacity can reach 748.7mAh/g, the first charge specific capacity can reach 573.4mAh/g, the first coulomb efficiency can reach 76.59%, the discharge specific capacity after 30 cycles is 752.9mAh/g, the charge specific capacity can reach 749.1mAh/g, and the coulomb efficiency can reach 99.50%.
As is clear from fig. 1 to 3, the materials in examples 1, 2 are superior to the material in comparative example 1 in both the charge and discharge specific capacity and the first coulombic efficiency, and the overall performance of example 1 is significantly superior to that of comparative example 1.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the composite silicon oxide anode material is characterized by comprising the following steps of:
(1) Preparing a binder: adding sodium carboxymethylcellulose into deionized water, and stirring at room temperature for a certain time until the sodium carboxymethylcellulose is completely dissolved to obtain a binder;
(2) Preparing auxiliary materials: drying conductive carbon black for a certain time, then putting the dried conductive carbon black into a mortar for grinding until the mixture is uniform, then adding aqueous single-wall carbon nanotube slurry into the uniformly ground conductive carbon black, continuously grinding the mixture into two raw materials, fully mixing the two raw materials to obtain a mixture A, adding the mixture A into the binder obtained in the step (1), and grinding the mixture A until the mixture is uniform to obtain auxiliary materials;
(3) Preparing an active material: drying SiO and artificial graphite, and then putting into a mortar for grinding until the SiO and the artificial graphite are uniform, thus obtaining an active material;
(4) Preparing a composite anode material: adding the active material obtained in the step (3) into the auxiliary material obtained in the step (2), grinding uniformly to obtain a mixture B, adding the piezoelectric material into the mixture B, continuously grinding uniformly, transferring the mixture into a beaker, and stirring and mixing to obtain the composite silicon oxide anode material.
2. The method for preparing the composite silicon oxide anode material according to claim 1, wherein the method comprises the following steps: in the step (1), the stirring time is 2-3 h, and the mass fraction of the sodium carboxymethyl cellulose in the binder is 1.5%.
3. The method for preparing the composite silicon oxide anode material according to claim 1, wherein the method comprises the following steps: in the step (2), the solid content of the aqueous single-walled carbon nanotube slurry is 0.4%.
4. The method for preparing a composite silicon oxide negative electrode material according to claim 3, wherein: in the step (2), the drying temperature is 60-80 ℃ and the drying time is 12 hours; the time of each grinding is 0.5 h-1.0 h.
5. The method for preparing a composite silicon oxide negative electrode material according to claim 3, wherein: the mass ratio of the conductive carbon black in the step (2), the single-walled carbon nano tube and the sodium carboxymethyl cellulose in the step (1) is 8.5:1.5:10.
6. The method for preparing the composite silicon oxide anode material according to claim 1, wherein the method comprises the following steps: in the step (3), the mass ratio of SiO to artificial graphite is 1:3, the drying temperature is 60-80 ℃, the drying time is 12h, and the grinding time is 0.5-1.0 h.
7. The method for preparing the composite silicon oxide anode material according to claim 1, wherein the method comprises the following steps: in the step (4), the mass ratio of the active material to the auxiliary material is 16:1-16:4, the mass ratio of the active material to the piezoelectric material is 16:1-16:3, the two mass ratios do not contain the mass of water and other solvents, and the piezoelectric material is lead titanate.
8. The method for preparing the composite silicon oxide anode material according to claim 1, wherein the method comprises the following steps: in the step (4), the grinding time is 0.5-1.0 h, and the stirring time is 3-4 h.
9. The composite silicon oxide negative electrode material produced by the production method according to any one of claims 1 to 8.
10. The use of the composite silicon oxide negative electrode material as defined in claim 9 as a negative electrode material for a lithium ion battery.
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