CN116722129B - High-performance silicon-oxygen anode material and preparation method and application thereof - Google Patents
High-performance silicon-oxygen anode material and preparation method and application thereof Download PDFInfo
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- CN116722129B CN116722129B CN202310997740.6A CN202310997740A CN116722129B CN 116722129 B CN116722129 B CN 116722129B CN 202310997740 A CN202310997740 A CN 202310997740A CN 116722129 B CN116722129 B CN 116722129B
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- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000010405 anode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007773 negative electrode material Substances 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- -1 niobium tungsten titanium oxide Chemical compound 0.000 abstract description 16
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052814 silicon oxide Inorganic materials 0.000 description 11
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000004584 polyacrylic acid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 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
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000007873 sieving Methods 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
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000009728 shiwei Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—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
- H01M4/606—Polymers containing aromatic main chain polymers
-
- 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 high-performance silicon-oxygen anode material and a preparation method and application thereof, belonging to the technical field of lithium ion batteries, wherein the preparation method comprises the following steps: compounding a silica material with hydroxyl-terminated hyperbranched poly (amine-ester) to prepare silica-terminated hyperbranched poly (amine-ester) particles; compounding silica-terminated hyperbranched poly (amine-ester) particles with graphene oxide to prepare GO/HP/SiO X A material; GO/HP/SiO with metallic niobium tungsten titanium oxide X Coating the material to obtain a metal niobium tungsten titanium oxide coated modified silicon oxide material; and (3) carrying out surface carbon coating on the modified silicon-oxygen material coated by the metal niobium tungsten titanium oxide to obtain a silicon-oxygen negative electrode material, wherein the negative electrode material can be used for preparing a negative electrode plate for a lithium ion battery. The invention can solve the problems of poor conductivity and large expansion of the silicon-oxygen anode material, thereby being beneficial to improving the cycle performance of the lithium battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-performance silicon-oxygen negative electrode material, and a preparation method and application thereof.
Background
The lithium ion battery has the characteristics of high energy density, long cycle life, wide application range and the like, and is widely applied to the fields of electronic equipment, electric automobiles and the like. Currently, with the demand for lightweight electronic devices and electric vehicles, there is an increasing demand for high energy density lithium ion batteries.
The traditional negative electrode material of the lithium ion battery adopts graphite, but the gram capacity of the traditional graphite negative electrode material can not meet the requirement, and silicon has excellent theoretical capacity, so that the lithium ion battery has great application prospect, and the development of the silicon-based negative electrode material has become the main stream of the development of the negative electrode material of the lithium ion battery. However, silicon materials have problems such as poor conductivity, swelling, etc., resulting in poor cycle performance of lithium batteries, and improvements are still needed.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-performance silicon-oxygen anode material, a preparation method and application thereof, which can solve the problems of poor conductivity and large expansion of the silicon-oxygen anode material and is beneficial to improving the cycle performance of a lithium battery.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a high-performance silicon-oxygen negative electrode material, which comprises the steps of firstly compounding hydroxyl-terminated hyperbranched poly (amine-ester) with a silicon-oxygen material, and then compounding with graphene oxide to obtain GO/HP/SiO X The material is prepared by the steps of firstly using metal niobium tungsten titanium oxide to perform the reaction on GO/HP/SiO X And coating the material, and then coating the surface carbon of the obtained material to obtain the high-performance silicon-oxygen anode material.
Preferably, the method specifically comprises the following steps:
(1) Dropwise adding the hydroxyl-terminated hyperbranched poly (amine-ester) solution into the dispersion liquid of the silica material under stirring, continuously stirring, ultrasonically dispersing, washing, centrifuging and drying to obtain silica-terminated hyperbranched poly (amine-ester) particles;
(2) Adding silica-terminated hyperbranched poly (amine-ester) particles into graphene oxide aqueous solution, performing ultrasonic dispersion, washing, centrifuging and drying to obtain GO/HP/SiO X A material;
(3) GO/HP/SiO X Mixing and stirring the material with the metal niobium tungsten titanium oxide, ball milling, drying, sintering and cooling to obtain the metal niobium tungsten titanium oxide coated modified silicon oxide material;
(4) Uniformly mixing a metallic niobium tungsten titanium oxide coated modified silicon oxide material with a carbon source, and then spray-drying, sintering and carbonizing to obtain a high-performance silicon oxide negative electrode material;
synthesis of hyperbranched poly (amine-esters) and investigation of their photocuring reactions based on literature (in culture, zheng Yaping, shiwei et al [ J)]The "one-step process" mentioned in university of northwest industries, university of northwest, 2010,28 (04): 637-642) produces hydroxyl-terminated hyperbranched poly (amine-esters), specifically: adding trimethylolpropane, N-dihydroxyethyl-3-amino methyl propionate monomer (molar ratio 1:3) and proper amount of p-toluenesulfonic acid into a reaction kettle, and introducing N 2 Stirring and mixing uniformly, heating to 120 ℃ and keeping for 2.5 hours, and vacuumizing to remove the generated methanol to obtain the hydroxyl-terminated hyperbranched poly (amine-ester).
Preferably, in the step (1), the silicon oxide material is silicon oxide, and the mass ratio of the hydroxyl-terminated hyperbranched poly (amine-ester) to the silicon oxide material is 0.2-2.0: 1, a step of; the hydroxyl-terminated hyperbranched poly (amine-ester) solution is an ethanol solution of the hydroxyl-terminated hyperbranched poly (amine-ester), and the silica material dispersion is an ethanol dispersion of the silica material.
In the step (1), the stirring time is 2-6h, and the ultrasonic dispersion time is 2-3h.
Preferably, in the step (2), the mass ratio of the silicon-oxygen terminal hydroxyl hyperbranched poly (amine-ester) particles to the graphene oxide is 0.5-2.0: 1.
in the step (2), the ultrasonic dispersion time is 2-3h.
Preferably, in the step (3), the metal niobium tungsten titanium oxide is Nb 2 O 5 、WO 3 And a titanium source, and Nb 2 O 5 、WO 3 And the molar ratio of the titanium source is 9-14:1-3:0.2-1, wherein the titanium source is titanium dioxide and/or tetrabutyl titanate.
Preferably, in the step (3), ball milling is carried out in a high-speed ball mill, wherein the ball milling rotating speed is 420-800r/min, and the time is 6-12h; the sintering temperature is 1050-1350 ℃ and the sintering time is 2-6h under nitrogen atmosphere.
Preferably, in the step (4), the carbon source is pitch or phenolic resin, and the carbon source is added in an amount to ensure that the carbon content introduced into the silicon-oxygen anode material by the carbon source is 3-6%, and the thickness of the coating layer formed by surface carbon coating is 50-100 nm.
Preferably, in the step (4), the sintering and carbonizing temperature is 900-1050 ℃ and the sintering and carbonizing time is 2-4h.
The invention also relates to a high-performance silicon-oxygen anode material which is prepared by adopting the preparation method.
The negative electrode plate for the lithium ion battery comprises the high-performance silicon oxide negative electrode material.
Preferably, the lithium ion battery further comprises a conductive agent and a binder, wherein the mass ratio of the silicon oxygen anode material to the conductive agent to the binder is (70-95): (1.5-20): (3.5 to 10), more preferably 90:4:6.
preferably, the conductive agent is at least two of carbon black, carbon nanotubes, and graphene; the binder is preferably PAA.
Preferably, the coating material also comprises an edge coating material which is a mixture of ceramic powder, PVDF (polyvinylidene fluoride) and PAA (polyacrylic acid), wherein the mass content of the ceramic powder is 80-90%, the mass content of the PVDF is 5-10%, and the mass content of the PAA is 5-10%.
The preparation method of the negative electrode plate for the lithium ion battery comprises the following steps: uniformly mixing a silicon-oxygen anode material, a conductive agent, a binder and water to obtain slurry with the solid content of 40-60%, uniformly coating the slurry on at least one surface of the positive and negative sides of the copper foil, and drying to obtain the pole piece.
Preferably, the ceramic powder, PVDF and PAA are uniformly dispersed in water, then the obtained material is coated on the edge of the pole piece, and the pole piece is dried to obtain the negative pole piece with the edge coating layer, wherein the thickness of the edge coating layer is 30-80 mu m.
The beneficial effects of the invention are as follows:
(1) The invention provides a high-performance silicon-oxygen negative electrode material, which is prepared by mixing and modifying a silicon-oxygen material and hydroxyl-terminated hyperbranched poly (amine-ester), taking a macromolecule as a framework, adding a conductive material of graphene to form a fast ion channel, facilitating rapid entry and removal of lithium ions, having very good high-rate circularity, and the hydroxyl-terminated hyperbranched poly (amine-ester) modified silicon-oxygen material has higher mechanical strength and hardness, can effectively inhibit volume expansion of silicon oxide when receiving expansion force of lithium intercalation, keeps the structure of the negative electrode material stable, and prevents particles from mutually approaching to each other in a dispersing process to generate agglomeration, and ensures the performance of a negative electrode plate;
(2) The doped metal element can react with the silicon-oxygen material to form an inert substance metal silicon-oxygen complex, so that the content of oxygen element is reduced, the conductivity is improved, and the first-week coulomb efficiency of the material is improved.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
fig. 1 is a graph showing discharge capacities of assembled full cells of the high performance silicon oxygen anode material provided in example 1 of the present invention and full cells assembled of the silicon oxygen anode material of comparative example 1 at different rates;
FIG. 2 is a cycle comparison plot of an assembled full cell of high performance negative electrode material of silicon oxide provided in example 1 of the present invention and a full cell assembled of negative electrode material of comparative example 1;
FIG. 3 is a scanning electron microscope image of a silica negative electrode material in a negative electrode plate of a full battery assembled by a high-performance silica negative electrode material provided in the embodiment 1 of the invention after 1000 cycles;
fig. 4 is a scanning electron microscope image of a silicon oxygen anode material in an anode tab of a full cell assembled with the silicon oxygen anode material after 1000 cycles.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The hydroxyl-terminated hyperbranched poly (amine-ester) used in the following examples was synthesized using a one-step method, specifically: adding trimethylolpropane, N-dihydroxyethyl-3-amino methyl propionate monomer (molar ratio 1:3) and proper amount of p-toluenesulfonic acid into a reaction kettle, and introducing N 2 Stirring and mixing uniformly, heating to 120 ℃ and keeping for 2.5 hours, and vacuumizing to remove the generated methanol to obtain the hydroxyl-terminated hyperbranched poly (amine-ester).
Example 1
Step (1): dropwise adding the hydroxyl-terminated hyperbranched poly (amine-ester) ethanol solution (mass fraction is 1%) into ethanol dispersion liquid (mass fraction is 1%) of silicon oxide under stirring, continuously stirring for 2h, ultrasonically dispersing for 2h, washing, centrifuging and drying to obtain silicon-oxygen hydroxyl-terminated hyperbranched poly (amine-ester) particles; wherein the mass ratio of the hydroxyl-terminated hyperbranched poly (amine-ester) to the silica is 0.2:1.
step (2): adding silica hydroxyl hyperbranched poly (amine-ester) particles into graphene oxide aqueous solution (the mass ratio of graphene oxide to water is 0.5:99.5), performing ultrasonic dispersion for 2 hours, washing, centrifuging and drying to obtain GO/HP/SiO X A material; wherein the mass ratio of the silicon-oxygen terminal hydroxyl hyperbranched poly (amine-ester) particles to the graphene oxide is 0.5:1.
step (3): GO/HP/SiO X The material was mixed with the metal niobium tungsten titanium oxide and ball milled in a high speed ball mill at 420 r/min for 6h. Drying, placing in a tube furnace, sintering at 1050 ℃ for 2 hours under nitrogen atmosphere, cooling, grinding, sieving for standby, and preparing the metal niobium tungsten titanium oxide coated modified silicon oxide material; wherein the metal niobium tungsten titanium oxide is Nb 2 O 5 、WO 3 And a titanium source (titanium dioxide and tetrabutyl titanate are mixed according to a mass ratio of 1:1), nb 2 O 5 、WO 3 And a titanium source molar ratio of 9:1:0.2.
Step (4): uniformly mixing a modified silicon-oxygen material coated by metal niobium tungsten titanium oxide with asphalt, then spray-drying, sintering and carbonizing for 2 hours at 900 ℃ to obtain the high-performance silicon-oxygen negative electrode material, wherein the adding proportion of asphalt ensures that the carbon content introduced into the silicon-oxygen negative electrode material by asphalt is 3%, and the thickness of a coating layer is 50nm.
Example 2
Step (1): dropwise adding the hydroxyl-terminated hyperbranched poly (amine-ester) ethanol solution (mass fraction is 1.5%) into ethanol dispersion liquid (mass fraction is 1.5%) of silicon oxide under stirring, continuously stirring for 2 hours, ultrasonically dispersing for 2 hours, washing, centrifuging and drying to obtain silicon-oxygen hydroxyl-terminated hyperbranched poly (amine-ester) particles; wherein the mass ratio of the hydroxyl-terminated hyperbranched poly (amine-ester) to the silica is 0.2:1.
step (2): adding silica hydroxyl hyperbranched poly (amine-ester) particles into graphene oxide aqueous solution (mass fraction is 0.5%), performing ultrasonic dispersion for 2h, washing, centrifuging, and drying to obtain GO/HP/SiO X A material; wherein the mass ratio of the silicon-oxygen terminal hydroxyl hyperbranched poly (amine-ester) particles to the graphene oxide is 1:1.
step (3): GO/HP/SiO X The material was mixed with the metal niobium tungsten titanium oxide and ball milled in a high speed ball mill at 420 r/min for 6h. Drying, placing in a tube furnace, sintering at 1050 ℃ for 2 hours under nitrogen atmosphere, cooling, grinding, sieving for standby, and preparing the metal niobium tungsten titanium oxide coated modified silicon oxide material; wherein the metal niobium tungsten titanium oxide is Nb 2 O 5 、WO 3 And a titanium source (titanium dioxide and tetrabutyl titanate are mixed according to a mass ratio of 1:1), nb 2 O 5 、WO 3 And a titanium source molar ratio of 10:1.5:1.
Step (4): uniformly mixing a metal niobium tungsten titanium oxide coated modified silicon-oxygen material with phenolic resin, then spray drying, sintering and carbonizing for 2 hours at 900 ℃ to obtain the high-performance silicon-oxygen anode material, wherein the adding proportion of the phenolic resin ensures that the carbon content introduced into the silicon-oxygen anode material by the phenolic resin is 5%, and the thickness of a coating layer is 100nm.
Comparative example 1
Mixing the silicon oxide and the asphalt uniformly, then spray drying, sintering and carbonizing for 2 hours at 900 ℃ to obtain the silicon oxide anode material coated with carbon. Wherein the addition proportion of the asphalt ensures that the carbon content of the silicon-oxygen anode material introduced by the asphalt is 3 percent, and the thickness of the coating layer is 50nm.
The high-performance silicon-oxygen negative electrode material prepared in the example 1 and the carbon-coated silicon-oxygen negative electrode material prepared in the comparative example 1 are respectively used as silicon-oxygen negative electrode materials, and a negative electrode plate is prepared according to the following method, and specifically comprises the following steps:
1) The silicon-oxygen cathode material, the conductive agent SP, the conductive agent single-arm carbon nano tube and the adhesive PAA according to the mass ratio of 92:2:0.8:5.2, uniformly mixing to prepare an aqueous solution with the solid content of 50%, uniformly coating the obtained material on copper foil, coating the copper foil on two sides, and drying to obtain a pole piece;
2) Mixing ceramic powder, PVDF and PAA according to a mass ratio of 90:5:5, uniformly mixing, then mixing the mixture with water, wherein the solid content is 50%, uniformly dispersing, coating the obtained material on the edge of the pole piece, and drying to obtain the negative pole piece with the edge coating layer, wherein the thickness of the edge coating layer is 50 mu m.
The negative electrode tab prepared using the high performance silicon oxygen negative electrode material of example 1 and the negative electrode tab prepared using the carbon-coated silicon oxygen negative electrode material of comparative example 1 were used to assemble a full battery for testing.
Fig. 1 shows a discharge curve obtained by charging two full batteries to 4.2V respectively and then discharging the full batteries at a constant current according to a discharge current of 8C, wherein the discharge capacity corresponds to the position of the abscissa, the discharge capacity is from 4.2V to 2.5V, the discharge capacity corresponds to example 1 at 3.7Ah, and the discharge capacity corresponds to comparative example 1 at 3.5Ah.
Fig. 2 is a graph of two full cell cycle tests, the abscissa is the number of cycles, and the ordinate is the capacity retention, 2C charge 8C discharge. Comparative example 1, capacity decayed at 300 more turns, cycle ended; the capacity retention rate of 800 cycles of charge and discharge cycle of example 1 can be maintained at 95% or more. The cycle performance of example 1 is better than that of comparative example 1.
In addition, the expansion of the negative electrode tabs of the full batteries corresponding to example 1 and comparative example 1, which were cycled for 600 weeks at an 8C discharge rate, was 16% and 40%, respectively. The calculation method of the expansion data comprises the following steps: a set of example 1 and comparative example 1 was first disassembledThe thickness of the corresponding full battery is measured, and the initial thickness of the corresponding negative electrode plate is respectively marked as a 0 And b 0 The method comprises the steps of carrying out a first treatment on the surface of the Taking another group of full batteries corresponding to the example 1 and the comparative example 1 for testing, after the full batteries circulate for 600 weeks at the 8C discharge rate, disassembling the corresponding full batteries, measuring the thickness of the negative electrode plate in the full batteries, wherein the thicknesses of the negative electrode plates of the full batteries corresponding to the example 1 and the comparative example 1, which circulate for 600 weeks at the 8C discharge rate, are respectively recorded as a 1 And b 1 The corresponding expansion ratios are (a) 1 - a 0 )/ a 0 =16%，(b 1 - b 0 )/ b 0 The tool for measuring the thickness of the negative electrode plate is a micrometer, and when the battery is disassembled to measure the thickness of the negative electrode plate, the battery is disassembled under the condition of 3.7V, and then the negative electrode plate is taken out for thickness measurement.
As shown in fig. 3, the electron microscope image of the silicon-oxygen negative electrode material in the negative electrode plate after circulation is shown, wherein the silicon-oxygen negative electrode material can keep a better appearance, is not pulverized and has cracks, and has high mechanical strength; as shown in fig. 4, the silicon-oxygen negative electrode material of comparative example 1 was used, which corresponds to an electron microscopic image of the silicon-oxygen negative electrode material in the negative electrode sheet after the cycle, in which the silicon-oxygen negative electrode material had been damaged by particles.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (10)
1. The preparation method of the silicon-oxygen anode material is characterized by comprising the following steps of:
(1) Dropwise adding the hydroxyl-terminated hyperbranched poly (amine-ester) solution into the dispersion liquid of the silica material under stirring, continuously stirring, performing ultrasonic dispersion, washing, centrifuging and drying to obtain silica-terminated hyperbranched poly (amine-ester) particles;
(2) Adding silica-terminated hyperbranched poly (amine-ester) particles into graphene oxide aqueous solution, performing ultrasonic dispersion, washing, centrifuging and drying to obtain GO/HP/SiO X A material;
(3) GO/HP/SiO X Material and Nb 2 O 5 、WO 3 Mixing with the mixture of the titanium source, stirring, ball milling, drying, sintering and cooling; wherein the titanium source is titanium dioxide and/or tetrabutyl titanate, and the sintering conditions are as follows: sintering at 1050-1350 deg.c for 2-6 hr in nitrogen atmosphere;
(4) And (3) coating the surface carbon of the material obtained in the step (3) to obtain the silicon-oxygen anode material.
2. The method according to claim 1, wherein the specific process of step (4) is: and (3) uniformly mixing the material obtained in the step (3) with a carbon source, and then spray-drying, sintering and carbonizing to obtain the silicon-oxygen anode material.
3. The preparation method of claim 2, wherein in the step (1), the silica material is silica, and the mass ratio of the hydroxyl-terminated hyperbranched poly (amine-ester) to the silica material is 0.2-2.0: 1, a step of; the hydroxyl-terminated hyperbranched poly (amine-ester) solution is an ethanol solution of the hydroxyl-terminated hyperbranched poly (amine-ester), and the silica material dispersion is an ethanol dispersion of the silica material.
4. The preparation method of claim 2, wherein in the step (2), the mass ratio of the silicon-oxygen terminal hydroxyl hyperbranched poly (amine-ester) particles to the graphene oxide is 0.5-2.0: 1.
5. the method according to claim 2, wherein in step (3), nb 2 O 5 、WO 3 And the molar ratio of the titanium source is 9-14:1-3:0.2-1.
6. The method according to claim 2, wherein in the step (3), the ball milling is performed in a high-speed ball mill at a rotational speed of 420-800r/min for 6-12 hours.
7. The method according to claim 2, wherein in the step (4), the carbon source is pitch or phenolic resin, and the carbon source is added in an amount such that the carbon content of the silicon-oxygen anode material introduced through the carbon source is 3 to 6%, and the thickness of the coating layer formed by surface carbon coating is 50nm to 100nm.
8. The method according to claim 2, wherein in the step (4), the sintering and carbonization are performed at a temperature of 900 to 1050 ℃ for a time of 2 to 4 hours.
9. A silicon-oxygen anode material, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. A negative electrode sheet for a lithium ion battery, comprising the silicon-oxygen negative electrode material according to claim 9.
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