CN115050952B - Silica anode material and preparation method and application thereof - Google Patents
Silica anode material and preparation method and application thereof Download PDFInfo
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- CN115050952B CN115050952B CN202210959559.1A CN202210959559A CN115050952B CN 115050952 B CN115050952 B CN 115050952B CN 202210959559 A CN202210959559 A CN 202210959559A CN 115050952 B CN115050952 B CN 115050952B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000010405 anode material Substances 0.000 title claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title abstract description 43
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000919 ceramic Substances 0.000 claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000010406 cathode material Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000007791 liquid phase Substances 0.000 claims abstract description 22
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 15
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 98
- 239000007773 negative electrode material Substances 0.000 claims description 57
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- 239000007789 gas Substances 0.000 claims description 23
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
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- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 3
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
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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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a silicon-oxygen cathode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: the porous ceramic is used as a framework, and the silicon oxide and the doping elements are uniformly dispersed and distributed in pores of the porous ceramic by a liquid phase method or a solid phase method; the doping elements comprise metal doping elements and/or nonmetal doping elements; the metal doping element comprises one or more of Al, na, li, mg, ca, ti, mn, co, ni, cu, zn, zr, mo, ge and Sn; the non-metal doping element comprises one or more of substances of any one of B, N, P, S, C, as and Se; the silicon-oxygen anode material has the characteristics of low volume expansion, high cycle and high initial efficiency.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a silica negative electrode material and a preparation method and application thereof.
Background
As one of the most important energy storage systems, lithium ion batteries have been widely used in the fields of portable electronic devices, electric vehicles, and the like. As a lithium ion battery cathode material, a silica cathode has a wide application prospect due to higher theoretical capacity and safer lithiation potential.
Due to the lithium alloying mechanism of lithium, the silicon-oxygen negative electrode can generate huge volume change (up to 160 percent) in the charging and discharging processes, and the problems of active material cracking, electrode structure crushing, active material peeling and the like are easily caused, so that capacity loss is caused; unstable SEI films are formed during delithiation/lithiation, also resulting in capacity loss. In addition, the silicon-oxygen cathode material also has the problems of low first-cycle coulombic efficiency (ICE) and low inherent conductivity.
Disclosure of Invention
The invention provides a silicon-oxygen cathode material and application thereof, aiming at solving the problems of larger volume expansion rate, poor conductivity, low first coulombic efficiency, poor battery cycle performance and the like of a silicon-oxide cathode material. Because the porous ceramic skeleton has higher mechanical strength and hardness, when the porous ceramic skeleton is subjected to the expansion force of embedded lithium, on one hand, the porous structure can reserve a space for the expansion of the silicon monoxide; on the other hand, the high-strength porous ceramic skeleton structure can effectively inhibit the volume expansion of the silicon monoxide and keep the structure of the cathode material stable. Meanwhile, the doped metal element reacts with silicon dioxide in the silicon monoxide material to form a metal silicon oxygen complex, so that the first-week coulombic efficiency of the battery can be obviously improved; on the other hand, the formed inert material metal silicon oxygen composite body can also slow down the volume expansion. The doped non-metallic elements can also accelerate the internal conduction rate of lithium ions and improve the conductivity of the silicon monoxide, thereby realizing low volume expansion, high cycle and high first efficiency of the battery.
In a first aspect, an embodiment of the present invention provides a silicon oxygen anode material, where the silicon oxygen anode material includes: porous ceramics, silicon monoxide and doping elements;
the porous ceramic is used as a framework, and the silicon oxide and the doping elements are uniformly dispersed in pores of the porous ceramic by a liquid phase method or a solid phase method;
the doping element comprises a metal doping element and/or a non-metal doping element;
the metal doping element comprises one or more of Al, na, li, mg, ca, ti, mn, co, ni, cu, zn, zr, mo, ge and Sn;
the non-metal doping element comprises one or more substances of any one doping element of B, N, P, S, C, as and Se;
the doping element accounts for 0.1-20% of the mass of the silicon monoxide.
Preferably, the porous ceramic includes: one or more of porous SiC, porous silicon nitride, porous gallium nitride, porous titanium nitride and porous boron nitride; the particle size Dv50 of the porous ceramic is between 500nm and 100 μm; the pore diameter of the pores of the porous ceramic is between 200nm and 20 mu m; the porosity of the porous ceramic is between 30% and 90%;
when the doping element substance is solid, the particle diameter Dv50 of the doping element substance is between 0.5nm and 10 mu m.
Preferably, the doping element accounts for 0.5 to 10 percent of the mass of the silicon monoxide;
the total mass of the silicon monoxide and the doping elements accounts for 50-90% of the total mass of the silicon-oxygen anode material; the porous ceramic accounts for 10-50% of the total mass of the silica negative electrode material.
Preferably, the silicon-oxygen anode material further comprises a carbon coating layer; the mass of the carbon coating layer accounts for 0-20% of the total mass of the silicon-oxygen negative electrode material.
In a second aspect, an embodiment of the present invention provides a preparation method of the silicon oxygen anode material described in the first aspect, where the preparation method includes:
compounding the porous ceramic, the silicon monoxide and the substance containing the doping elements to obtain a silicon-oxygen cathode material;
the compounding method comprises the following steps: liquid phase and/or solid phase processes;
wherein the doping element comprises a metal doping element and/or a non-metal doping element;
the metal doping element comprises one or more of Al, na, li, mg, ca, ti, mn, co, ni, cu, zn, zr, mo, ge and Sn;
the non-metal doping element comprises one or more substances of any one doping element of B, N, P, S, C, as and Se;
the porous ceramic includes: one or more of porous SiC, porous silicon nitride, porous gallium nitride, porous titanium nitride and porous boron nitride; the particle size Dv50 of the porous ceramic is between 500nm and 100 mu m; the pore diameter of the pores of the porous ceramic is between 200nm and 20 mu m; the porosity of the porous ceramic is between 30% and 90%;
when the doping element substance is solid, the particle diameter Dv50 of the doping element substance is between 0.5nm and 10 mu m.
Preferably, the liquid phase process comprises: uniformly dispersing the silicon monoxide and the doping element-containing substance in an organic solvent to obtain a premixed solution;
adding the porous ceramic into the premixed solution, and continuously and uniformly dispersing to obtain a mixed solution;
placing the mixed solution in a high-temperature furnace, heating to 700-1000 ℃, preserving heat for 2-5 hours, and crushing and screening after discharging to obtain the silica negative electrode material;
wherein the organic solvent comprises: one or more of toluene, isopropanol, dimethylformamide, sulfolane, a glycol dimethyl ether solution containing biphenyl, a naphthalene solution containing pyrene or tetrahydrofuran containing p-terphenyl;
the uniformly dispersing apparatus includes: one of a ball mill, a dispersion machine or an ultrasonic stirrer.
Preferably, the solid phase method comprises;
placing the porous ceramic, the silicon monoxide and the substance containing the doping elements in a ball mill, and carrying out ball milling and mixing for 10-48 hours in an argon or nitrogen atmosphere to disperse the silicon monoxide and the doping elements in pores of the porous ceramic to obtain a precursor material;
placing the precursor material in a heating furnace, heating to 600-1000 ℃ in an argon or nitrogen atmosphere, preserving heat for 3-10 hours, and performing high-temperature heat treatment to obtain a silica negative electrode precursor material;
crushing and screening the silicon-oxygen negative electrode precursor material to obtain the silicon-oxygen negative electrode material;
wherein, the heating furnace includes: box-type heating furnaces or tube-type heating furnaces.
Preferably, the preparation method further comprises: carrying out carbon coating on the silicon-oxygen cathode material, and then carrying out graded demagnetization;
the carbon coating method comprises the following steps: one of gas phase coating, liquid phase coating or solid phase coating;
the mass of the carbon coating layer accounts for 0-20% of the total mass of the silicon-oxygen negative electrode material.
In a third aspect, an embodiment of the present invention provides a negative electrode tab, where the negative electrode tab includes the silica negative electrode 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 tab of the third aspect.
The embodiment of the invention provides a silicon-oxygen negative electrode material, which is prepared by compounding porous ceramic, silicon monoxide and a doping element in a liquid phase or solid phase mode, wherein the porous ceramic is used as a framework, and the silicon monoxide and the doping element are in pores of the porous ceramic. Because the porous ceramic skeleton has higher mechanical strength and hardness, when the porous ceramic skeleton is subjected to the expansion force of lithium intercalation, on one hand, the porous structure can reserve a space for the expansion of the silicon monoxide; on the other hand, the high-strength porous ceramic skeleton structure can effectively inhibit the volume expansion of the silicon monoxide and keep the structure of the cathode material stable. Meanwhile, the doped metal elements react with silicon dioxide in the silicon monoxide material to form a metal silicon oxygen complex, so that on one hand, the coulombic efficiency of the first week of the battery can be remarkably improved, and on the other hand, the formed inert substance metal silicon oxygen complex can also slow down the volume expansion. The doped non-metallic elements can also accelerate the internal conduction rate of lithium ions and improve the conductivity of the silicon monoxide, thereby realizing low volume expansion, high cycle and high initial efficiency of the battery.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a flow chart of a preparation method for preparing a silicon-oxygen anode material by using a liquid phase method according to an embodiment of the present invention.
Fig. 2 is a flow chart of a preparation method for preparing a silicon-oxygen anode material by using a solid-phase method according to an embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a silicon-oxygen anode material containing a carbon coating layer according to embodiment 1 of the present invention.
Fig. 4 is a graph of cycling curves for an assembled cell of a silicon oxygen anode material provided in example 8 of the present invention and an assembled cell of a silicon-based anode material of comparative example 2.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way, i.e., not as limiting the scope of the invention.
The embodiment of the invention provides a silicon-oxygen anode material, which comprises the following components: porous ceramics, silicon monoxide and doping elements.
Wherein, porous ceramics are used as a framework, and the silicon oxide and the doping elements are uniformly dispersed and distributed in the pores of the porous ceramics by a liquid phase method or a solid phase method; the doping elements comprise metal doping elements and/or nonmetal doping elements; the percentage of the doping element in the silicon monoxide is 0.1-20 wt%, preferably 0.5-10 wt%.
The metal doping element comprises one or more of Al, na, li, mg, ca, ti, mn, co, ni, cu, zn, zr, mo, ge and Sn; the non-metal doping element comprises one or more substances of any one doping element of B, N, P, S, C, as and Se.
The porous ceramic includes: one or more of porous SiC, porous silicon nitride, porous gallium nitride, porous titanium nitride and porous boron nitride; the particle size Dv50 of the porous ceramic is between 500nm and 100 mu m; the pore diameter of the pores of the porous ceramic is between 200nm and 20 mu m; the porosity of the porous ceramic is between 30% and 90%.
When the doping element substance is solid, the particle diameter Dv50 of the doping element substance is between 0.5nm and 10 mu m.
The total mass of the silicon monoxide and the doping elements accounts for 50-90% of the total mass of the silicon-oxygen cathode material; the porous ceramic accounts for 10-50% of the total mass of the silica negative electrode material.
In an optional scheme, the silicon-oxygen anode material further comprises a carbon coating layer; the mass of the carbon coating layer accounts for 0-20% of the total mass of the silicon-oxygen cathode material.
The embodiment of the invention provides a preparation method of the silicon-oxygen anode material, which comprises the following steps:
compounding the porous ceramic, the silicon monoxide and the substance containing the doping elements to obtain a silicon-oxygen cathode material; the compounding method comprises the following steps: liquid phase and/or solid phase processes.
When the substance doped with the element is a solid, the particle diameter Dv50 of the substance doped with the element is between 0.5nm and 10 mu m.
When the preparation method adopts a liquid phase method, the preparation process is shown in figure 1 and specifically comprises the following steps.
Wherein, the doping element comprises a metal doping element and/or a non-metal doping element; the metal doping element comprises one or more of Al, na, li, mg, ca, ti, mn, co, ni, cu, zn, zr, mo, ge and Sn; the non-metal doping element comprises one or more substances of any one doping element of B, N, P, S, C, as and Se.
The organic solvent includes: one or more of toluene, isopropanol, dimethylformamide, sulfolane, a glycol dimethyl ether solution containing biphenyl, a naphthalene solution containing pyrene or tetrahydrofuran containing p-terphenyl.
The uniformly dispersing apparatus includes: one of a ball mill, a dispersion machine or an ultrasonic stirrer.
And step 120, adding the porous ceramic into the premixed solution, and continuously and uniformly dispersing to obtain a mixed solution.
Wherein the porous ceramic includes: one or more of porous SiC, porous silicon nitride, porous gallium nitride, porous titanium nitride and porous boron nitride; the particle size Dv50 of the porous ceramic is between 500nm and 100 mu m; the pore diameter of the pores of the porous ceramic is between 200nm and 20 mu m; the porosity of the porous ceramic is between 30% and 90%.
And step 130, placing the mixed solution in a high-temperature furnace, heating to 700-1000 ℃, preserving heat for 2-5 hours, discharging, and crushing and screening to obtain the silicon-oxygen cathode material.
When the preparation method adopts a solid phase method, the preparation process is shown in figure 2 and specifically comprises the following steps.
And step 220, placing the precursor material in a heating furnace, heating to 600-1000 ℃ in an argon or nitrogen atmosphere, preserving heat for 3-10 hours, performing high-temperature heat treatment, discharging, and then crushing and screening to obtain the silica negative electrode material.
Wherein, the heating furnace includes: box-type heating furnaces or tube-type heating furnaces.
In an alternative embodiment, the preparation method further comprises: carbon coating is carried out on the silicon-oxygen cathode material, and then grading demagnetization is carried out; the carbon coating method comprises the following steps: one of gas phase coating, liquid phase coating or solid phase coating; the mass of the carbon coating layer accounts for 0-20% of the total mass of the silicon-oxygen cathode material.
The embodiment of the invention provides a silica negative electrode material which can be used as a negative active material in a negative electrode pole piece, and the negative electrode pole piece can be applied to a lithium battery.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the preparation process and characteristics of the silicon-oxygen anode material of the invention.
Example 1
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, and adopts a solid phase method, and the specific preparation process is as follows.
1) Uniformly mixing 900g of porous silicon nitride, 2kg of silicon monoxide, 110g of manganese oxide and 10g of black phosphorus, placing the mixture in a ball mill, setting the rotating speed to 700r/min under the argon atmosphere, positively rotating and reversely rotating, and carrying out ball milling for 20 hours to disperse the silicon monoxide, the manganese oxide and the black phosphorus in pores of the porous silicon nitride to obtain the silicon-based composite precursor material.
2) And (3) placing the silicon-based composite precursor material in a high-temperature furnace, heating to 800 ℃, preserving heat for 3 hours, and crushing and screening after discharging to obtain the silica negative electrode material.
The silicon-oxygen anode material prepared in this example was carbon-coated: putting 1kg of silicon-oxygen negative electrode material into a rotary furnace, heating to 1000 ℃ under the condition of protective atmosphere, and mixing the materials in a volume ratio of 2:1 introducing argon and acetylene gas with the same quantity as the argon for gas phase coating, keeping the temperature for 1.5 hours, closing an organic gas source, cooling to room temperature, discharging and grading to obtain the silicon-oxygen cathode material with the carbon coating layer.
The structure of the silicon-oxygen anode material containing the carbon coating layer prepared in the embodiment of the invention is schematically shown in fig. 3.
The silicon-oxygen negative electrode material containing the carbon coating layer prepared in the embodiment is used for preparing a negative electrode plate, and a button type half battery and a button type full battery are assembled for testing.
Preparation method and test of button half cell: mixing a silicon-oxygen negative electrode material containing a carbon coating layer, conductive additive carbon black and an adhesive (1:1 sodium carboxymethyl cellulose and styrene butadiene rubber) according to a mass ratio of 95%:2%: weighing 3%, preparing slurry by a beater, coating, drying, cutting into pieces, and assembling into a button type half cell in a glove box. The prepared button half cell was subjected to constant current charge and discharge mode test using a charge and discharge instrument at a discharge cut-off voltage of 0.005V and a charge cut-off voltage of 2V at a current density of 0.1C for the first week of charge and discharge test, and the test data are shown in table 1.
Preparation method and test of the full cell: preparing a negative pole piece: preparing a composite of a silicon-oxygen negative electrode material containing a carbon coating layer and graphite with the specific capacity of 450mAh/g, and a conductive additive and an adhesive according to the proportion of 95%:2%:3 percent of the raw materials are weighed and mixed; at room temperature, putting the mixed material and solvent deionized water into a pulping machine to prepare slurry; uniformly coating the prepared slurry on a copper foil at a coating speed of 2.2-3.5 m/min and a drying tunnel temperature of a coating machine of 70-100 ℃; and drying the two sides of the coating machine to obtain the negative pole piece.
Preparing a positive pole piece: according to the proportion of 96%:2%: weighing and mixing a nickel cobalt lithium manganate (NMC) ternary positive electrode material, a conductive additive and a binder according to a proportion of 2%; at room temperature, putting the mixed material and a solvent N-methyl pyrrolidone into a pulping machine to prepare slurry; uniformly coating the prepared slurry on an aluminum foil at a coating speed of between 2.0 and 3.0m/min and at a baking track temperature of between 90 and 120 ℃; and coating and drying the two sides of the anode plate by a coating machine to obtain the anode plate.
Preparing a battery: winding the prepared positive and negative electrode sheets and a diaphragm into a naked electric core, then packaging the electric core by an aluminum plastic film through a heat sealing process, removing water in the battery through high-temperature vacuum baking, and then injecting 1 mol of electrolyte, wherein the electrolyte is LiPF 6 And preparing a battery cell with a mixed solution of ethylene carbonate/dimethyl carbonate (EC/DMC), and vacuum sealing to obtain the battery.
And (3) testing: the constant current charge and discharge mode test was performed using a charge and discharge instrument with a discharge cut-off voltage of 2.75V and a charge cut-off voltage of 4.2V, and the discharge test after the first week was performed at a current density of 1C.
Testing the expansion rate of the pole piece: at 1C, when the first circle of the battery is in a full state and the 600 circles of the battery are in a full state, 5 groups of batteries are disassembled, the negative pole pieces of the batteries are taken, the thickness of 10 different areas of each group of the pole pieces is measured by a thickness gauge respectively, and the average value is taken. And obtaining the average thickness value of the pole piece in the initial state under the same test condition.
The calculation formula is as follows: the full-electricity expansion rate of the pole piece = (the average thickness of the pole piece when different turns of the pole piece are fully electrified-the initial average thickness of the pole piece)/the initial average thickness of the pole piece; the expansion rate of the negative pole piece can be tested, and the test data are shown in table 1 in detail.
The initial efficiency, 0.1C reversible capacity, 600 cycles of cycle retention rate test at 1C rate of the full cell and the expansion rate of the first and 600 cycles of the full cell of the half cell prepared in this example are detailed in table 1.
Example 2
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, and adopts a liquid phase method, and the specific preparation process is as follows.
1) Dissolving 4kg of silicon monoxide, 37.2g of metal lithium and 20g of graphene in a naphthalene solution containing pyrene, placing the solution in a dispersion machine, setting the rotation speed of a dispersion disc to be 1300r/min, and fully stirring the solution at room temperature for 24 hours to obtain a premixed solution.
2) Adding 1.2kg of porous boron nitride into the premixed solution, continuously dispersing in a dispersion machine, setting the rotating speed of a dispersion plate to be 1800r/min, and fully stirring for 42 hours at room temperature to obtain a mixed solution.
3) And (3) placing the mixed solution in a high-temperature furnace, heating to 730 ℃, preserving heat for 2 hours, and crushing and screening after discharging to obtain the silicon-oxygen cathode material.
The silicon-oxygen anode material prepared in this example was carbon-coated: putting 1kg of silica negative electrode material into a rotary furnace, heating to 800 ℃ under a protective atmosphere, and mixing the materials according to a volume ratio of 3:2 introducing argon and mixed gas of natural gas and propane for gas phase coating, wherein the volume ratio of the natural gas to the propane is 1:1, keeping the temperature for 2 hours, then closing an organic gas source, cooling to room temperature, discharging and grading to obtain the silicon-oxygen cathode material containing the carbon coating layer.
The negative electrode plate is prepared by using the silica negative electrode material containing the carbon coating layer prepared in the embodiment, and the battery is assembled for testing, wherein the specific process is the same as that in the embodiment 1. The test data are detailed in table 1.
Example 3
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, and adopts a solid phase method, and the specific preparation process is as follows.
1) 1kg of porous titanium nitride, 4kg of silicon monoxide and 200g of lithium hydride are uniformly mixed, placed in a ball mill, and subjected to ball milling for 36 hours in an argon atmosphere at a set rotating speed of 800r/min in forward and reverse rotation so that the silicon monoxide and the lithium hydride are dispersed in pores of the porous titanium nitride to obtain a precursor material.
2) And (3) placing the precursor material in a tube furnace, heating to 900 ℃, preserving heat for 2 hours, and crushing and screening after discharging to obtain the silicon-oxygen cathode material.
Carbon coating was performed on the silicon-oxygen negative electrode material prepared in this example: mixing 11kg of silicon-oxygen negative electrode material with petroleum asphalt according to the mass ratio of 15 to 1, placing the mixture in a high-temperature furnace, preserving the heat of the mixture for 100min at 900 ℃ in a protective atmosphere, cooling the mixture to room temperature, discharging and grading the mixture to obtain the silicon-oxygen negative electrode material containing the carbon coating layer.
The silica negative electrode material containing the carbon coating layer prepared in the embodiment is used for preparing a negative electrode piece and assembling a battery for testing, and the specific process is the same as that in embodiment 1. The test data are detailed in table 1.
Example 4
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, and adopts a solid phase method, and the specific preparation process is as follows.
1) 1.2kg of porous gallium nitride, 5kg of silicon monoxide and 180g of sulfur powder are uniformly mixed, placed in a ball mill, and ball-milled for 30 hours in a nitrogen atmosphere at a set rotating speed of 1500r/min in forward and reverse rotation to disperse the silicon monoxide and the sulfur powder in pores of the porous silicon nitride, so as to obtain a precursor material.
2) And (3) placing the precursor material in a tube furnace, heating to 1000 ℃, preserving heat for 2.5 hours, and crushing and screening after discharging to obtain the silicon-oxygen cathode material.
The silicon-oxygen anode material prepared in this example was carbon-coated: mixing 1kg of silicon-oxygen negative electrode material with asphalt emulsion according to the mass ratio of 13.
The negative electrode plate is prepared by using the silica negative electrode material containing the carbon coating layer prepared in the embodiment, and the battery is assembled for testing, wherein the specific process is the same as that in the embodiment 1. The test data are detailed in table 1.
Example 5
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, and adopts a liquid phase method, and the specific preparation process is as follows.
1) 5kg of silicon monoxide, 400g of aluminum oxide and 90g of selenium dioxide are dispersed in a toluene solution, and the toluene solution is placed in an ultrasonic stirrer, the ultrasonic frequency is 35KHz, and the solution is stirred ultrasonically for 9 hours to obtain a premixed solution.
2) Adding 1.2kg of porous titanium nitride into the mixed solution, continuously and uniformly dispersing in an ultrasonic machine, wherein the ultrasonic frequency is 35KHz, and ultrasonically stirring for 37 hours to obtain the mixed solution.
3) And (3) placing the mixed solution in a high-temperature furnace, heating to 850 ℃, preserving heat for 2.5 hours, discharging, crushing and screening to obtain the silicon-oxygen cathode material.
The silicon-oxygen anode material prepared in this example was carbon-coated: putting 1kg of silica material into a rotary furnace, heating to 1000 ℃ under a protective atmosphere, and mixing the materials according to a volume ratio of 2:1, introducing argon and propylene gas for gas phase coating, preserving the heat for 2 hours, closing an organic gas source, cooling to room temperature, discharging and grading to obtain the silicon-oxygen cathode material containing the carbon coating layer.
The negative electrode plate is prepared by using the silica negative electrode material containing the carbon coating layer prepared in the embodiment, and the battery is assembled for testing, wherein the specific process is the same as that in the embodiment 1. The test data are detailed in table 1.
Example 6
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, and adopts a liquid phase method, and the specific preparation process is as follows.
1) 2kg of silicon monoxide, 280g of carbamide and 150g of nickel oxide are dispersed in ethylene glycol dimethyl ether solution, the solution is placed in an ultrasonic stirrer, the ultrasonic frequency is set to be 40KHz, and the solution is stirred ultrasonically for 10 hours to obtain a premixed solution.
2) Adding 1.5kg of porous SiC into the premixed solution, continuously stirring in an ultrasonic stirrer, setting the ultrasonic frequency to be 30KHz, and ultrasonically stirring for 20 hours to obtain a mixed solution.
3) And (3) placing the mixed solution in a tubular furnace, heating to 1000 ℃, preserving heat for 2 hours, and crushing and screening after discharging to obtain the silicon-oxygen cathode material.
The silicon-oxygen anode material prepared in this example was carbon-coated: putting 1kg of silicon-oxygen negative electrode material into a rotary furnace, heating to 1050 ℃ under a protective atmosphere, and mixing the materials in a volume ratio of 3:1 introducing argon and propylene gas for gas phase coating, keeping the temperature for 1.5 hours, closing an organic gas source, cooling to room temperature, then discharging and grading, and finally obtaining the silicon-oxygen cathode material containing the carbon coating layer.
The negative electrode plate is prepared by using the silica negative electrode material containing the carbon coating layer prepared in the embodiment, and the battery is assembled for testing, wherein the specific process is the same as that in the embodiment 1. The test data are detailed in table 1.
Example 7
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, which adopt a liquid phase method, and the specific preparation process is as follows.
1) 2.1kg of silicon monoxide, 360g of tin-nickel alloy, 145g of melamine and 21L of isopropanol solution are jointly placed in a sand mill, and the sand mill is carried out for 24 hours under the argon atmosphere at the linear speed of 10m/s to obtain the premixed solution.
2) Adding 800g of porous gallium nitride into the premixed solution, sanding for 12 hours in a sand mill under the nitrogen atmosphere at a linear speed of 15m/s to obtain a mixed solution.
3) And (3) placing the mixed solution in a high-temperature furnace, heating to 800 ℃, preserving heat for 3 hours, and crushing and screening after discharging to obtain the silica negative electrode material.
The silica negative electrode material prepared in the embodiment is used for preparing a negative electrode plate and assembling a battery for testing, and the specific process is the same as that in embodiment 1. The test data are detailed in table 1.
Example 8
The embodiment provides a preparation process and a performance test of a silicon-oxygen anode material, and adopts a liquid phase method, and the specific preparation process is as follows.
1) 2.5kg of silicon monoxide, 110g of dinitrogen pentoxide and 90g of zinc oxide are dispersed in an absolute ethanol solution, the mixture is placed in a ball mill, the rotating speed of the ball mill is set to be 900r/min under the nitrogen atmosphere, the mixture is rotated in the forward direction and the reverse direction, and the ball milling is carried out for 6 hours, so as to obtain a premixed solution.
2) Adding 1.4kg of porous silicon nitride into the premixed solution, setting the rotating speed of the ball mill to 1200r/min in a ball mill under the nitrogen atmosphere, positively rotating and reversely rotating, and wet-grinding for 24 hours to obtain a mixed solution.
3) And (3) placing the mixed solution in a tubular furnace, heating to 850 ℃, preserving heat for 6 hours, discharging, crushing and screening to obtain the silicon-oxygen cathode material.
Carbon coating was performed on the silicon-oxygen negative electrode material prepared in this example: putting 1kg of silicon-oxygen negative electrode material into a rotary furnace, heating to 950 ℃ under a protective atmosphere, and mixing the materials in a volume ratio of 3:2 introducing argon and acetylene and propane mixed gas which is equal to the argon for gas phase coating, wherein the volume ratio of the acetylene to the propane is 2:1, keeping the temperature for 2 hours, and then closing an organic gas source to obtain the silicon-oxygen cathode material containing the carbon coating layer.
The assembled battery cycle curve of the silicon-oxygen anode material prepared by the embodiment of the invention is shown in fig. 4.
The negative electrode plate is prepared by using the silica negative electrode material containing the carbon coating layer prepared in the embodiment, and the battery is assembled for testing, wherein the specific process is the same as that in the embodiment 1. The test data are detailed in table 1.
Example 9
The embodiment provides a preparation process and a performance test of a silicon-oxygen cathode material, wherein a liquid phase method is adopted, and a preparation method adopts the liquid phase method, and the specific preparation process is as follows.
1) 2.2kg of silicon monoxide, 130g of phosphorus pentoxide, 100g of magnesium chloride and 18L of toluene solution are placed in an ultrasonic machine, ultrasonic frequency is set to be 30KHz, and ultrasonic dispersion is carried out for 3 hours to obtain a premixed solution.
2) Adding 1kg of porous boron nitride into the premixed solution, and continuously carrying out uniform dispersion in an ultrasonic machine, wherein the ultrasonic frequency is set to be 30KHz, and carrying out ultrasonic dispersion for 16 hours to obtain a mixed solution.
3) And (3) placing the mixed solution in a high-temperature furnace, heating to 850 ℃, preserving heat for 2.5 hours, discharging, crushing and screening to obtain the silica negative electrode material.
The silicon-oxygen anode material prepared in this example was carbon-coated: dissolving 1kg of silicon-oxygen negative electrode material and phenolic resin in acetone according to the proportion of 23.
The negative electrode plate is prepared by using the silica negative electrode material containing the carbon coating layer prepared in the embodiment, and the battery is assembled for testing, wherein the specific process is the same as that in the embodiment 1. The test data are detailed in table 1.
To better illustrate the effects of the examples of the present invention, comparative examples were compared with the above examples.
Comparative example 1
The comparative example provides a preparation process and performance test of a conventional undoped silicon-based negative electrode material. The preparation process is as follows.
1) 1kg of silicon powder and 1.2kg of silicon dioxide powder are uniformly mixed, placed in a vacuum high-temperature furnace, vacuumized to 140Pa, heated to 1750 ℃, and kept warm for 2 hours to obtain mixed gas.
2) And cooling and depositing the mixed gas on a stainless steel substrate to obtain a deposition material.
3) And crushing and screening the deposited material to obtain the conventional silicon-based negative electrode material.
And (3) carrying out carbon coating on the silicon-based negative electrode material prepared in the comparative example: mixing 1kg of silicon-based negative electrode material with petroleum asphalt according to the mass ratio of 24.
The negative electrode plate is made of the conventional silicon-based negative electrode material containing the carbon coating layer prepared in the comparative example, and the battery is assembled for testing, wherein the specific process is the same as that in example 1. The test data are detailed in table 1.
Comparative example 2
The comparative example provides a preparation process and performance test of a silicon-based anode material which adopts porous ceramic as a matrix and is not doped. The preparation process is as follows.
1) 2.3kg of silica and 15L of an absolute ethanol solution were placed in a dispersion machine, the rotation speed of a dispersion plate of the dispersion machine was set to 1300r/min, and the mixture was sufficiently stirred at room temperature for 4 hours to obtain a premixed solution.
2) And adding 700g of porous SiC into the premixed solution, setting the rotating speed at 1300r/min, and continuously dispersing for 18 hours in a dispersion machine to obtain a mixed solution.
3) And (3) placing the mixed solution in a high-temperature furnace, heating to 100 ℃, preserving the heat for 10 hours, discharging, and then crushing and screening to obtain the undoped silicon-based negative electrode material.
The undoped silicon-based negative electrode material prepared in this example was carbon-coated: 1kg of undoped silicon-based negative electrode material is placed in a rotary furnace, the temperature is raised to 900 ℃ under the protective atmosphere, and the volume ratio of the material to the material is 1:2, introducing argon and acetylene and propane mixed gas for gas phase coating, wherein the volume ratio of acetylene to propane is 1:1, keeping the temperature for 90min, closing an organic gas source, cooling to room temperature, discharging and grading to obtain the undoped silicon-based negative electrode material containing the carbon coating layer.
As shown in fig. 4, it can be seen from the graph that the cycle capacity retention of the full battery prepared in example 8 is higher than that of the full battery prepared in comparative example 2 at 200-600 cycles, which illustrates that the silica negative electrode material obtained by depositing the silicon oxide doped with the non-metal element and the metal element into the pores of the porous ceramic has better cycle performance than the undoped silica negative electrode material.
The undoped silica negative electrode material containing the carbon coating layer prepared in the embodiment is used for preparing a negative electrode piece and assembling a battery for testing, and the specific process is the same as that in embodiment 1. The test data are detailed in table 1.
The negative electrode materials in examples 1 to 9 and comparative examples 1 to 2 were subjected to initial efficiency and reversible capacity tests of charging, cycle retention rate of 600 cycles and expansion rate tests of the first and 600 cycles of negative electrode sheets at 1C rate of the full cell, and the test results are shown in table 1.
As can be seen from the comparison of the test data in table 1, the initial efficiency of the button half cells of examples 1-3 and 5-9 is better than that of the undoped button half cells of comparative examples 1 and 2 under the same test conditions because the metal elements, which can slow the volume expansion and improve the first-week coulombic efficiency, are doped in examples 1-3 and 5-9. In contrast, in example 4, since the metal element was not doped, the initial efficiency was similar to that of comparative examples 1 to 2.
The cycle performance and the expansion rate of the electrode plates of the examples 1 to 9 are superior to those of the comparative examples 1 and 2, because the porous ceramics are adopted as the frameworks in the examples 1 to 9, and the silicon oxide and the doped elements are distributed in the pores of the porous ceramics, the structure of the silicon-oxygen negative electrode material can be effectively stabilized due to the characteristics of high strength and high hardness of the porous ceramics, the volume expansion is buffered in the charging and discharging process, the alloy pulverization is inhibited, and meanwhile, the doped elements can accelerate the internal conduction rate of lithium ions.
The invention provides a silica negative electrode material and a preparation method and application thereof, aiming at solving the problems of larger volume expansion rate, poor conductivity, low first coulombic efficiency, poor battery cycle performance and the like of a silica negative electrode material. Because the porous ceramic skeleton has higher mechanical strength and hardness, when the porous ceramic skeleton is subjected to the expansion force of lithium intercalation, on one hand, the porous structure can reserve a space for the expansion of the silicon monoxide; on the other hand, the high-strength porous ceramic skeleton structure can effectively inhibit the volume expansion of the silicon monoxide and keep the structure of the negative electrode material stable. Meanwhile, the doped metal elements react with silicon dioxide in the silicon monoxide material to form a metal silicon oxygen complex, so that on one hand, the first-cycle coulombic efficiency of the battery can be remarkably improved, and on the other hand, the formed inert material metal silicon oxygen complex can also slow down volume expansion. The doped non-metallic elements can also accelerate the internal conduction rate of lithium ions and improve the conductivity of the silicon monoxide, thereby realizing low volume expansion, high cycle and high initial efficiency of the battery.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A silicon oxygen anode material, wherein the silicon oxygen anode material comprises: porous ceramics, silicon monoxide and doping elements;
the porous ceramic is used as a framework, and the silicon oxide and the doping elements are uniformly dispersed in pores of the porous ceramic by a liquid phase method or a solid phase method;
the doping element comprises a metal doping element and/or a non-metal doping element;
the metal doping element comprises one or more of Ca, ti, mn, co, ni, zr, mo and Ge doping element substances;
the non-metal doping element comprises one or more substances of any one of C, as and Se;
the doping element accounts for 0.1 to 20 percent of the mass of the silicon monoxide;
the porous ceramic includes: one or more of porous SiC, porous silicon nitride, porous gallium nitride and porous boron nitride;
the particle size Dv50 of the porous ceramic is between 500nm and 100 mu m; the pore diameter of the pores of the porous ceramic is between 200nm and 20 mu m.
2. The silicon-oxygen anode material according to claim 1, wherein the porosity of the porous ceramic is between 30% and 90%;
when the doping element substance is solid, the particle diameter Dv50 of the doping element substance is between 0.5nm and 10 mu m.
3. The silicon-oxygen anode material as claimed in claim 1, wherein the doping element accounts for 0.5-10% of the silicon monoxide by mass;
the total mass of the silicon monoxide and the doping elements accounts for 50-90% of the total mass of the silicon-oxygen anode material; the porous ceramic accounts for 10-50% of the total mass of the silica negative electrode material.
4. The silicon oxygen anode material of claim 1, further comprising a carbon cladding layer; the mass of the carbon coating layer accounts for 0-20% of the total mass of the silicon-oxygen negative electrode material.
5. A method for preparing a silicon-oxygen anode material according to any one of the claims 1 to 4, wherein the method comprises the following steps:
compounding the porous ceramic, the silicon monoxide and the substance containing the doping elements to obtain a silicon-oxygen cathode material;
the compounding method comprises the following steps: liquid phase and/or solid phase processes;
wherein the doping element comprises a metal doping element and/or a non-metal doping element;
the metal doping element comprises one or more of Al, na, li, mg, ca, ti, mn, co, ni, cu, zn, zr, mo, ge and Sn;
the non-metal doping element comprises one or more substances of any one doping element of B, N, P, S, C, as and Se;
the porous ceramic includes: one or more of porous SiC, porous silicon nitride, porous gallium nitride and porous boron nitride; the particle size Dv50 of the porous ceramic is between 500nm and 100 mu m; the pore diameter of the pores of the porous ceramic is between 200nm and 20 mu m; the porosity of the porous ceramic is between 30% and 90%;
when the doping element substance is solid, the particle diameter Dv50 of the doping element substance is between 0.5nm and 10 mu m.
6. The production method according to claim 5, characterized in that the liquid phase method comprises: uniformly dispersing the silicon monoxide and the doping element-containing substance in an organic solvent to obtain a premixed solution;
adding the porous ceramic into the premixed solution, and continuously and uniformly dispersing to obtain a mixed solution;
placing the mixed solution in a high-temperature furnace, heating to 700-1000 ℃, preserving heat for 2-5 hours, and crushing and screening after discharging to obtain the silicon-oxygen cathode material;
wherein the organic solvent comprises: one or more of toluene, isopropanol, dimethylformamide, sulfolane, a glycol dimethyl ether solution containing biphenyl, a naphthalene solution containing pyrene or tetrahydrofuran containing p-terphenyl;
the uniformly dispersing apparatus includes: one of a ball mill, a dispersion machine or an ultrasonic stirrer.
7. The method according to claim 5, wherein the solid phase method comprises;
placing the porous ceramic, the silicon monoxide and the substance containing the doping elements in a ball mill, and carrying out ball milling and mixing for 10-48 hours in an argon or nitrogen atmosphere to disperse the silicon monoxide and the doping elements in pores of the porous ceramic to obtain a precursor material;
placing the precursor material in a heating furnace, heating to 600-1000 ℃ in an argon or nitrogen atmosphere, preserving heat for 3-10 hours, and performing high-temperature heat treatment to obtain a silica negative electrode precursor material;
crushing and screening the silicon-oxygen negative electrode precursor material to obtain the silicon-oxygen negative electrode material;
wherein, the heating furnace includes: box-type heating furnaces or tube-type heating furnaces.
8. The method of manufacturing according to claim 5, further comprising: carrying out carbon coating on the silicon-oxygen cathode material, and then carrying out graded demagnetization;
the carbon coating method comprises the following steps: one of gas phase coating, liquid phase coating or solid phase coating;
the mass of the carbon coating layer accounts for 0-20% of the total mass of the silicon-oxygen negative electrode material.
9. A negative pole piece is characterized by comprising the silica negative pole material of any one of claims 1 to 4.
10. A lithium battery comprising the negative electrode sheet as claimed in claim 9.
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