CN115986068A - Low-polarization silicon-oxygen anode material and preparation method and application thereof - Google Patents
Low-polarization silicon-oxygen anode material and preparation method and application thereof Download PDFInfo
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- CN115986068A CN115986068A CN202211422046.3A CN202211422046A CN115986068A CN 115986068 A CN115986068 A CN 115986068A CN 202211422046 A CN202211422046 A CN 202211422046A CN 115986068 A CN115986068 A CN 115986068A
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- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 19
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 claims description 33
- -1 aluminum compound Chemical class 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 20
- 238000001816 cooling Methods 0.000 description 14
- 238000012216 screening Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
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- 229910021392 nanocarbon Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 101000821827 Homo sapiens Sodium/nucleoside cotransporter 2 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 102100021541 Sodium/nucleoside cotransporter 2 Human genes 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- 125000005912 ethyl carbonate group Chemical group 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000011534 incubation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 belongs to the technical field of battery materials, and discloses a low-polarization silica anode material, and a preparation method and application thereof. The silicon-oxygen cathode material sequentially comprises silicon monoxide, a mixture layer coating the silicon monoxide and a carbon layer coating the surface of the mixture layer from inside to outside; the silicon monoxide comprises crystal silicon dioxide; the mixture layer includes a compound of lithium phosphate and aluminum. The capacity retention rate of the silicon-oxygen anode material in 50-week circulation exceeds 94%, and the first coulombic efficiency is not lower than 80%.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a low-polarization silica anode material, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long service life, no memory effect and the like, and is the most widely applied energy storage battery at present. With the continuous change of application fields, the requirements on the energy density of the lithium ion battery are higher and higher, and the energy density of the lithium ion battery is required to be further improved for mobile phone batteries and electric vehicle batteries. Because the theoretical capacity of the silicon cathode can reach 3580mAh/g, which is much higher than that of the traditional graphite cathode (the theoretical capacity is only 372 mAh/g), the silicon cathode is one of the most core materials for improving the performance of the lithium ion battery in the industry at present. However, the silicon negative electrode has a large volume expansion degree in the charging and discharging processes, which causes instability of the negative electrode sheet structure, and thus the battery has a short service life, i.e., poor cycle performance. The volume expansion degree of the silicon-oxygen cathode material in the charging and discharging process is relatively small, but the silicon-oxygen cathode material has relatively slow ion mobility and high polarization degree due to the existence of oxygen, and the performance degradation caused by polarization is not beneficial to the silicon-oxygen cathode material to obtain excellent cycle performance. And the first coulombic efficiency of the silicon-oxygen cathode material in the prior art is low, which is not favorable for the practical application of the lithium ion battery.
Therefore, it is highly desirable to provide a new silicon-oxygen anode material with low polarization, low expansion, good cycle performance, and high first coulombic efficiency.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a low-polarization silica negative electrode material, and a preparation method and application thereof. The silica cathode material has low polarization degree, small expansion degree, good cycle performance and high first coulombic efficiency.
The invention conception of the invention is as follows: the silicon-oxygen negative electrode material comprises silicon oxide, lithium phosphate, an aluminum compound and a carbon layer, wherein a mixture layer formed by the lithium phosphate and the aluminum compound covers the silicon oxide, and the surface of the mixture layer is covered with the carbon layer. The mixture layer may or may not completely coat the silica particles. According to the invention, the lithium phosphate is introduced to improve the ionic conductivity and structural stability of the silicon oxide, and reduce the polarization of the material in the charging and discharging processes. In addition, the silicon monoxide contains crystal silicon dioxide and amorphous silicon dioxide, and the crystal silicon dioxide is beneficial to improving the first coulombic efficiency of the silicon oxygen cathode material. The capacity retention rate of the silicon-oxygen anode material exceeds 94% after 50-week circulation, and the first coulombic efficiency is not lower than 80%.
A first aspect of the invention provides a low polarization silicon oxygen anode material.
Specifically, the low-polarization silicon-oxygen negative electrode material sequentially comprises, from inside to outside, silicon monoxide, a mixture layer coating the silicon monoxide, and a carbon layer coating the surface of the mixture layer;
the silicon monoxide comprises crystal silicon dioxide;
the mixture layer comprises a lithium phosphate, aluminum compound.
Preferably, the crystal form of the crystalline silica is at least one of a quartz phase and a cristobalite phase.
Preferably, the silicon monoxide comprises crystal silicon.
Preferably, the particle size range of the crystal form silicon is less than 5nm; it is further preferred that the crystalline silicon has a particle size in the range of less than 4nm, for example 1-3nm. The smaller the size of the crystal silicon is, the smaller the expansion degree is, the more stable the structure of the silicon-oxygen cathode material is, and the better the cycle performance of the silicon-oxygen cathode material is.
The silicon monoxide also comprises amorphous silicon dioxide. The less amorphous silicon dioxide in the silicon monoxide provided by the invention, the higher the first coulombic efficiency of the silicon oxygen negative electrode material is.
Preferably, the carbon layer has a thickness of 2 to 53nm; further preferably, the carbon layer has a thickness of 5 to 50nm; more preferably, the carbon layer has a thickness of 10 to 20nm. The carbon layer has a thickness of the order of nanometers and may be referred to as a nano-carbon layer.
Preferably, the weight of the lithium phosphate accounts for 0.5-7% of the total weight of the silicon-oxygen negative electrode material; more preferably, the weight of the lithium phosphate accounts for 0.5-5% of the total weight of the silicon-oxygen negative electrode material.
Preferably, the weight of the aluminum compound accounts for 0.5-15.5% of the total weight of the silicon-oxygen negative electrode material; more preferably, the weight of the carbon nano tube accounts for 1-12% of the total weight of the silicon-oxygen cathode material.
Preferably, the weight of the carbon layer accounts for 2-12% of the total weight of the silicon oxygen anode material; further preferably, the weight of the carbon layer accounts for 2-10% of the total weight of the silicon-oxygen negative electrode material; more preferably, the weight of the carbon layer accounts for 3-5% of the total weight of the silicon oxygen negative electrode material.
The second aspect of the present invention provides a method for preparing the low-polarization silicon-oxygen negative electrode material.
Specifically, the preparation method of the low-polarization silicon-oxygen negative electrode material comprises the following steps:
mixing silicon monoxide with a substance containing phosphate radicals and aluminum ions to obtain a material A;
heating the material A, adding a carbon source, and carrying out heat preservation to obtain a material B;
and mixing the material B with a lithium source to obtain a material C, and then carrying out heating treatment to obtain the silicon-oxygen cathode material.
Preferably, the phosphate and aluminum ion-containing substance includes phosphate and aluminum salts.
Preferably, the phosphate is at least one selected from ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, aluminum monohydrogen phosphate, aluminum dihydrogen phosphate and aluminum phosphate.
Preferably, the aluminum salt is selected from at least one of aluminum trichloride, aluminum hydroxide, aluminum nitrate, aluminum monohydrogen phosphate, aluminum dihydrogen phosphate and aluminum phosphate.
Preferably, the mass ratio of the silica to the phosphate to the aluminum salt is 1000: (15-60): (20-80), preferably 1000: (20-50): (30-50).
Preferably, the substance containing phosphate groups and aluminum ions is aluminum phosphate, aluminum monohydrogen phosphate or aluminum dihydrogen phosphate. The aluminum phosphate, monohydrogen aluminum phosphate or dihydrogen aluminum phosphate contains both phosphate and aluminum ions, and therefore, there is no need to separately add phosphate and aluminum salt.
Preferably, the mixing of the silica with the phosphate and aluminum ion-containing substance is carried out in a solvent.
Further preferably, the solvent comprises water or ethanol. The amount of the solvent added may be adjusted as necessary.
Preferably, the temperature for heating the material A is 700-1000 ℃; preferably 750-950 ℃.
Preferably, the temperature of the material A is raised under a protective gas.
Preferably, the protective gas comprises nitrogen, argon or helium.
Preferably, the temperature for heating the material A is 700-1000 ℃, then the temperature is kept for 1-2 hours, and then a carbon source is added.
Preferably, the carbon source is a gaseous carbon source.
Further preferably, the carbon source is selected from at least one of methane, ethylene, propylene, or acetylene.
Preferably, the incubation is carried out for 0.5 to 4 hours, preferably 1 to 4 hours, after the addition of the carbon source. And after the heat preservation is finished, cooling to room temperature to obtain a material B.
Preferably, the lithium source is selected from at least one of metallic lithium powder, lithium hydroxide, lithium carbonate, lithium hydride, or lithium aluminum hydride.
Preferably, the mass ratio of the lithium source to the phosphate is 30-180: (30-100), preferably 40-150: (30-100).
Preferably, the material C is obtained and then subjected to temperature raising treatment at a temperature of 500-900 ℃, preferably 600-850 ℃. The temperature raising treatment allows the lithium source to penetrate the carbon layer and react with phosphate radicals inside the carbon layer to generate lithium phosphate.
Preferably, the material C is obtained, then the temperature of the heating treatment is 500-900 ℃, and the time of heat preservation is 2-4 hours.
Preferably, the temperature raising treatment of the material C is carried out under protective gas.
Preferably, the protective gas comprises nitrogen, argon or helium.
Preferably, the heating treatment of the material C further comprises the processes of cooling, screening and demagnetizing. The demagnetization process is a conventional process in the art, and aims to remove magnetic impurities.
The third aspect of the invention provides an application of the silicon-oxygen anode material.
In particular to application of the silicon-oxygen anode material in preparing a battery.
A battery comprises the silicon-oxygen negative electrode material.
Preferably, the battery is a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The silicon-oxygen cathode material sequentially comprises silicon monoxide, a mixture layer coating the silicon monoxide and a carbon layer coating the surface of the mixture layer from inside to outside; the silicon monoxide comprises crystalline silicon dioxide; the mixture layer includes a compound of lithium phosphate and aluminum. According to the invention, the lithium phosphate is introduced to improve the ionic conductivity and structural stability of the silicon oxide, and reduce the polarization of the material in the charging and discharging processes. In addition, the silicon monoxide contains crystal silicon dioxide, so that the first coulombic efficiency of the silicon oxygen cathode material is improved. Lithium phosphate in the mixture layer coating the silicon oxide can improve the lithium ion migration rate, and can ensure that an SEI film (solid electrolyte interface film) formed on the surface of the silicon oxide particles is more stable, thereby reducing the consumption of electrolyte. The capacity retention rate of the silicon-oxygen anode material exceeds 94% after 50-week circulation, and the first coulombic efficiency is not lower than 80%.
(2) The preparation method of the silicon-oxygen cathode material is simple in process, beneficial to industrial mass production and low in cost.
Drawings
FIG. 1 is an X-ray diffraction pattern of a silicon oxygen anode material prepared in example 1;
FIG. 2 is a surface topography of the silicon-oxygen anode material prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention more clearly apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1: preparation of silicon-oxygen cathode material
A low-polarization silicon-oxygen negative electrode material sequentially comprises a silicon monoxide, a mixture layer coated with the silicon monoxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon monoxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer includes a compound of lithium phosphate and aluminum.
A preparation method of a low-polarization silicon-oxygen anode material comprises the following steps:
(1) Adding 30g of ammonium monohydrogen phosphate, 30g of aluminum hydroxide and 1000g of silica particles into a V-shaped stirring tank, and rotationally stirring for 60 minutes to obtain a material A;
(2) Placing the material A in a rotary furnace, heating to 800 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, charging 3L/min of acetylene, preserving heat for 2 hours, cooling to room temperature of 20 ℃ under the nitrogen atmosphere, discharging and screening to obtain a material B;
(3) And adding the material B and 50g of lithium hydroxide into a V-shaped stirring tank, rotationally stirring for 90 minutes to obtain a material C, placing the material C into a rotary furnace, heating to 750 ℃ under the protection of nitrogen atmosphere, preserving heat for 3 hours, cooling to 20 ℃ under the protection of nitrogen atmosphere, screening, and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 2: preparation of silicon-oxygen cathode material
A low-polarization silicon-oxygen negative electrode material sequentially comprises a silicon monoxide, a mixture layer coated with the silicon monoxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon monoxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer includes a compound of lithium phosphate and aluminum.
A preparation method of a low-polarization silicon-oxygen negative electrode material comprises the following steps:
(1) Adding 60g of aluminum phosphate and 2kg of silica particles into 4kg of ethanol solvent, stirring for 60 minutes, centrifuging, taking solid matter, drying for 10 hours at 60 ℃ in vacuum, and screening to obtain a material A;
(2) Placing the material A in a rotary furnace, heating to 800 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, charging 5L/min of acetylene, preserving heat for 3 hours, cooling to room temperature of 20 ℃ under the nitrogen atmosphere, discharging and screening to obtain a material B;
(3) And adding the material B and 150g of lithium carbonate into a V-shaped stirring tank, rotationally stirring for 60 minutes to obtain a material C, placing the material C into a rotary furnace, heating to 800 ℃ under the protection of nitrogen atmosphere, preserving heat for 3 hours, cooling to 20 ℃ under the protection of nitrogen atmosphere, sieving, and demagnetizing to obtain the silica negative electrode material.
Example 3: preparation of silicon-oxygen cathode material
A low-polarization silicon-oxygen negative electrode material sequentially comprises a silicon monoxide, a mixture layer coated with the silicon monoxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon monoxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer includes a compound of lithium phosphate and aluminum.
A preparation method of a low-polarization silicon-oxygen negative electrode material comprises the following steps:
(1) Adding 100g of ammonium monohydrogen phosphate, 150g of aluminum chloride and 5kg of silica particles into 15kg of water, stirring for 60 minutes, filtering, and vacuum-drying a solid (namely the solid obtained by filtering) at 80 ℃ for 10 hours to obtain a material A;
(2) Placing the material A in a rotary furnace, heating to 850 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, charging 3L/min of acetylene, preserving heat for 2 hours, cooling to room temperature of 20 ℃ under the nitrogen atmosphere, discharging and screening to obtain a material B;
(3) And adding the material B and 50g of lithium hydride into a V-shaped stirring tank, rotationally stirring for 60 minutes to obtain a material C, placing the material C into a rotary furnace, heating to 650 ℃ under the protection of nitrogen atmosphere, preserving heat for 3 hours, cooling to 20 ℃ under the protection of nitrogen atmosphere, sieving, and demagnetizing to obtain the silica negative electrode material.
Example 4: preparation of silicon-oxygen cathode material
A low-polarization silicon-oxygen negative electrode material sequentially comprises a silicon monoxide, a mixture layer coated with the silicon monoxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon monoxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer includes a compound of lithium phosphate, aluminum.
A preparation method of a low-polarization silicon-oxygen negative electrode material comprises the following steps:
(1) Adding 30g of ammonium dihydrogen phosphate, 50g of aluminum dihydrogen phosphate and 1000g of silicon monoxide particles into a V-shaped stirring tank, and rotationally stirring for 60 minutes to obtain a material A;
(2) Placing the material A in a rotary furnace, heating to 950 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, charging 5L/min of methane, preserving heat for 2 hours, cooling to room temperature of 20 ℃ under the nitrogen atmosphere, discharging and screening to obtain a material B;
(3) And adding the material B and 40g of lithium aluminum hydride into a V-shaped stirring tank, rotationally stirring for 60 minutes to obtain a material C, placing the material C into a rotary furnace, heating to 650 ℃ under the protection of nitrogen atmosphere, preserving heat for 3 hours, cooling to 20 ℃ under the protection of nitrogen atmosphere, screening, and demagnetizing to obtain the silicon-oxygen negative electrode material.
Comparative example 1 (without aluminium salt)
A preparation method of a silicon-oxygen anode material comprises the following steps:
(1) Adding 30g of ammonium monohydrogen phosphate and 1000g of silicon monoxide particles into a V-shaped stirring tank, and rotationally stirring for 60 minutes to obtain a material A;
(2) Placing the material A in a rotary furnace, heating to 800 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, charging 3L/min of acetylene, preserving heat for 2 hours, cooling to room temperature of 20 ℃ under the nitrogen atmosphere, discharging and screening to obtain a material B;
(3) And adding the material B and 50g of lithium hydroxide into a V-shaped stirring tank, rotationally stirring for 90 minutes to obtain a material C, placing the material C into a rotary furnace, heating to 750 ℃ under the protection of nitrogen atmosphere, preserving heat for 3 hours, cooling to 20 ℃ under the protection of nitrogen atmosphere, sieving, and demagnetizing to obtain the silica negative electrode material.
COMPARATIVE EXAMPLE 2 (without lithium source)
A preparation method of a silicon-oxygen anode material comprises the following steps:
(1) Adding 30g of ammonium monohydrogen phosphate, 30g of aluminum hydroxide and 1000g of silicon monoxide particles into a V-shaped stirring tank, and rotationally stirring for 60 minutes to obtain a material A;
(2) Placing the material A in a rotary furnace, heating to 800 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, charging 3L/min of acetylene, preserving heat for 2 hours, cooling to room temperature of 20 ℃ under the nitrogen atmosphere, discharging and screening to obtain a material B;
(3) And (3) placing the material B in a rotary furnace, heating to 750 ℃ under the protection of nitrogen atmosphere, preserving the heat for 3 hours, cooling to 20 ℃ under the protection of nitrogen atmosphere, screening, and demagnetizing to obtain the silicon-oxygen negative electrode material.
Product effectiveness testing
1. Example 1 structural characterization of silicon-oxygen anode materials
FIG. 1 is an X-ray diffraction pattern of a silicon-oxygen negative electrode material obtained in example 1. As can be seen from fig. 1 (Intensity is shown by ordinate "Intensity" in fig. 1), the silica negative electrode material contains silica in a quartz phase and lithium phosphate, and a broad peak between 16 and 26 degrees represents amorphous silica.
FIG. 2 is a surface topography of the silicon-oxygen anode material prepared in example 1.
2. Performance test of silica cathode material
Mixing the silica negative electrode material prepared in the embodiment 1, PAA (polyacrylic acid), a conductive agent Super-P and HCNT2 (single-walled carbon nanotube) according to a weight ratio of 84.9 6 The solution (the solvent in the solution has the composition of ethyl carbonate EC: dimethyl carbonate DMC: fluoroethylene carbonate FEC =4:5.5 (volume ratio)), the diaphragm is assembled into a CR2016 coin cell using a polypropylene microporous membrane, and the charge-discharge test uses a current density of 150mA/g for constant current discharge to 0.005V, then a current density of 30mA/g for constant current discharge to 0.005V, and then a current density of 150mA/g for constant current charge to 1.5V, to obtain the corresponding electrical properties, and the results are shown in table 1.
The silicon oxide negative electrode materials prepared in examples 2 to 4 and comparative examples 1 to 2 were also tested for their respective electrical properties in the manner described above, and the results are shown in table 1.
As can be seen from Table 1, after the silicon-oxygen cathode materials prepared in the embodiments 1-4 are assembled into a battery, the corresponding first coulombic efficiency is high, the capacity retention rate after 50 weeks of circulation is high, and the performance is obviously superior to the corresponding performance of the comparative examples 1-2.
As can be further seen from table 1, comparative example 1, in which no aluminum salt was used to prepare the silicon-oxygen negative electrode material, resulted in a significant decrease in the first coulombic efficiency, and comparative example 2, in which no lithium source was used to prepare the silicon-oxygen negative electrode material, resulted in a significant decrease in the cycle performance. Therefore, in the preparation process of the silicon-oxygen cathode material, the aluminum salt has the effect of remarkably improving the first coulombic efficiency, and the lithium phosphate formed by adding the lithium source has the effect of improving the cycle performance.
Claims (10)
1. The silicon-oxygen cathode material is characterized by sequentially comprising silicon monoxide, a mixture layer coating the silicon monoxide and a carbon layer coating the surface of the mixture layer from inside to outside;
the silicon monoxide comprises crystal silicon dioxide;
the mixture layer comprises a lithium phosphate, aluminum compound.
2. The silicon oxygen cathode material of claim 1, wherein the crystalline form of the crystalline form silicon dioxide is at least one of a quartz phase and a cristobalite phase.
3. The silicon oxy anode material of claim 1, wherein the silicon monoxide comprises crystalline silicon, and wherein the crystalline silicon has a particle size range of less than 5nm.
4. The silicon oxygen anode material of claim 1, wherein the carbon layer has a thickness of 2-53nm.
5. The silicone anode material of claim 1, wherein the weight of the lithium phosphate is 0.5-7% of the total weight of the silicone anode material; the weight of the aluminum compound accounts for 0.5-15.5% of the total weight of the silicon-oxygen negative electrode material; the weight of the carbon layer accounts for 2-12% of the total weight of the silicon-oxygen anode material.
6. The method for preparing a silicon oxygen anode material of any one of claims 1 to 5, characterized by comprising the following steps:
mixing silicon monoxide with a substance containing phosphate radicals and aluminum ions to obtain a material A;
heating the material A, adding a carbon source, and carrying out heat preservation to obtain a material B;
and mixing the material B with a lithium source to obtain a material C, and then carrying out heating treatment to obtain the silicon-oxygen cathode material.
7. The production method according to claim 6, wherein the substance containing phosphate and aluminum ions includes phosphate and aluminum salts.
8. The production method according to claim 7, wherein the phosphate is at least one selected from the group consisting of ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, aluminum monohydrogen phosphate, aluminum dihydrogen phosphate, and aluminum phosphate; the aluminum salt is selected from at least one of aluminum trichloride, aluminum hydroxide, aluminum nitrate, aluminum monohydrogen phosphate, aluminum dihydrogen phosphate and aluminum phosphate; the lithium source is at least one selected from metallic lithium powder, lithium hydroxide, lithium carbonate, lithium hydride or lithium aluminum hydride.
9. Use of the silicon oxygen anode material of any of claims 1 to 5 in the preparation of batteries.
10. A battery comprising the silicon oxygen negative electrode material according to any one of claims 1 to 5.
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| CN104022257A (en) * | 2014-06-16 | 2014-09-03 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon dioxide composite anode material for lithium ion battery, as well as preparation method and application of silicon dioxide composite anode material |
| CN110620223A (en) * | 2019-09-25 | 2019-12-27 | 福建翔丰华新能源材料有限公司 | Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof |
| CN111048756A (en) * | 2019-12-04 | 2020-04-21 | 兰溪致德新能源材料有限公司 | High-conductivity silica negative electrode material and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104022257A (en) * | 2014-06-16 | 2014-09-03 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon dioxide composite anode material for lithium ion battery, as well as preparation method and application of silicon dioxide composite anode material |
| CN110620223A (en) * | 2019-09-25 | 2019-12-27 | 福建翔丰华新能源材料有限公司 | Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof |
| CN111048756A (en) * | 2019-12-04 | 2020-04-21 | 兰溪致德新能源材料有限公司 | High-conductivity silica negative electrode material and application thereof |
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