CN115986068B - 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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- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000010405 anode material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000463 material Substances 0.000 claims abstract description 59
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 54
- 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
- 229910052799 carbon Inorganic materials 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
- 239000000377 silicon dioxide Substances 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
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- -1 aluminum ions Chemical class 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- 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 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 239000006012 monoammonium phosphate Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 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
- 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 4
- 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
- 239000000126 substance 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 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
- 230000008569 process Effects 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 5
- 229910021392 nanocarbon Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 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
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
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- 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
- 238000001035 drying Methods 0.000 description 2
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- 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
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- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000821827 Homo sapiens Sodium/nucleoside cotransporter 2 Proteins 0.000 description 1
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- 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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- 238000013508 migration Methods 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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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 silicon-oxygen anode material, and a preparation method and application thereof. The silicon-oxygen negative electrode material sequentially comprises silicon oxide, a mixture layer coated with the silicon oxide and a carbon layer coated on the surface of the mixture layer from inside to outside; the silicon oxide comprises crystal silicon dioxide; the mixture layer comprises a compound of lithium phosphate and aluminum. The capacity retention rate of the silicon oxygen anode material for 50 weeks is over 94 percent, and the initial coulombic efficiency is not lower than 80 percent.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a low-polarization silicon-oxygen 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 used energy storage battery at present. Along with the continuous change of application sites, the requirement on the energy density of the lithium ion battery is higher and higher, such as the energy density of the lithium ion battery required by a mobile phone battery and an electric automobile battery is further improved. Because the theoretical capacity of the silicon negative electrode can reach 3580mAh/g, the silicon negative electrode is much higher than the traditional graphite negative electrode (the theoretical capacity is only 372 mAh/g), and the silicon negative electrode is one of the most core materials used 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 charge and discharge process, so that the structure of the negative electrode plate is unstable, and the service life of the battery is short, namely the cycle performance is poor. The volume expansion degree of the silicon-oxygen anode material in the charge and discharge process is relatively small, but the silicon-oxygen anode material has relatively low ion mobility and high polarization degree due to the existence of oxygen, and the performance degradation caused by polarization is unfavorable for the silicon-oxygen anode material to obtain excellent cycle performance. In addition, the first coulomb efficiency of the silicon oxide anode material in the prior art is low, which is not beneficial to the practical application of the lithium ion battery.
Therefore, it is desirable to provide a new silicon oxygen anode material which has low polarization degree, small expansion degree, good cycle performance and high initial coulombic efficiency.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a low-polarization silicon-oxygen anode material, and a preparation method and application thereof. The silicon-oxygen anode material has low polarization degree, small expansion degree, good cycle performance and high first coulombic efficiency.
The invention is characterized in that: the silicon-oxygen anode 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 coats the silicon oxide, and the surface of the mixture layer is coated with a carbon layer. The mixture layer may or may not completely encapsulate the silica particles. According to the invention, lithium phosphate is introduced to improve the ionic conductivity and structural stability of the silicon oxide, and the polarization of the material in the charge and discharge processes is reduced. In addition, the silicon oxide contains crystal silicon dioxide and amorphous silicon dioxide, and the crystal silicon dioxide is helpful for improving the first coulombic efficiency of the silicon oxide anode material. The capacity retention rate of the silicon-oxygen anode material in 50 weeks of circulation exceeds 94%, and the initial coulombic efficiency is not lower than 80%.
A first aspect of the present invention provides a low polarization silicon oxygen anode material.
Specifically, a low-polarization silicon oxide anode material sequentially comprises silicon oxide, a mixture layer coating the silicon oxide and a carbon layer coating the surface of the mixture layer from inside to outside;
the silicon oxide comprises crystal silicon dioxide;
the mixture layer comprises a lithium phosphate and aluminum compound.
Preferably, the crystal form of the crystal form silicon dioxide is at least one of quartz phase and cristobalite phase.
Preferably, the silicon oxide includes crystalline silicon.
Preferably, the grain size range of the crystalline silicon is less than 5nm; further preferred, the particle size range of the crystalline silicon is less than 4nm, for example 1-3nm. The smaller the size of the crystal form silicon is, the smaller the expansion degree is, the more stable the structure of the silicon-oxygen anode material is, and the better the cycle performance of the silicon-oxygen anode material is.
Amorphous silica is also included in the silica. The less amorphous silica in the silica of the present invention, the higher the first coulombic efficiency of the silicon oxide negative electrode material.
Preferably, the thickness of the carbon layer is 2-53nm; further preferably, the thickness of the carbon layer is 5-50nm; more preferably, the thickness of the carbon layer is 10-20nm. The thickness of the carbon layer is on the order of nanometers and may be referred to as a nanocarbon layer.
Preferably, the weight of the lithium phosphate accounts for 0.5-7% of the total weight of the silicon-oxygen anode material; further preferably, the weight of the lithium phosphate accounts for 0.5-5% of the total weight of the silicon-oxygen anode material.
Preferably, the weight of the aluminum compound accounts for 0.5-15.5% of the total weight of the silicon-oxygen anode material; further preferably, the weight of the carbon nanotubes is 1-12% of the total weight of the silicon oxygen anode 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 anode material; more preferably, the weight of the carbon layer accounts for 3-5% of the total weight of the silicon-oxygen anode material.
A second aspect of the present invention provides a method for preparing the low-polarization silicon oxide negative electrode material.
Specifically, the preparation method of the low-polarization silicon-oxygen anode material comprises the following steps:
mixing silicon oxide with substances containing phosphate radicals and aluminum ions to obtain a material A;
heating the material A, adding a carbon source, and preserving heat to obtain a material B;
and mixing the material B with a lithium source to obtain a material C, and then heating to obtain the silicon-oxygen anode material.
Preferably, the phosphate and aluminum ion-containing material includes phosphate and aluminum salt.
Preferably, the phosphate is at least one selected from monoammonium phosphate, ammonium phosphate, monoaluminum phosphate, and aluminum phosphate.
Preferably, the aluminum salt is at least one selected from aluminum trichloride, aluminum hydroxide, aluminum nitrate, aluminum monohydrogen phosphate, aluminum dihydrogen phosphate and aluminum phosphate.
Preferably, the mass ratio of the silicon oxide to the phosphate to the aluminum salt is 1000: (15-60): (20-80), preferably 1000: (20-50): (30-50).
Preferably, the substance containing phosphate radicals and aluminum ions is aluminum phosphate, aluminum monohydrogen phosphate or aluminum dihydrogen phosphate. Aluminum phosphate, aluminum monohydrogen phosphate or aluminum dihydrogen phosphate contains both phosphate and aluminum ions, and thus, it is not necessary to add phosphate and aluminum salt separately.
Preferably, the mixing of the silica with the phosphate and aluminum ion containing material is performed in a solvent.
Further preferably, the solvent comprises water or ethanol. The amount of the solvent to be added is adjusted as needed.
Preferably, the temperature for heating the material A is 700-1000 ℃; preferably 750-950 ℃.
Preferably, the heating of the material A is carried out under a protective gas.
Preferably, the shielding gas includes nitrogen, argon or helium.
Preferably, the temperature of 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, after the carbon source is added, the temperature is maintained for 0.5 to 4 hours, preferably 1 to 4 hours. 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, material C is obtained and then subjected to a temperature increase treatment at a temperature of 500-900℃and preferably 600-850 ℃. The temperature-raising treatment can enable the lithium source to permeate the carbon layer and react with phosphate radical inside the carbon layer to generate lithium phosphate.
Preferably, material C is obtained, then the temperature of the heating treatment is 500-900 ℃, and the heat preservation time is 2-4 hours.
Preferably, the temperature-raising treatment of the material C is performed under a protective gas.
Preferably, the shielding gas includes nitrogen, argon or helium.
Preferably, after the material C is subjected to temperature rising treatment, the method further comprises the processes of cooling, screening and demagnetizing. The demagnetizing process is a conventional process in the art, with the aim of removing magnetic impurities.
A third aspect of the invention provides the use of a silicon oxygen anode material.
Specifically, the silicon-oxygen anode material is applied to the preparation of batteries.
A battery comprising the silicon oxygen anode material.
Preferably, the battery is a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The silicon oxide anode material sequentially comprises silicon oxide, a mixture layer coating the silicon oxide and a carbon layer coating the surface of the mixture layer from inside to outside; the silicon oxide comprises crystal silicon dioxide; the mixture layer comprises a lithium phosphate and aluminum compound. According to the invention, lithium phosphate is introduced to improve the ionic conductivity and structural stability of the silicon oxide, and the polarization of the material in the charge and discharge processes is reduced. In addition, the silicon oxide contains crystal silicon dioxide, so that the first coulombic efficiency of the silicon oxide anode material is improved. Lithium phosphate in the mixture layer coating the silicon oxide can not only improve the migration rate of lithium ions, but also enable SEI films (solid electrolyte interface films) formed on the surfaces of silicon oxide particles to be more stable, and reduce the consumption of electrolyte. The capacity retention rate of the silicon-oxygen anode material in 50 weeks of circulation exceeds 94%, and the initial coulombic efficiency is not lower than 80%.
(2) The preparation method of the silicon-oxygen anode material has simple process, is beneficial to industrial mass production and has low cost.
Drawings
FIG. 1 is an X-ray diffraction chart of a silicon oxide negative electrode 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 apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1: preparation of silicon-oxygen negative electrode material
The low-polarization silicon oxide anode material sequentially comprises silicon oxide, a mixture layer coated with the silicon oxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon oxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer comprises 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 monoammonium phosphate, 30g of aluminum hydroxide and 1000g of silicon oxide particles into a V-shaped stirring tank, and stirring in a rotating way 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, stirring for 90 minutes in a rotating way 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 room temperature of 20 ℃ under the nitrogen atmosphere, sieving, and demagnetizing to obtain the silicon-oxygen anode material.
Example 2: preparation of silicon-oxygen negative electrode material
The low-polarization silicon oxide anode material sequentially comprises silicon oxide, a mixture layer coated with the silicon oxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon oxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer comprises a compound of lithium phosphate and aluminum.
A preparation method of a low-polarization silicon-oxygen anode material comprises the following steps:
(1) Adding 60g of aluminum phosphate and 2kg of silicon oxide particles into 4kg of ethanol solvent, stirring for 60 minutes, centrifuging, taking solid, drying at 60 ℃ in vacuum for 10 hours, 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, stirring for 60 minutes in a rotating way 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 room temperature of 20 ℃ under the nitrogen atmosphere, sieving, and demagnetizing to obtain the silicon-oxygen anode material.
Example 3: preparation of silicon-oxygen negative electrode material
The low-polarization silicon oxide anode material sequentially comprises silicon oxide, a mixture layer coated with the silicon oxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon oxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer comprises a compound of lithium phosphate and aluminum.
A preparation method of a low-polarization silicon-oxygen anode material comprises the following steps:
(1) Adding 100g of monoammonium phosphate, 150g of aluminum chloride and 5kg of silica particles into 15kg of water, stirring for 60 minutes, filtering, and taking a solid (i.e. the solid obtained by filtering) and drying in vacuum 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, stirring for 60 minutes in a rotating way 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 room temperature of 20 ℃ under the nitrogen atmosphere, sieving, and demagnetizing to obtain the silicon-oxygen anode material.
Example 4: preparation of silicon-oxygen negative electrode material
The low-polarization silicon oxide anode material sequentially comprises silicon oxide, a mixture layer coated with the silicon oxide and a nano carbon layer coated on the surface of the mixture layer from inside to outside;
the silicon oxide comprises crystal silicon dioxide and amorphous silicon dioxide;
the mixture layer comprises 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 monoammonium phosphate, 50g of monoaluminum phosphate and 1000g of silica particles into a V-shaped stirring tank, and stirring in a rotating way 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, filling 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, stirring for 60 minutes in a rotating way 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 room temperature of 20 ℃ under the nitrogen atmosphere, sieving, and demagnetizing to obtain the silicon-oxygen anode material.
Comparative example 1 (without aluminium salt)
A preparation method of a silicon-oxygen anode material comprises the following steps:
(1) Adding 30g of monoammonium phosphate and 1000g of silicon oxide particles into a V-shaped stirring tank, and stirring in a rotating way 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, stirring for 90 minutes in a rotating way 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 room temperature of 20 ℃ under the nitrogen atmosphere, sieving, and demagnetizing to obtain the silicon-oxygen anode material.
Comparative example 2 (without adding lithium source)
A preparation method of a silicon-oxygen anode material comprises the following steps:
(1) Adding 30g of monoammonium phosphate, 30g of aluminum hydroxide and 1000g of silicon oxide particles into a V-shaped stirring tank, and stirring in a rotating way 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 heat for 3 hours, cooling to room temperature of 20 ℃ under the nitrogen atmosphere, sieving, and demagnetizing to obtain the silicon-oxygen anode material.
Product effect test
1. Example 1 silicon oxygen negative electrode Material structural characterization
FIG. 1 is an X-ray diffraction chart of the silicon oxide negative electrode material prepared in example 1. As can be seen from FIG. 1 (the ordinate "Intensity" of FIG. 1 shows the Intensity), the silica negative electrode material contains silica phase silica and lithium phosphate, and the 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 silicon-oxygen negative electrode material
The silicon oxygen cathode material prepared in example 1, PAA (polyacrylic acid) and conductive agent Super-P, HCNT2 (single-walled carbon nano tube) are mixed according to the weight ratio of 84.9:5:10:0.1, deionized water is added as a dispersing agent to prepare slurry, the slurry is coated on copper foil, and the slurry is subjected to vacuum drying, rolling and sheet punching to prepare a pole piece, wherein the counter electrode is a metal lithium sheet, and the electrolyte adopts 1.0mol/L LiPF 6 The solution (solvent composition in the solution is ethyl carbonate EC: dimethyl carbonate DMC: fluoroethylene carbonate FEC=4:5.5:0.5 (volume ratio)), the membrane adopts a polypropylene microporous membrane to assemble a CR2016 button cell, the charge and discharge test uses 150mA/g current density to conduct constant current discharge to 0.005V, then 30mA/g current density to conduct constant current discharge to 0.005V, and then 150mA/g constant current charge to 1.5V, and corresponding electrical properties are obtained, and the results are shown in Table 1.
The silicon oxygen anode materials prepared in examples 2 to 4 and comparative examples 1 to 2 were also tested for the corresponding electrical properties by the above-mentioned method, and the results are shown in Table 1.
As can be seen from Table 1, after the silicon-oxygen anode materials prepared in examples 1-4 of the present invention are assembled into a battery, the corresponding first coulomb efficiency and the cycle 50 week capacity retention rate are high, which are significantly better than the corresponding performances of comparative examples 1-2.
As can be further seen from table 1, the comparative example 1, in which the aluminum salt was not used to prepare the silicon oxygen anode material, resulted in a significant reduction in initial coulombic efficiency, and the comparative example 2, in which the lithium source was not used to prepare the silicon oxygen anode material, resulted in a significant reduction in cycle performance. Therefore, in the preparation process of the silicon-oxygen anode material, the aluminum salt has the effect of obviously improving the first coulombic efficiency, and the lithium phosphate formed by adding the lithium source has the effect of improving the cycle performance.
Claims (7)
1. The preparation method of the silicon-oxygen anode material is characterized by comprising the following steps of:
mixing silicon oxide with substances containing phosphate radicals and aluminum ions to obtain a material A;
heating the material A, adding a carbon source, and preserving heat to obtain a material B;
and mixing the material B with a lithium source to obtain a material C, and then heating to obtain the silicon-oxygen anode material.
2. The method of claim 1, wherein the phosphate and aluminum ion containing material comprises a phosphate and an aluminum salt.
3. The method according to claim 2, wherein the phosphate is at least one selected from the group consisting of monoammonium phosphate, ammonium phosphate, monoaluminum phosphate, and aluminum phosphate; the aluminum salt is at least one selected from aluminum trichloride, aluminum hydroxide, aluminum nitrate, aluminum monohydrogen phosphate, aluminum dihydrogen phosphate and aluminum phosphate; the lithium source is at least one selected from metal lithium powder, lithium hydroxide, lithium carbonate, lithium hydride or lithium aluminum hydride.
4. The preparation method according to claim 1, wherein the silicon-oxygen negative electrode material comprises silicon oxide, a mixture layer coating the silicon oxide and a carbon layer coating the surface of the mixture layer from inside to outside in sequence;
the silicon oxide comprises crystal silicon dioxide;
the mixture layer comprises a compound of lithium phosphate and aluminum;
the crystal form of the crystal form silicon dioxide is at least one of quartz phase and cristobalite phase.
5. The method according to claim 4, wherein the silicon oxide comprises crystalline silicon, and the particle size range of the crystalline silicon is less than 5nm.
6. The method according to claim 4, wherein the thickness of the carbon layer is 2-53nm.
7. The preparation method according to claim 4, wherein the weight of the lithium phosphate is 0.5-7% of the total weight of the silicon-oxygen negative electrode material; the weight of the aluminum compound accounts for 0.5-15.5% of the total weight of the silicon-oxygen anode material; the weight of the carbon layer accounts for 2-12% of the total weight of the silicon-oxygen anode material.
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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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| 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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