CN115706221A - Silicon monoxide composite material, preparation method and application thereof, and lithium ion battery - Google Patents
Silicon monoxide composite material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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- CN115706221A CN115706221A CN202110943636.XA CN202110943636A CN115706221A CN 115706221 A CN115706221 A CN 115706221A CN 202110943636 A CN202110943636 A CN 202110943636A CN 115706221 A CN115706221 A CN 115706221A
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 68
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002821 niobium Chemical class 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 150000003681 vanadium Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical group [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 102220043159 rs587780996 Human genes 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a silicon monoxide composite material, a preparation method and application thereof, and a lithium ion battery. The preparation method of the silicon monoxide composite material comprises the following steps: granulating and calcining the mixed material; wherein the mixed material is a mixture of a premix compound formed by mixing metal oxide and a carbon source and silicon monoxide; the D50 particle size of the premix is less than or equal to 5nm; the D50 particle size of the mixed material is less than or equal to 100nm; the grain diameter of the mixed material is larger than that of the premix; the metal oxide comprises one or more of lithium titanate, niobium pentoxide and vanadium pentoxide. The preparation method has the advantages of low production cost, high production safety, convenient operation and easy large-scale mass production and use; the prepared silicon monoxide composite material has lower expansion rate, can ensure the electric capacity of the battery after being used for the battery, and has better cycle performance.
Description
Technical Field
The invention relates to a silicon monoxide composite material, a preparation method and application thereof, and a lithium ion battery.
Background
The maximum theoretical specific capacity of silicon can reach 4200mAh/g, and the silicon negative electrode material cannot realize wide-range commercial application in time because the silicon negative electrode material has several disadvantages while having many advantages. Firstly, the silicon negative electrode material undergoes volume change of more than 300% in the charging and discharging processes, such high volume expansion and shrinkage easily leads to the pulverization of the electrode material, the separation of the electrode material from the contact with the current collector and the electrode conductive network, and the volume change brings about the generation of new surfaces, so that a new solid-electrolyte interface (SEI) needs to be formed, thereby leading to the large consumption of the electrolyte and further leading to the substantial reduction of the cycle life. On the other hand, the electrical conductivity and lithium ion diffusion speed of silicon are lower than those of graphite, which limits the performance of silicon under high-current and high-power conditions.
The theoretical specific capacity of the silicon monoxide is more than 2000mAh/g, although the capacity is reduced compared with the silicon, the cycle performance is greatly improved because the lithium ions and the silica material react to generate Li in the first charge-discharge process of the silicon monoxide 2 O and Li 2 SiO 4 The volume expansion of the negative electrode material can be effectively relieved, but the volume change still experiences 200wt% in the charging and discharging process, and the normal graphite expansion is about 10%; after the material compounded by the silicon oxide and the graphite expands and contracts during charging and discharging, the graphite and the silicon oxide are changed from the initial surface contact into point contact, so that the silicon oxide loses electric contact and is deactivated, and the reason is that the battery cycle performance of the silicon carbon material as an electrode material is rapidly attenuated.
At present, commercial silicon oxide composite negative electrode materials are generally subjected to carbon coating and/or compounding with zero strain materials so as to improve the pulverization of electrode materials and avoid the direct contact of the silicon oxide materials with electrolyte, thereby improving the cycle performance of the battery:
for example, CN111170364a in the prior art discloses a carbon-coated silicon-based titanium-niobium composite material, a preparation method thereof, and a lithium ion battery, wherein a titanium source and a niobium source are used as raw materials to perform a first calcination process, and then the silicon source, a first calcination product, and a carbon source are mixed to perform a second calcination process; the carbon-coated silicon-based titanium-niobium composite material prepared by the secondary calcination method has a smaller volume effect in the charge-discharge process, and after the carbon-coated silicon-based titanium-niobium composite material is used as a negative electrode material of a lithium ion battery, the first discharge gram capacity can reach more than 1000mAh/g, but the gram capacity can only be kept below 400mAh/g after 50 cycles, and the capacity retention rate is only 40%.
Therefore, in view of the above problems, there is a need in the art for an electrode material capable of improving the expansion and contraction of the silicon oxide, and when the electrode material is used as a negative electrode material of a battery, the cycle performance of the battery can be further improved while the capacity of the battery is ensured.
Disclosure of Invention
The invention aims to solve the technical problem that the volume change problem caused by expansion and contraction of the silicon oxide composite material in the prior art is still solved, so that the defect that the cycle performance of a battery is quickly attenuated after the battery is subsequently applied is overcome, and the silicon oxide composite material, the preparation method and the application thereof and the lithium ion battery are provided. The preparation method of the composite material can improve the cycle performance of the battery and ensure the electric capacity of the battery.
The invention solves the technical problems by the following scheme:
the invention provides a preparation method of a silicon monoxide composite material, which comprises the following steps:
granulating and calcining the mixed material; wherein the mixed material is a mixture of a premix of metal oxide and a carbon source and silicon monoxide;
the D50 particle size of the premix is less than or equal to 5nm; the D50 particle size of the mixed material is less than or equal to 100nm; the particle size of the mixed material is larger than that of the premix;
the metal oxide comprises one or more of lithium titanate, niobium pentoxide and vanadium pentoxide.
In the present invention, the premix may generally comprise a solvent conventional in the art, e.g., water, C 1-4 Alcohol solvent of (1), C 3～6 Ketone solvent and C 1～3 Preferably water.
Wherein the water is generally deionized water.
Wherein, the C 1～4 The alcoholic solvent of (b) is typically one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol, preferably methanol and/or ethanol.
Wherein, the C 3～6 The ketone solvent of (a) is typically one or more of acetone, butanone, pentanone and hexanone, preferably acetone.
Wherein, the C 1～3 The amide of (a) is typically N-methylformamide and/or dimethylformamide.
Wherein, the premix can also comprise a dispersant conventional in the art, preferably an aqueous dispersant, such as an organic aqueous dispersant, and further such as PVP. The content of the dispersant is preferably 0.2 to 5% by weight, for example 0.5% by weight, based on the total mass.
Wherein, when the premix includes a solvent, the premix is a slurry, and the solid content of the slurry may be conventional in the art, preferably 10wt% to 70wt%.
In the present invention, the premix may further include a conductive carbon material. The conductive carbon material may be a carbon-based conductive agent conventional in the art, such as one or more of carbon nanotubes, carbon fibers (VGCF), graphene, acetylene black, ketjen black, conductive carbon black (SuperP), and conductive graphite.
Wherein the content of the conductive carbon material is preferably 0.1wt% to 1wt%, for example 0.2wt% or 0.5wt%, based on the total substance content.
In the present invention, it is preferable that the D50 particle size of the premix is 0.02 to 0.5nm, for example, 0.2nm.
In the present invention, the D50 particle size of the mixture is preferably 0.2 to 50nm.
In the present invention, the particle size of the premix and/or the mixed material may be controlled in a manner conventional in the art, such as grinding, followed by, for example, sanding. Preferably, the grinding is followed by a sieving step. The screen employed in the screening step is conventionally selected according to the maximum particle size (Dmax).
In the present invention, the content of the metal oxide is preferably 0.8wt% to 10wt%, for example, 5wt% or 9wt%, based on the total content of the material.
In the present invention, the lithium titanate may be commercially available or prepared by a conventional method, for example, by a titanium source and a lithium source. The titanium source may be titanium tetrachloride, tetrabutyl titanate or titanic acid. The lithium source may be lithium nitrate, lithium hydroxide, or lithium carbonate.
In the present invention, the niobium pentoxide may be commercially available or may be prepared by a conventional method, for example, by a niobium salt. The niobium salt can be ammonium niobium oxalate, niobium ethoxide or niobium pentachloride.
In the present invention, the vanadium pentoxide may be commercially available or may be prepared by a conventional method, for example, by a vanadium salt. The vanadium salt may be ammonium metavanadate or potassium vanadate.
In the present invention, preferably, the niobium pentoxide has a hexagonal crystal form or an orthorhombic crystal form.
In the present invention, the D50 particle size of the silica may be conventional in the art, and is preferably 50nm to 120nm, more preferably 80nm to 100nm.
In the present invention, the content of the silica is preferably 50wt% to 98wt%, more preferably 75wt% to 98wt%, for example 94wt% or 90wt%, based on the total material content.
In the present invention, the silica is silica commercially available in the art. The silica may be in the form of irregular, spherical or spheroidal particles. When the silica is in the form of irregular particles, it is preferably subjected to sanding before use.
In the present invention, the content of the carbon source is preferably 0.1wt% to 10wt%, more preferably 0.5wt% to 2wt%, for example, 1wt% or 1.5wt%, based on the total material content.
In the present invention, the carbon source may be conventional in the art, such as soft carbon and/or hard carbon; preferably one or more of citric acid, glucose, cellulose, sucrose, sugar polymers, polysaccharides, polyimides, polyacrylonitrile and polystyrene, more preferably glucose or sucrose.
In the present invention, the manner of granulation may be conventional in the art, such as spray drying. The conditions for the spray drying may be conventional in the art, for example, the spray drying apparatus may have an inlet temperature of 180 to 200 ℃ and an outlet temperature of 80 to 100 ℃.
In the present invention, the calcination may be followed by a step of pulverization and sieving.
In the present invention, the temperature of the calcination may be conventional in the art, for example, 500 to 2800 ℃, preferably 500 to 800 ℃.
In the present invention, the calcination time may be conventional in the art, and is preferably 2 to 5 hours, for example 4 hours.
In the present invention, the atmosphere for the calcination is generally an inert atmosphere. The inert atmosphere generally refers to an atmosphere which does not participate in the reaction of the system during the calcination process, and is not limited to an atmosphere formed by inert gas. Such as an argon atmosphere and/or a nitrogen atmosphere.
In the present invention, the "total content of substances" is the content of other substances not containing a solvent.
The invention also provides a silicon monoxide composite material prepared by the preparation method.
In the present invention, the D50 particle size of the silica composite is preferably 3 to 10nm, for example, 5nm.
The invention also provides an application of the silicon monoxide composite material as a negative active material in a battery.
The invention also provides a lithium ion battery, and an electrode material of the lithium ion battery comprises the silicon oxide composite material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the preparation method of the silicon monoxide negative electrode material has the advantages of low production cost, high production safety, convenient operation and easy large-scale mass production and use.
The silicon oxide negative electrode material prepared by the invention has lower expansion rate, can ensure the electric capacity of the battery after being used for the battery, and has better cycle performance.
Drawings
FIG. 1 is an SEM surface topography of a silica composite material prepared in example 1 of the present application.
Fig. 2 is a graph showing the capacity retention rate test of examples 1 and 2 and comparative examples 1 and 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Weighing Nb 2 O 5 (0.50kg, 5.0wt%) and glucose (0.1kg, 1wt%) were subjected to sanding, and mixed to prepare a premix; wet grinding the premix in a ball mill, wherein the grinding electric quantity is 10kwh/kg, the particle size D50=0.2nm, then adding 9.4kg of silicon oxide (94 wt%) to obtain a mixed material, performing secondary simple sand grinding, and performing spray drying, wherein the inlet temperature of a spray drying device is 200 ℃ and the outlet temperature is 100 ℃; and calcining the dried material in an atmosphere tubular furnace at 800 ℃ for 2h in nitrogen atmosphere. The calcined product was sieved using a 200 mesh screen to obtain a silica composite material D50=5nm, and the sem surface morphology is shown in fig. 1.
Example 2
Nb 2 O 5 (0.90kg, 9wt%) and glucose (0.1kg, 1wt%), and mixing to prepare a premix with the solid content of 20%; wet grinding the premix in a ball mill, wherein the grinding electric quantity is 10kwh/kg, the particle size D50=0.2nm, then adding 9.0kg of nano-silica (90 wt%) to obtain a mixed material, performing secondary simple sand grinding, and performing spray drying, wherein the inlet temperature of a spray drying device is 200 ℃ and the outlet temperature is 100 ℃; and calcining the dried material in an atmosphere tubular furnace at 800 ℃ for 2h in nitrogen atmosphere. The calcined product was subjected to a sieving treatment using a 200-mesh sieve, to obtain a silica composite material D50=5nm.
Comparative example 1
Only differs from example 1 in that Nb is added 2 O 5 (0.50kg, 9.0 wt.%), glucose (0.1kg, 1wt.%), and 9kg of silica (9.4 wt.%) were uniformly mixed, and the resulting mixture was ground (particle size D50=50 nm), granulated, and calcined, with the other steps, conditions, and in accordance with example 1.
Comparative example 2
The difference from example 1 is that only 9kg of silica was ground (particle size D50=50 nm), granulated, and calcined, and the other steps, conditions, and the example 1 were kept the same.
Effects of the embodiment
The silica composites prepared in example 1, example 2, comparative example 1 and comparative example 2 were mixed with commercially available graphite in mass ratios of 13: 2:1:1:1, dispersing, pulping, preparing a negative plate after the working procedures of coating, rolling, slitting and the like, preparing a positive plate from an NCM65 single crystal material, and assembling the positive plate into a lithium ion full cell by adopting a conventional electrolyte and a conventional diaphragm to carry out corresponding tests. Constant-current charging and discharging are carried out under the condition that the charging and discharging multiplying power is 1C/1C, and a battery tester is adopted to test the first discharging capacity, the coulomb efficiency and the cycle performance of the lithium ion battery, as shown in the following figure 2 and table 1; the test standard of the full-electricity rebound of the negative plate is as follows: (full-electricity thickness of the negative plate-empty-electricity thickness of the negative plate)/(empty-electricity thickness of the negative plate-foil thickness).
TABLE 1
Claims (10)
1. A preparation method of a silicon oxide composite material is characterized by comprising the following steps:
granulating and calcining the mixed material; wherein the mixed material is a mixture of a premix of metal oxide and a carbon source and silicon monoxide;
the D50 particle size of the premix is less than or equal to 5nm; the D50 particle size of the mixed material is less than or equal to 100nm; the particle size of the mixed material is larger than that of the premix;
the metal oxide comprises one or more of lithium titanate, niobium pentoxide and vanadium pentoxide.
2. The method of preparing a silica composite according to claim 1, wherein the premix comprises a solvent, preferably water, C 1-4 Alcohol solvent of (1), C 3～6 Ketone solvent and C 1～3 One or more of the amides of (a);
said C is 1～4 The alcohol solvent of (a) is preferably one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and t-butanol, more preferably methanol and/or ethanol;
said C is 3～6 The ketone solvent of (b) is preferably one or more of acetone, butanone, pentanone and hexanone;
said C is 1～3 The amide of (b) is preferably N-methylformamide and/or dimethylformamide.
3. The method for preparing a silica composite material according to claim 2, wherein the premix further comprises a dispersant, preferably an aqueous dispersant such as an organic aqueous dispersant such as PVP; the content of the dispersant is preferably 0.2 to 5wt%, for example 0.5wt%, based on the total mass;
and/or, when the premix comprises a solvent, the premix is a slurry, and the solid content of the slurry is 10wt% -70wt%.
4. The method for preparing a silica composite material according to claim 1, wherein the premix further comprises a conductive carbon material;
the conductive carbon material is preferably a carbon-based conductive agent such as one or more of carbon nanotubes, carbon fibers, graphene, acetylene black, ketjen black, conductive carbon black, and conductive graphite;
wherein the content of the conductive carbon material is preferably 0.1wt% to 1wt%, for example 0.2wt% or 0.5wt%, based on the total substance content.
5. The method for preparing a silica composite material according to claim 1, wherein the premix has a D50 particle size of 0.02 to 0.5nm, such as 0.2nm;
and/or the D50 particle size of the mixed material is 0.2-50 nm;
and/or the particle size of the premix and/or the mixed material is controlled by grinding, such as sanding; preferably, the grinding step is followed by a sieving step;
and/or the metal oxide is present in an amount of 0.8 wt.% to 10 wt.%, for example 5 wt.% or 9 wt.%, based on the total mass content;
and/or the lithium titanate is prepared by a titanium source and a lithium source; the titanium source is preferably titanium tetrachloride, tetrabutyl titanate or titanic acid; the lithium source is preferably lithium nitrate, lithium hydroxide or lithium carbonate;
and/or the niobium pentoxide is prepared from a niobium salt; the niobium salt is preferably ammonium niobium oxalate, niobium ethoxide or niobium pentachloride;
and/or the vanadium pentoxide is prepared from a vanadium salt; the vanadium salt is preferably ammonium metavanadate or potassium vanadate;
and/or the niobium pentoxide is in a hexagonal crystal form or an orthorhombic crystal form;
and/or the D50 particle size of the silicon monoxide is 50nm-120nm, preferably 80nm-100nm;
and/or the content of the silica is 50wt% to 98wt%, preferably 75wt% to 98wt%, for example 94wt% or 90wt%, based on the total material content;
and/or the silica is irregular-shaped, spherical or spheroidal particles; when the silica is in the form of irregularly shaped particles, it is preferably sanded prior to use.
6. The method of preparing a silica composite material according to claim 1, wherein the carbon source is present in an amount of 0.1wt% to 10wt%, preferably 0.5wt% to 2wt%, such as 1wt% or 1.5wt%, based on the total mass content;
and/or the carbon source is soft carbon and/or hard carbon; the soft carbon is preferably one or more of citric acid, glucose, cellulose, sucrose, sugar polymer, polysaccharide, polyimide, polyacrylonitrile and polystyrene, more preferably glucose or sucrose;
and/or the granulation mode is spray drying; preferably, the inlet temperature of the spray drying device is 180-200 ℃, and the outlet temperature is 80-100 ℃;
and/or, the calcination also comprises the steps of crushing and screening;
and/or the temperature of the calcination is 500-2800 ℃, preferably 500-800 ℃;
and/or the calcination time is 2 to 5h, for example 4h.
7. A silica composite material produced by the method for producing a silica composite material according to any one of claims 1 to 6.
8. The silica composite material according to claim 7, having a D50 particle size of from 3 to 10nm, for example 5nm.
9. Use of the silica composite material according to claim 7 or 8 as a negative active material in a battery.
10. A lithium ion battery whose electrode material comprises the silica composite material according to claim 7 or 8.
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