CN115692677A - High-power low-expansion silica metal oxide composite material and preparation method thereof - Google Patents
High-power low-expansion silica metal oxide composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- -1 silica metal oxide Chemical class 0.000 title claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 52
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 45
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 239000010416 ion conductor Substances 0.000 claims abstract description 12
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004020 conductor Substances 0.000 claims description 35
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 238000004070 electrodeposition Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 238000007740 vapor deposition Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- USSPOUWDLNTHFM-UHFFFAOYSA-N lithium difluorooxyborinate Chemical compound B(OF)(OF)[O-].[Li+] USSPOUWDLNTHFM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000007788 liquid Substances 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000002153 silicon-carbon composite material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- QJSASPRXSWOLOS-UHFFFAOYSA-N [SH2]=N.[Li] Chemical compound [SH2]=N.[Li] QJSASPRXSWOLOS-UHFFFAOYSA-N 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000013098 chemical test method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
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- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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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 relates to the technical field of lithium ion battery materials, and discloses a high-power low-expansion silica metal oxide composite material and a preparation method thereof. The silica composite material utilizes the fast ion conductor of the shell to improve the ion transmission rate in the charging and discharging process, utilizes the porous metal of the inner core to reduce expansion and improve electronic conductivity, and utilizes the network structure of the carbon nano tube to restrict the expansion of silicon, improve liquid retention and improve the cycle performance. The silicon-oxygen composite material prepared by the invention is applied to lithium ion batteries and has the characteristics of low expansion, good power performance, excellent cycle performance and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a high-power low-expansion silica metal oxide composite material and a preparation method thereof.
Background
The silica material is a preferred cathode material of the high-energy-density lithium ion battery due to the advantages of high energy density, good cycle performance, low price and the like. However, due to the electronic conductivity deviation of the silica material, the rate performance deviation of the material is caused, and the quick charging performance of the battery is influenced, and meanwhile, the full-electricity expansion of the silica material is large, so that the repeated expansion of a pole piece causes repeated repair of SEI (solid electrolyte interface), lithium ions are consumed, and the cycle and storage performance of the battery are reduced. However, although the above measures can reduce the expansion and the impedance, the uniformity is poor, and the storage and the cycle performance are deteriorated, and the industrialization is difficult.
Disclosure of Invention
In order to improve the power performance and reduce the expansion of the silicon-oxygen material, porous metal is prepared, silicon-oxygen and carbon nano tubes are deposited on the surface of the porous metal through an electrochemical deposition method, the porous metal is dried, and finally a fast ion composite conductor is deposited on the surface of the porous metal through an atomic vapor deposition method, so that the silicon-oxygen metal oxide composite material coated with the fast ion conductor is obtained.
The technical scheme of the invention is as follows: a high-power low-expansion silicon-oxygen metal oxide composite material is characterized in that: the composite material is of a core-shell structure, the core is made of porous metal, the middle layer is made of nano silicon and carbon nano tubes, the shell is a fast ion composite conductor, and the mass ratio of the core to the middle layer to the shell is 10-30:30-60:1-10.
The other technical scheme of the invention is as follows: a preparation method of a high-power low-expansion silica metal oxide composite material is characterized by comprising the following steps:
1) Adopting electrochemical deposition method, using porous carbon as matrix and as cathode, 0.1mol/L metal chloride solution as solvent, metal bar as anode, adopting constant current method, current density is 1-10A/cm 2 Carrying out electrochemical deposition for 10-120min, then washing, carrying out vacuum drying, transferring to a tube furnace, and introducing oxygen mixed gas for sintering to obtain a porous metal compound;
2) Adopting an electrochemical deposition method, taking the porous metal compound prepared in the step 1) as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a mixed solution of a silane coupling agent and a carbon nano tube as a solvent, adopting a cyclic voltammetry method, circulating for 10-100 weeks under the conditions of-2V-2V voltage and a scanning speed of 0.5-5mV/S, then washing with dilute hydrochloric acid, drying in vacuum, and carbonizing for 1-6 hours at 800 ℃ to obtain silicon oxide and carbon nano tube loaded porous metal oxide;
3) Transferring the silicon-oxygen and carbon nanotube-loaded porous metal oxide prepared in the step 2) into a tubular furnace, depositing a fast ion composite conductor by adopting an atomic vapor deposition method, and then naturally cooling to room temperature to obtain the fast ion conductor-coated silicon-oxygen metal oxide composite material.
Further, the method comprises the following steps of; the metal chloride in the metal chloride solution in the step 1) is selected from one of nickel chloride, copper chloride, cobalt chloride, manganese chloride and ferric chloride; the metal rod is selected from one of a nickel rod, a copper rod, a cobalt rod, a manganese rod and an iron rod, and the purity of the metal rod is more than or equal to 99%.
Further, the step of; the preparation method of the mixed solution of the silane coupling agent and the carbon nano tube in the step 2) comprises the steps of weighing 1-10 parts of the silane coupling agent and 1-10 parts of the carbon nano tube by weight, adding the silane coupling agent and the carbon nano tube into 500 parts of N-methylpyrrolidone, uniformly dispersing by using ultrasonic waves, then adding 0.1-1 part of lithium difluoro borate, and uniformly dispersing by using ultrasonic waves to obtain the mixed solution.
Further, the step of; the silane coupling agent is selected from one of gamma-chloropropyltrimethoxysilane, vinyl trichlorosilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxysilane.
Further, the method comprises the following steps of; the fast ion composite conductor in the step 3) is an organic fast ion composite conductor, and the preparation method of the fast ion composite conductor comprises the following steps of uniformly mixing organic lithium salt, a binder and a conductive agent, wherein the mass ratio of the organic lithium salt to the binder to the conductive agent is 10:1-2:1-2, hot pressing at 25-100 ℃ to obtain the fast ion composite conductor.
Further, the method comprises the following steps of; the organic lithium salt is lithium sulfonylimido salt or lithium difluoro oxalato borate; the binder is selected from one of polymethyl methacrylate, polyacrylate, polyvinyl alcohol and polyvinylidene fluoride; the conductive agent is selected from one of polyaniline, polythiophene and polypyrrole.
The invention has the beneficial effects that:
1) The porous metal compound prepared by the invention has the characteristics of high electronic conductivity and the like, and the rate capability is improved.
2) The fast ion composite conductor is deposited by adopting an atomic vapor deposition method, the fast charging performance is improved by depending on the characteristic of high electronic conductivity of the fast ion conductor, and the fast charging performance can be improved by combining the characteristic of high electronic conductivity of the carbon nano tube through the fast ion conductor and the carbon nano tube.
Drawings
Fig. 1 is an SEM image of the fast ion conductor coated silicon oxygen metal oxide composite prepared in example 1.
Detailed Description
Example 1:
a preparation method of a high-power low-expansion silica metal oxide composite material comprises the following steps:
1) An electrochemical deposition method is adopted, porous carbon is used as a substrate and is used as a cathode, 0.1mol/L nickel chloride solution is used as a solvent, a nickel rod is used as an anode, and a constant current method (current density: 5A/cm 2 ) The electrochemical deposition is carried out for 60min, then the washing is carried out, the vacuum drying is carried out for 24h at the temperature of 80 ℃, then the tube furnace is transferred, and the oxygen mixed gas (volume ratio, oxygen: argon =1:10 ) sintering at 800 ℃ for 3h to obtain a porous metal compound;
2) Adopting an electrochemical deposition method, taking the porous metal compound prepared in the step 1) as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a mixed solution of a silane coupling agent and a carbon nano tube as a solvent, adopting a cyclic voltammetry method, circulating for 10 weeks under the conditions of-2V-2V voltage and a scanning speed of 0.5mV/S, then washing with dilute hydrochloric acid, drying in vacuum at 80 ℃ for 24h, and carbonizing at 800 ℃ for 3h to obtain silicon oxide and carbon nano tube loaded porous metal oxide;
3) Transferring the porous metal oxide loaded with the silicon oxide and the carbon nano tube prepared in the step 2) into a tube furnace, depositing a lithium sulfimide-based composite conductor by adopting an atomic vapor deposition method, and then naturally cooling to room temperature to obtain the silicon oxide metal oxide composite material coated with the fast ion conductor (short for: silicon carbon composite).
The preparation method of the mixed solution of the silane coupling agent and the carbon nano tube in the step 2) comprises the following steps: respectively weighing 5g of gamma-chloropropyltrimethoxysilane and 5g of carbon nano tube, adding the gamma-chloropropyltrimethoxysilane and the carbon nano tube into 500g of N-methylpyrrolidone, uniformly dispersing by ultrasonic, then adding 0.5g of lithium difluoroborate, and uniformly dispersing by ultrasonic to obtain a mixed solution of the silane coupling agent and the carbon nano tube.
The preparation method of the lithium sulfonylimido composite conductor in the step 3) comprises the following steps: respectively weighing 10g of lithium sulfonylimido salt, 2g of polyvinyl alcohol and 2g of polyaniline, uniformly mixing, and carrying out hot pressing for 1 hour at the temperature of 60 ℃ to obtain the lithium sulfonylimido salt composite conductor.
The atomic vapor deposition method in the step 3) comprises the following steps: taking the sulfimidyl lithium salt composite conductor as a target material, vacuumizing a vacuum cavity, keeping the pressure of 0.1Torr, heating to 500 ℃, and introducing the sulfimidyl lithium salt composite conductor and an oxygen source into a reaction cabin for cyclic deposition, wherein the cyclic deposition is carried out by the following set procedures: and (2) introducing the sulfimidyl lithium salt composite conductor for 0.5 second, purging with nitrogen for 60 seconds, introducing an oxygen source for 5 seconds, purging with nitrogen for 5 seconds, introducing water for 0.05 second, purging with nitrogen for 50 seconds, and circulating for 50 weeks from the time of introducing the sulfimidyl lithium salt composite conductor for 0.5 second.
Example 2:
a preparation method of a high-power low-expansion silica metal oxide composite material comprises the following steps:
1) An electrochemical deposition method was used, in which porous carbon was used as a substrate and a cathode, a 0.1mol/L copper chloride solution was used as a solvent, a copper rod was used as an anode, and then a constant current method (current density: 1A/cm 2 ) And performing electrochemical deposition for 10min, washing, vacuum drying at 80 ℃ for 24h, transferring to a tube furnace, and introducing oxygen mixed gas (volume ratio, oxygen: argon =1:10 ) sintering at 800 ℃ for 3h to obtain a porous metal compound;
2) Adopting an electrochemical deposition method, taking the porous metal compound prepared in the step 1) as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a mixed solution of a silane coupling agent and a carbon nano tube as a solvent, adopting a cyclic voltammetry method, circulating for 10 weeks under the conditions of-2V-2V voltage and a scanning speed of 0.5mV/S, then washing with dilute hydrochloric acid, drying in vacuum at 80 ℃ for 24h, and carbonizing at 800 ℃ for 1h to obtain silicon oxide and carbon nano tube loaded porous metal oxide;
3) Transferring the silicon-oxygen and carbon nanotube loaded porous metal oxide prepared in the step 2) into a tube furnace, depositing a lithium difluorooxalato-borate composite conductor by adopting an atomic vapor deposition method, and then naturally cooling to room temperature to obtain the fast ionic conductor coated silicon-oxygen metal oxide composite material (short: silicon carbon composite).
The preparation method of the silane coupling agent and carbon nanotube mixed solution in the step 2) comprises the following steps: respectively weighing 1g of vinyl trichlorosilane and 1g of carbon nano tube, adding the vinyl trichlorosilane and the carbon nano tube into 500g of N-methylpyrrolidone, uniformly dispersing the mixture by ultrasonic, then adding 0.1g of lithium difluoroborate, and uniformly dispersing the mixture by ultrasonic to obtain a mixed solution of the silane coupling agent and the carbon nano tube (a mixed solution of the vinyl trichlorosilane and the carbon nano tube).
The preparation method of the lithium difluoro-oxalato-borate composite conductor in the step 3) comprises the following steps: respectively weighing 10g of lithium difluoro-oxalato-borate, 1g of polyvinylidene fluoride and 1g of polythiophene, uniformly mixing, and carrying out hot pressing for 2 hours at the temperature of 25 ℃ to obtain the lithium difluoro-oxalato-borate composite conductor.
The atomic vapor deposition method in the step 3) comprises the following steps: the lithium difluoro oxalato borate composite conductor is used as a target material, a vacuum cavity is vacuumized, the pressure of 0.1Torr is kept, the temperature is increased to 500 ℃, the lithium difluoro oxalato borate composite conductor and an oxygen source are led into a reaction chamber for cyclic deposition, and the setting procedure of the cyclic deposition is that the lithium sulfonimidoyl borate composite conductor is led for 0.5 second, nitrogen is blown for 60 seconds, the oxygen source is led for 5 seconds, nitrogen is blown for 5 seconds, water is led for 0.05 second, nitrogen is blown for 50 seconds, and the cycle is started for 10 weeks from the time when the lithium difluoro oxalato borate composite conductor is led for 0.5 second.
Example 3:
a preparation method of a high-power low-expansion silica metal oxide composite material comprises the following steps:
1) An electrochemical deposition method was used, in which porous carbon was used as a substrate and as a cathode, a 0.1mol/L ferric chloride solution was used as a solvent, metallic iron was used as an anode, and then a constant current method (current density: 10A/cm 2 ) The electrochemical deposition is carried out for 120min, then the washing is carried out, the vacuum drying is carried out for 24h at the temperature of 80 ℃, then the tube furnace is transferred, and the oxygen mixed gas (volume ratio, oxygen: argon =1:10 ) sintering at 800 ℃ for 3h to obtain a porous metal compound;
2) Adopting an electrochemical deposition method, taking the porous metal compound prepared in the step 1) as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a mixed solution of a silane coupling agent and a carbon nano tube as a solvent, adopting a cyclic voltammetry method, circulating for 100 weeks under the conditions of-2V-2V voltage and 5mV/S scanning speed, then washing with dilute hydrochloric acid, carrying out vacuum drying at 80 ℃ for 24h, and carbonizing at 800 ℃ for 1h to obtain silicon oxide and carbon nano tube loaded porous metal oxide;
3) Transferring the silicon-oxygen and carbon nanotube loaded porous metal oxide prepared in the step 2) into a tube furnace, depositing a lithium difluorooxalato-borate composite conductor by adopting an atomic vapor deposition method, and then naturally cooling to room temperature to obtain the fast ionic conductor coated silicon-oxygen metal oxide composite material (short: silicon carbon composite).
The preparation method of the silane coupling agent and carbon nanotube mixed solution in the step 2) comprises the following steps: respectively weighing 10g of vinyl tri (2-methoxyethoxy) silane and 1g of carbon nano tube, adding the vinyl tri (2-methoxyethoxy) silane and the carbon nano tube into 500 parts of N-methylpyrrolidone, uniformly dispersing by ultrasonic, then adding 1g of lithium difluoro borate, and uniformly dispersing by ultrasonic to obtain a mixed solution of the silane coupling agent and the carbon nano tube.
The preparation method of the lithium difluoro-oxalato-borate composite conductor in the step 3) comprises the following steps: respectively weighing 10g of lithium difluoro (oxalato) borate, 1g of polymethyl methacrylate and 1g of polypyrrole, uniformly mixing, and carrying out hot pressing at the temperature of 100 ℃ for 0.5h to obtain the lithium difluoro (oxalato) borate composite conductor.
The atomic vapor deposition method in the step 3) comprises the following steps: the lithium difluoro oxalato borate composite conductor is used as a target material, a vacuum chamber is vacuumized and kept at the pressure of 0.1Torr, the temperature is increased to 500 ℃, and the lithium difluoro oxalato borate composite conductor and an oxygen source are led into a reaction chamber for cyclic deposition, wherein the cyclic deposition is set according to the program that the lithium difluoro oxalato borate composite conductor is led for 0.5 second, nitrogen is blown for 60 seconds, the oxygen source is led for 5 seconds, nitrogen is blown for 5 seconds, water is led for 0.05 second, nitrogen is blown for 50 seconds, and the cycle is started for 100 weeks from the time that the lithium difluoro oxalato borate composite conductor is led for 0.5 second.
Comparative example 1:
a method for preparing a fast ion conductor/silicon-based/carbon nanotube coated metal oxide material comprises the following steps:
1) Adopting an electrochemical deposition method, taking a nickel rod as a working electrode, and obtaining silicon oxide and carbon nanotube loaded metal oxide in the same way as the step 2) of the embodiment 1;
2) The silicon oxide and the carbon nanotube-loaded metal oxide prepared in the step 1) are transferred to a tube furnace, and the rest is the same as the step 3) in the example 1, so that the fast ion conductor/silicon-based/carbon nanotube-coated metal oxide material is obtained.
Comparative example 2:
taking 100mL of the mixed solution of the vinyl trichlorosilane and the carbon nano tube prepared in the embodiment 2, adding 10g of nickel chloride, uniformly dispersing, filtering, carrying out vacuum drying at 80 ℃ for 24h, transferring to a tubular furnace, introducing methane gas to remove air in the tube, carbonizing at 800 ℃ for 1h, and crushing to obtain the silicon-carbon composite material.
Test experiment one
1. Physical and chemical testing
(1) Topography testing
SEM tests were performed on the silicon carbon composite material prepared in example 1, and the test results are shown in fig. 1. As can be seen from FIG. 1, the material has a granular structure, and the size distribution of the grains of the material is uniform and reasonable, and the amorphous carbon material is arranged among the grains, and the grain size of the grains is between 2 and 8 μm.
(2) And (3) testing the specific surface area, tap density and carbon content of the silicon-based composite material by referring to GB/T38823-2020 silicon carbon, and testing the conductivity of the silicon-carbon composite material by adopting a four-probe tester.
(3) Full electric expansion: the rolled button cell plates were tested for negative plate thickness D1, the button cells were then fully charged to 100% SOC and dissected for full negative plate thickness D2, and the expansion ratio (expansion ratio = (D2-D1)/D1 × 100%) was calculated
The test results are shown in table 1.
2. Electrochemical Performance test
(1) Button cell test
The silicon-carbon composite materials in examples 1-3 and comparative examples 1-2 are used as the negative electrode materials of the lithium ion batteries to prepare button batteries according to the following method:
adding a binder, a conductive agent and a solvent into the silicon-carbon composite material, stirring and pulping, coating the mixture on copper foil, and drying and rolling to prepare a negative plate; the binder is polyvinylidene fluoride (PVDF), the conductive agent is conductive carbon black (SP), the solvent is N-methyl pyrrolidone (NMP), and the silicon and the carbon are compoundedThe dosage proportion of the materials, SP, PVDF and NMP is 95g; the electrolyte is lithium hexafluorophosphate (LiPF) 6 ) A solution as an electrolyte at a concentration of 1mol/L, wherein the solvent is a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1; the metal lithium sheet is used as a counter electrode, and the diaphragm is a polypropylene (PP) film. Button cell assembly was performed in an argon-filled glove box.
The electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.005V to 2.0V, and the charging and discharging rate is 0.1C.
The test results are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the specific capacity and the first efficiency of the silicon-carbon composite material prepared by the invention are obviously superior to those of the comparative example. The reason is that: the silica material is deposited by an electrochemical deposition method, so that the density is high, the impedance is reduced, the defect degree of the material is reduced, the primary efficiency is improved, and meanwhile, the porous structure of the porous metal material has the advantages of high specific surface area and improvement on the electronic conductivity of the material; and reduces the expansion of the material.
Test experiment 2
The silicon-carbon composite materials of examples 1-3 and comparative examples 1-2 were doped with 90% of artificial graphite as a negative electrode material and a positive electrode ternary material (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) The electrolyte and the diaphragm are assembled into the 5Ah soft package battery. Wherein the diaphragm is celegard 2400, and the electrolyte is LiPF 6 Solution (solvent is a mixed solution of EC and DEC in a volume ratio of 1, liPF 6 The concentration of (1.3 mol/L). The prepared soft package batteries (lithium ion batteries) are respectively marked as A-2, B-2, C-2 and D-2, and E-2.
The following performance tests were performed on the pouch cells:
1. imbibition ability test
And (3) adopting a 1mL burette, absorbing the electrolyte VML, dripping a drop on the surface of the pole piece, timing until the electrolyte is absorbed completely, recording the time t, and calculating the liquid absorption speed V/t of the pole piece. The test results are shown in table 2.
2. Liquid retention test
Calculating the theoretical liquid absorption mL of the pole piece according to the pole piece parameters, weighing the weight m2 of the pole piece, then placing the pole piece into electrolyte to soak for 24 hours, weighing the weight m3 of the pole piece, calculating the liquid absorption m3-m2 of the pole piece, and calculating according to the following formula: liquid retention rate = (m 3-m 2) × 100%/mL. The test results are shown in table 2.
TABLE 2
| Imbibition speed (mL/min) | Liquid retention rate | |
| Example 1 | 5.4 | 90.1％ |
| Example 2 | 5.9 | 91.2％ |
| Example 3 | 4.5 | 89.4％ |
| Comparative example 1 | 2.5 | 84.9％ |
| Comparative example 2 | 1.5 | 82.7％ |
As can be seen from Table 2, the liquid absorption and retention capacities of the silicon carbon composites obtained in examples 1to 3 are significantly higher than those of the comparative examples. The reason for this is that: the specific surface of the silicon-carbon composite material prepared in the embodiment 1-3 is larger, and the liquid absorption and retention capacity of the material is improved.
3. Multiplying power and cycle performance thereof
And (4) carrying out cycle performance test and rate test on the soft package batteries A-2-E-2. The cycle test conditions were: the charge-discharge voltage range is 2.5-4.2V, the temperature is 25 +/-3.0 ℃, the charge-discharge multiplying power is 0.5C/1.0C, and the cycle times are 500 times. The multiplying power test conditions are as follows: testing the constant current ratio of its material under 2C conditions, followed by 100% SOC charged to dissect the battery, testing the full charge rebound of the pole piece before; the test results are shown in table 3.
TABLE 3
As can be seen from table 3, the cycle performance of the soft-package lithium ion battery prepared by using the silicon-carbon composite material of the present invention is superior to that of the comparative example, because the silicon-carbon composite material of the present invention is electrochemically deposited on the porous metal to reduce expansion and has a higher specific surface area, the liquid retention performance of the material is improved, and the cycle performance is improved; meanwhile, the silicon-carbon composite material is doped with a metal compound with high electronic conductivity, so that the impedance is reduced, and the rate capability (constant current ratio) is improved; meanwhile, the invention adopts porous metal as a substrate and deposits silicon-based material on the surface of the substrate to reduce the expansion.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (7)
1. A high-power low-expansion silicon-oxygen metal oxide composite material is characterized in that: the composite material is of a core-shell structure, the inner core is made of porous metal, the middle layer is made of nano silicon and carbon nano tubes, the shell is a fast ion composite conductor, and the mass ratio of the inner core to the middle layer to the shell is 10-30:30-60:1-10.
2. A method for preparing a high power low expansion silica metal oxide composite material according to claim 1, comprising the steps of:
1) Adopting electrochemical deposition method, using porous carbon as matrix and as cathode, 0.1mol/L metal chloride solution as solvent, metal bar as anode, adopting constant current method, current density is 1-10A/cm 2 Carrying out electrochemical deposition for 10-120min, then washing, carrying out vacuum drying, transferring to a tube furnace, and introducing oxygen mixed gas for sintering to obtain a porous metal compound;
2) Adopting an electrochemical deposition method, taking the porous metal compound prepared in the step 1) as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a mixed solution of a silane coupling agent and a carbon nano tube as a solvent, adopting a cyclic voltammetry method, circulating for 10-100 weeks under the conditions of-2V-2V voltage and a scanning speed of 0.5-5mV/S, then washing with dilute hydrochloric acid, drying in vacuum, and carbonizing for 1-6 hours at 800 ℃ to obtain silicon oxide and carbon nano tube loaded porous metal oxide;
3) Transferring the silicon-oxygen and carbon nanotube-loaded porous metal oxide prepared in the step 2) into a tubular furnace, depositing a fast ion composite conductor by adopting an atomic vapor deposition method, and then naturally cooling to room temperature to obtain the fast ion conductor-coated silicon-oxygen metal oxide composite material.
3. The method for preparing the high-power low-expansion silica metal oxide composite material according to claim 2, wherein the method comprises the following steps: the metal chloride in the metal chloride solution in the step 1) is selected from one of nickel chloride, copper chloride, cobalt chloride, manganese chloride and ferric chloride; the metal rod is selected from one of a nickel rod, a copper rod, a cobalt rod, a manganese rod and an iron rod, and the purity of the metal rod is more than or equal to 99%.
4. The method for preparing the high-power low-expansion silica metal oxide composite material according to claim 2, wherein the method comprises the following steps: the preparation method of the mixed solution of the silane coupling agent and the carbon nano tube in the step 2) comprises the steps of weighing 1-10 parts of the silane coupling agent and 1-10 parts of the carbon nano tube by weight, adding the silane coupling agent and the carbon nano tube into 500 parts of N-methylpyrrolidone, uniformly dispersing by using ultrasonic waves, then adding 0.1-1 part of lithium difluoro borate, and uniformly dispersing by using ultrasonic waves to obtain the mixed solution.
5. The method for preparing the high-power low-expansion silica metal oxide composite material according to claim 4, wherein the method comprises the following steps: the silane coupling agent is selected from one of gamma-chloropropyltrimethoxysilane, vinyl trichlorosilane, vinyl triethoxysilane, vinyl tri (2-methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxysilane.
6. The method for preparing the high-power low-expansion silica metal oxide composite material according to claim 2, wherein the method comprises the following steps: the fast ion composite conductor in the step 3) is an organic fast ion composite conductor, and the preparation method of the fast ion composite conductor comprises the following steps of uniformly mixing organic lithium salt, a binder and a conductive agent, wherein the mass ratio of the organic lithium salt to the binder to the conductive agent is 10:1-2:1-2, hot pressing at 25-100 ℃ to obtain the fast ion composite conductor.
7. The method for preparing high-power low-expansion silica metal oxide composite material according to claim 6, wherein the method comprises the following steps: the organic lithium salt is lithium sulfonylimido salt or lithium difluoro oxalato borate; the binder is selected from one of polymethyl methacrylate, polyacrylate, polyvinyl alcohol and polyvinylidene fluoride; the conductive agent is selected from one of polyaniline, polythiophene and polypyrrole.
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| CN116230911A (en) * | 2023-03-10 | 2023-06-06 | 内蒙古欣源石墨烯科技股份有限公司 | High-power silicon-carbon negative electrode composite material and preparation method thereof |
| CN116314671A (en) * | 2023-02-22 | 2023-06-23 | 胜华新材料集团股份有限公司 | Preparation method of silicon-carbon composite material and silicon-carbon composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116314671A (en) * | 2023-02-22 | 2023-06-23 | 胜华新材料集团股份有限公司 | Preparation method of silicon-carbon composite material and silicon-carbon composite material |
| CN116230911A (en) * | 2023-03-10 | 2023-06-06 | 内蒙古欣源石墨烯科技股份有限公司 | High-power silicon-carbon negative electrode composite material and preparation method thereof |
| CN116230911B (en) * | 2023-03-10 | 2024-04-16 | 内蒙古欣源石墨烯科技股份有限公司 | High-power silicon-carbon negative electrode composite material and preparation method thereof |
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