CN109148891A - A kind of nano porous copper-silicium cathode piece and preparation method thereof - Google Patents
A kind of nano porous copper-silicium cathode piece and preparation method thereof Download PDFInfo
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- CN109148891A CN109148891A CN201810886567.1A CN201810886567A CN109148891A CN 109148891 A CN109148891 A CN 109148891A CN 201810886567 A CN201810886567 A CN 201810886567A CN 109148891 A CN109148891 A CN 109148891A
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- copper
- silicium cathode
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052802 copper Inorganic materials 0.000 claims abstract description 82
- 239000010949 copper Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000011888 foil Substances 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 24
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000012686 silicon precursor Substances 0.000 claims description 6
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 4
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 4
- 229910003818 SiH2Cl2 Inorganic materials 0.000 claims description 4
- 229910003822 SiHCl3 Inorganic materials 0.000 claims description 4
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 4
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 claims description 4
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229910004014 SiF4 Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 3
- 230000008961 swelling Effects 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 28
- 229910052744 lithium Inorganic materials 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 16
- 239000007774 positive electrode material Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 239000011244 liquid electrolyte Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000004804 winding Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000011245 gel electrolyte Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000011856 silicon-based particle Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- ZGUQQOOKFJPJRS-UHFFFAOYSA-N lead silicon Chemical compound [Si].[Pb] ZGUQQOOKFJPJRS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021471 metal-silicon alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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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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Abstract
A kind of nano porous copper-silicium cathode piece and preparation method thereof, the nano porous copper-silicium cathode piece includes: collector matrix, has several nanometer micropores on the collector matrix, is deposited with silicon in the nanometer micropore.When preparation, copper alloy foil is pre-processed, the non-copper component in copper alloy foil is removed, obtains the nanoporous copper current collector with several nanometer micropores；Nanometer micropore copper current collector is subjected to siliceous deposits in the method for chemical vapor deposition, obtains nano porous copper-silicium cathode piece.The nano porous copper of the method for the present invention-silicium cathode piece, the energy density that can promote battery is improved, and improves cycle performance, and the thickness swelling of charging front and back negative electrode tab is also improved.
Description
Technical field
The invention belongs to the negative electrode tabs and its preparation side of technical field of lithium ion more particularly to a kind of lithium ion battery
Method.
Background technique
Lithium ion battery is widely used to due to having the characteristics that energy density is high, having extended cycle life and environmental-friendly
In various consumer electronics products and electric vehicle, and good application prospect is shown in large-scale energy storage field.At present
The negative electrode material of lithium ion battery is mostly graphite, and the theoretical specific capacity of graphite is limited, so that lithium ion battery energy density mentions
Height faces bottleneck.
Silicium cathode has very high theoretical specific capacity (4200mAh/g), is such as applied to cathode of lithium battery and is beneficial to mention
The energy density of high battery.But during lithium ion is embedded in huge volume change can occur for silica-base material, can lead
Silicon particle rupture, dusting in the cyclic process of pond are sent a telegraph, and is fallen off from collector, and huge volume change can make silicon particle
The SEI film on surface is constantly ruptured and is regenerated, and a large amount of lithium ions consumed in electrolyte eventually lead to battery capacity and decline rapidly
Subtract, poor circulation, seriously limits the commercial applications of silicium cathode.
In order to solve the problems, such as that volume change present in silicium cathode cyclic process, conventional thought are by silicon particle nanometer
Change, and coats protective layer on nano-silicon particle surface.The silicon materials handled by cladding are main according to the difference of protective layer
Two major classes can be divided into: one kind is to coat nano Si/C composite of carbon material, and another kind of is cladding amorphous silicon di-oxide
Resulting Si/SiO afterwards2Composite material (also referred to as aoxidizes sub- silicon materials).It can be changed to a certain extent by coating protective layer
The problem of kind silicon particle volume change bring granule atomization, so as to improve the cycle performance of battery, but also brings new simultaneously
The problem of --- the carbon material and amorphous silicon di-oxide of cladding will be greatly reduced the specific capacity of material entirety, also result in material
First charge-discharge efficiency significantly reduces.These new problems largely counteract the height ratio capacity using silicon based anode material
Characteristic prepares battery to promote the effect of energy density.
Using the metal foil with porous structure as collector matrix, limited using the pore structure of porous metals collector
The volume change of silicon processed is another resolving ideas for solving the problems, such as volume change present in silicium cathode cyclic process.Such as patent
Number for silicon-based anode disclosed in No. 201210127121.3 Chinese invention patents preparation method, used on porous current collector
Magnetron sputtering method by elemental silicon or elemental silicon and metal M cosputtering on collector, then in a vacuum or inert atmosphere at heat
Reason.Application No. is 201611028305.9 Chinese invention patent applications to disclose a kind of preparation method of silicon-based anode, more
In the metal foil of mesoporous metal, the metal mesh of surface roughening treatment or surface roughening treatment, using the method for physical vapour deposition (PVD)
Silicon-metal alloy active material is deposited in collection liquid surface, then uses one layer of carbon material protective layer of physical vapour deposition (PVD) again.More than
Porous metals collector used in patent is conventional foam copper, nickel foam, copper mesh etc., and aperture thereon is micron order, by
It is excessive in micron-sized pore size, the volume change of silicon can not be limited well, therefore actual effect is unsatisfactory.
Summary of the invention
The purpose of the present invention is to provide a kind of height ratio capacity, high first charge discharge efficiency and the excellent nanoporous of cycle performance
Copper-silicium cathode piece and preparation method thereof.
To achieve the goals above, the present invention takes following technical solution:
A kind of nano porous copper-silicium cathode piece, comprising: collector matrix has several nanometers on the collector matrix
Micropore is deposited with silicon in the nanometer micropore.
Further, the aperture of the nanometer micropore is 5nm~1000nm.
Further, the collector matrix with a thickness of 5 μm~100 μm.
Further, the collector matrix is binary copper alloys foil or ternary copper-alloy foil through removing the pre- of non-copper component
It is made after processing.
Further, the collector matrix be albronze foil, cupromanganese foil, corronil foil, copper-titanium alloy foil,
Copper zirconium alloy foil, copper magnesium alloy foil, clutch gold, copper-tin alloy foil, cu-zn-al alloy foil, batterium alloy goldleaf, copper aluminium tin
One of Alloy Foil is made after being removed the pretreatment of non-copper component.
Further, the mass percent of copper is 10~90% in the collector matrix.
Aforementioned nano porous copper-silicium cathode piece preparation method, comprising the following steps:
Copper alloy foil is pre-processed, the non-copper component in copper alloy foil is removed, obtains that there are several nanometer micropores
Nanoporous copper current collector；
Nanometer micropore copper current collector is subjected to siliceous deposits in the method for chemical vapor deposition, it is negative to obtain nano porous copper-silicon
Pole piece.
Further, copper alloy foil is carried out using chemical corrosion method or electrochemical erosion method or high-temperature vacuum facture pre-
Processing.
Further, when depositing silicon, nanometer micropore copper current collector is put into chemical vapor deposition stove, 0.01~
1000Pa pressure at 200~800 DEG C, is continually fed into silicon-containing precursor gas and carries out siliceous deposits, after deposition, by silicon forerunner
Body gas switches to nitrogen or argon gas, until stove is cooled to room temperature.
Further, the silicon precursor gas is SiH4、SiCl4、SiHCl3、SiH2Cl2、SiF4One of or it is several
Kind.
From the above technical scheme, obtain that there are the more of nanoscale hole hole after the present invention pre-processes copper alloy foil
Hole copper current collector, then silicon is deposited in the nano-pore of collector by the method for chemical vapor deposition, to obtain nanoporous
Copper-silicium cathode piece.Compared with the common porous metals collector such as foam copper, nickel foam, on porous copper current collector of the invention
Bore hole size be nanoscale, the skin effect of nano material imparts the new property of collector, make its show with it is common more
The biggish performance difference of mesoporous metal collector, firstly, the size for depositing silicon can be limited in nanoscale by nano-pore, silicon is in nanometer
The stress that scale volumetric expansion generates is smaller, therefore the structure of silicium cathode can preferably be inhibited to destroy, to promote circulation
Performance；Secondly, copper metal has extraordinary ductility and super-elasticity, and silicon is limited in small ruler by the small size of nano-pore structure
In very little range, the ductility and super-elasticity of copper metal can be given full play to, so as to preferably buffer in nano porous copper hole
Volume change of the silicon in charge and discharge process, to obtain preferable cycle performance.In order to cooperate the copper with nano-pore structure
Collector can deposit silicon, silicon meeting using chemical vapor deposition silicon to avoid other deposition methods, such as physical deposition methods
Preferential deposition is difficult to enter the situation in nano-pore outside nano-pore, is deposited on the silicon outside hole not by the small size of nano-pore
Limitation can not play the effect of nano-pore structure, select chemical vapor deposition that can just give full play of the work of nano-pore structure
With the effect being optimal.Negative electrode tab of the invention is applied to be remarkably improved the energy density of battery in lithium ion battery,
And guarantee preferable cycle performance, and preparation process of the invention is simple, and it is low in cost, it is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is nano porous copper of the present invention-silicium cathode piece structural schematic diagram.
Fig. 2 is nano porous copper of the embodiment of the present invention-silicium cathode piece scanning electron microscopic picture.
A specific embodiment of the invention is described in more detail below in conjunction with attached drawing
Specific embodiment
In order to above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention is cited below particularly,
And cooperate appended diagram, it is described below in detail.
As shown in Figure 1, nano porous copper of the invention-silicium cathode piece includes collector matrix 1, have on collector matrix 1
There is nanoscale hole 2, silicon 3 is deposited in hole 2.Collector matrix 1 is pre-processed therein to remove by copper alloy foil
After non-copper component be made, collector matrix 1 with a thickness of 5 μm~100 μm, by pretreated copper alloy foil have it is several
Nanoscale hole, the aperture of these holes are 5nm~1000nm.
Copper alloy foil used in the present invention can be albronze foil, cupromanganese foil, corronil foil, copper-titanium alloy
Binary copper alloys foil or the cu-zn-al alloys such as foil, copper zirconium alloy foil, copper magnesium alloy foil, clutch gold, copper-tin alloy foil
The ternary copper-alloys foils such as foil, batterium alloy goldleaf, copper mock silver foil.In copper alloy foil the mass percent of copper be 10~
90%.Chemical corrosion method can be used or electrochemical erosion method pre-processes copper alloy foil, for clutch gold and copper zinc
The Alloy Foil containing low boiling point metal such as alloy foil can also be pre-processed using high-temperature vacuum facture.
Silicon is deposited on the collector matrix for forming hole using the method for chemical vapor deposition, collector matrix is put
Enter in chemical vapor deposition stove, at 0.01~1000Pa pressure, 200~800 DEG C, is continually fed into silicon-containing precursor gas progress
Silicon precursor gas after deposition, is switched to nitrogen or argon gas by siliceous deposits, until stove is cooled to room temperature.Silicon precursor
The flow and sedimentation time of gas, can be optimal according to cvd furnace size and final required siliceous deposits amount selection without clearly limiting
Flow and sedimentation time.Silicon precursor gas can be SiH4, SiCl4, SiHCl3, SiH2Cl2, SiF4Deng.
Below by specific embodiment, the present invention is further illustrated.Reagent, the material arrived used in following the description
Material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available, institute
The reagent being related to can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
By the clutch gold of 20 μ m-thicks, (also referred to as filtter gold, wherein the mass percent of copper is 65%) at 800 DEG C
It is pre-processed in the method that high-temperature vacuum is handled, the nano porous copper that aperture is about 100nm will be obtained after the removal of non-copper component
Nanoporous copper current collector is placed in chemical vapor deposition stove by collector, at 0.1Pa pressure, 300 DEG C, with 300mL/min
Flow be continually fed into SiH41 hour progress siliceous deposits of gas, is then switched to argon gas, stove is cooled to room temperature to obtain nanometer
Porous Cu-silicium cathode piece.Fig. 2 is nano porous copper-silicium cathode piece scanning electron microscopic picture of the present embodiment.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are LiFePO4.Electrolyte is other than available liquid electrolyte, it is also possible to gel
Electrolyte or solid electrolyte (if diaphragm can not had to gel electrolyte or solid electrolyte).Anode used by positive plate is living
Property substance can be also cobalt acid lithium or nickel-cobalt-manganese ternary material or LiMn2O4 or nickel cobalt aluminium ternary material or nickel ion doped or rich lithium manganese
Sill.
Comparative example 1
The place different from embodiment 1 of comparative example 1 is: using nano-silicone wire/carbon composite negative pole material, passes through conventional lithium
Battery cathode ingredient and coating process are prepared into nano-silicone wire/carbon composite negative plate.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are LiFePO4.
Embodiment 2
By the clutch gold of 5 μ m-thicks, (also referred to as filtter gold, wherein the mass percent of copper is 90%) to be put into dilute hydrochloric acid
Middle immersion is pre-processed in the method for chemical attack, will obtain the nanoporous that aperture is about 80nm after the removal of non-copper component
Nanoporous copper current collector is placed in chemical vapor deposition stove by copper current collector, at 0.01Pa pressure, 200 DEG C, with 400mL/
The flow of min is continually fed into SiCl40.5 hour progress siliceous deposits of gas, is then switched to nitrogen, stove is cooled to room temperature
To nano porous copper-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into lamination process, collocation gel electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are cobalt acid lithium.
Comparative example 2
The place different from embodiment 2 of comparative example 2 is: using nano-silicone wire/carbon composite negative pole material, passes through conventional lithium
Battery cathode ingredient and coating process are prepared into nano-silicone wire/carbon composite negative plate.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into lamination process, collocation gel electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are cobalt acid lithium.
Embodiment 3
The albronze foil (wherein the mass percent of copper is 50%) of 100 μ m-thicks is put into sodium hydroxide solution and is soaked
Bubble, is pre-processed in the method for chemical attack, will obtain the nano porous copper collection that aperture is about 200nm after the removal of non-copper component
Obtained nanoporous copper current collector is placed in chemical vapor deposition stove by fluid, at 1Pa pressure, 800 DEG C, with 500mL/
The flow of min is continually fed into SiHCl32 hours progress siliceous deposits of gas, are then switched to argon gas, stove are cooled to room temperature
To nano porous copper-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into lamination process, collocation solid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel-cobalt-manganese ternary material.
Comparative example 3
The place different from embodiment 3 of comparative example 3 is: using sub- silicium cathode material is aoxidized, passing through conventional lithium battery
Cathode blending and coating process are prepared into aoxidizing sub- silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into lamination process, collocation solid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel-cobalt-manganese ternary material.
Embodiment 4
The copper magnesium alloy foil (wherein the mass percent of copper is 10%) of 50 μ m-thicks is put into dilute hydrochloric acid solution and is impregnated, with
The method of chemical attack is pre-processed, and will obtain the nano porous copper afflux of aperture about position 1000nm after the removal of non-copper component
Nanoporous copper current collector is placed in chemical vapor deposition stove by body, at 1000Pa pressure, 400 DEG C, with 500mL/min's
Flow is continually fed into SiH2Cl24 hours progress siliceous deposits of gas, are then switched to argon gas, stove are cooled to room temperature to obtain nanometer
Porous Cu-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel-cobalt-manganese ternary material.
Comparative example 4
The place different from embodiment 4 of comparative example 4 is: using sub- silicium cathode material is aoxidized, passing through conventional lithium battery
Cathode blending and coating process are prepared into aoxidizing sub- silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel-cobalt-manganese ternary material.
Embodiment 5
The cupromanganese foil (wherein the mass percent of copper is 30%) of 40 μ m-thicks is carried out in the method for electrochemical corrosion
Pretreatment will obtain the nanoporous copper current collector that aperture is about 400nm after the removal of non-copper component, by nanoporous copper current collector
It is placed in chemical vapor deposition stove, at 100Pa pressure, 350 DEG C, SiF is continually fed into the flow of 400mL/min4Gas 3 is small
Shi Jinhang siliceous deposits, is then switched to argon gas, and stove is cooled to room temperature to obtain nano porous copper-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation gel electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are manganate cathode material for lithium.
Comparative example 5
The place different from embodiment 5 of comparative example 5 is: using aperture is 2 μm of common porous copper current collector as collection
Fluid matrix carries out siliceous deposits using chemical vapour deposition technique with identical technique: the porous copper current collector is placed in chemical gas
In phase cvd furnace, at 100Pa pressure, 350 DEG C, SiF is continually fed into the flow of 400mL/min43 hours progress silicon of gas is heavy
Product, is then switched to argon gas, stove is cooled to room temperature to obtain Porous Cu-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation gel electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are manganate cathode material for lithium.
Embodiment 6
The copper zirconium alloy foil (wherein the mass percent of copper is 40%) of 30 μ m-thicks is put into hydrofluoric acid solution and is impregnated, with
The method of chemical attack is pre-processed, and will obtain the nanoporous copper current collector that aperture is about 5nm after the removal of non-copper component, will
Nanoporous copper current collector is placed in chemical vapor deposition stove, at 10Pa pressure, 300 DEG C, is continued with the flow of 400mL/min
It is passed through SiH42 hours progress siliceous deposits of gas, are then switched to argon gas, stove are cooled to room temperature to obtain nano porous copper-silicon
Negative electrode tab.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel lithium manganate cathode material.
Comparative example 6
The place different from embodiment 6 of comparative example 6 is: using aperture is 50 μm of common porous copper current collector as collection
Fluid matrix carries out siliceous deposits using chemical vapour deposition technique with identical technique: the porous copper current collector is placed in chemical gas
In phase cvd furnace, at 10Pa pressure, 300 DEG C, SiH is continually fed into the flow of 400mL/min42 hours progress silicon of gas is heavy
Product, is then switched to argon gas, stove is cooled to room temperature to obtain Porous Cu-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel lithium manganate cathode material.
Embodiment 7
The copper mock silver foil (wherein the mass percent of copper is 45%) of 10 μ m-thicks is put into sodium hydroxide solution and is soaked
Bubble, is pre-processed in the method for chemical attack, will obtain the nano porous copper collection that aperture is about 50nm after the removal of non-copper component
Nanoporous copper current collector is placed in chemical vapor deposition stove by fluid, at 10Pa pressure, 300 DEG C, with 400mL/min's
Flow is continually fed into SiH42 hours progress siliceous deposits of gas, are then switched to argon gas, are cooled to room temperature the stove to obtain nanometer more
Hole copper-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into lamination process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel cobalt aluminium ternary material positive electrode.
Comparative example 7
The place different from embodiment 7 of comparative example 7 is: using aperture is 200 μm of foamed nickel current collector as afflux
Body matrix carries out siliceous deposits using chemical vapour deposition technique with identical technique: foamed nickel current collector is placed in chemical vapor deposition
In product furnace, at 10Pa pressure, 300 DEG C, SiH is continually fed into the flow of 400mL/min42 hours progress siliceous deposits of gas, so
After switch to argon gas, stove is cooled to room temperature to obtain Porous Cu-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into lamination process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are nickel cobalt aluminium ternary material positive electrode.
Embodiment 8
By the batterium alloy goldleaf of 25 μ m-thicks (wherein the mass percent of copper is 40%) with the method for electrochemical corrosion into
Row pretreatment will obtain the nanoporous copper current collector that aperture is about 20nm after the removal of non-copper component, by nano porous copper afflux
Body is placed in chemical vapor deposition stove, at 1Pa pressure, 300 DEG C, is continually fed into SiH with the flow of 400mL/min4Gas 2.5
Hour carries out siliceous deposits, is then switched to argon gas, stove is cooled to room temperature to obtain nano porous copper-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are lithium-rich manganese-based anode material.
Comparative example 8
The place different from embodiment 8 of comparative example 8 is: using aperture is 200 μm of foam copper current collector as afflux
Body matrix carries out siliceous deposits using chemical vapour deposition technique with identical technique: foam copper current collector is placed in chemical vapor deposition
In product furnace, at 1Pa pressure, 300 DEG C, SiH is continually fed into the flow of 400mL/min42.5 hours progress siliceous deposits of gas,
It is then switched to argon gas, stove is cooled to room temperature to obtain Porous Cu-silicium cathode piece.
Negative electrode tab obtained and conventional positive plate and diaphragm are used into winding process, collocation liquid electrolyte be made lithium from
Sub- battery, the positive active material on positive plate are lithium-rich manganese-based anode material.
Energy density test is carried out to lithium ion battery made from embodiment 1-8 and comparative example 1-8, and in 25 DEG C, 1C/1C
The thickness swelling of negative electrode tab, test result are as shown in table 1 after lower test loop and 100 circulations.
Table 1
As can be known from the results of Table 1, lithium-ion electric made from nano porous copper-silicium cathode piece using the method for the present invention preparation
Pond compared to nano-silicone wire/carbon composite negative plate (comparative example 1-2), aoxidizes sub- silicium cathode piece (comparative example 3-4) and common porous gold
Belong to the lithium ion battery of resulting negative electrode tab (comparative example 5-8) preparation of collector deposition silicon, energy density is improved, charges
The thickness swelling of front and back negative electrode tab is also improved, and cycle performance increases substantially.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article
Widest range.
Claims (10)
1. a kind of nano porous copper-silicium cathode piece, comprising: collector matrix, which is characterized in that have on the collector matrix
Several nanometer micropores are deposited with silicon in the nanometer micropore.
2. nano porous copper as described in claim 1-silicium cathode piece, it is characterised in that: the aperture of the nanometer micropore is 5nm
~1000nm.
3. nano porous copper as described in claim 1-silicium cathode piece, it is characterised in that: the collector matrix with a thickness of 5
μm~100 μm.
4. nano porous copper as described in claim 1-silicium cathode piece, it is characterised in that: the collector matrix is binary copper
Alloy Foil or ternary copper-alloy foil are made after being removed the pretreatment of non-copper component.
5. nano porous copper as claimed in claim 1 or 2 or 3 or 4-silicium cathode piece, it is characterised in that: the collector matrix
For albronze foil, cupromanganese foil, corronil foil, copper-titanium alloy foil, copper zirconium alloy foil, copper magnesium alloy foil, ormolu
One of foil, copper-tin alloy foil, cu-zn-al alloy foil, batterium alloy goldleaf, copper mock silver foil are through removing non-copper component
It is made after pretreatment.
6. nano porous copper as claimed in claim 1 or 2 or 3 or 4-silicium cathode piece, it is characterised in that: the collector matrix
The mass percent of middle copper is 10~90%.
7. such as nano porous copper-silicium cathode piece preparation method of any one of claim 1 to 6, which is characterized in that including following
Step:
Copper alloy foil is pre-processed, the non-copper component in copper alloy foil is removed, obtains the nanometer with several nanometer micropores
Porous copper current collector；
Nanometer micropore copper current collector is subjected to siliceous deposits in the method for chemical vapor deposition, obtains nano porous copper-silicium cathode piece.
8. nano porous copper as claimed in claim 7-silicium cathode piece preparation method, it is characterised in that: use chemical attack
Method or electrochemical erosion method or high-temperature vacuum facture pre-process copper alloy foil.
9. nano porous copper as claimed in claim 7 or 8-silicium cathode piece preparation method, it is characterised in that: when deposition silicon,
Nanometer micropore copper current collector is put into chemical vapor deposition stove, at 0.01~1000Pa pressure, 200~800 DEG C, is persistently led to
Enter silicon-containing precursor gas and carry out siliceous deposits, after deposition, silicon precursor gas is switched into nitrogen or argon gas, until stove
It is cooled to room temperature.
10. nano porous copper as claimed in claim 9-silicium cathode piece preparation method, it is characterised in that: the silicon precursor
Gas is SiH4、SiCl4、SiHCl3、SiH2Cl2、SiF4One or more of.
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| CN114284505A (en) * | 2021-12-23 | 2022-04-05 | 山东大学 | Porous copper current collector, preparation method thereof and application thereof in zinc/sodium ion battery |
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