CN117127231A - Aluminum foil and processing technology thereof - Google Patents
Aluminum foil and processing technology thereof Download PDFInfo
- Publication number
- CN117127231A CN117127231A CN202311133608.7A CN202311133608A CN117127231A CN 117127231 A CN117127231 A CN 117127231A CN 202311133608 A CN202311133608 A CN 202311133608A CN 117127231 A CN117127231 A CN 117127231A
- Authority
- CN
- China
- Prior art keywords
- foil
- rolled material
- aluminum foil
- rolling
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011888 foil Substances 0.000 title claims abstract description 140
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 85
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000012545 processing Methods 0.000 title claims abstract description 21
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 80
- 239000010936 titanium Substances 0.000 claims abstract description 67
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 62
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000005096 rolling process Methods 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 230000003647 oxidation Effects 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 238000005266 casting Methods 0.000 claims abstract description 24
- 238000003723 Smelting Methods 0.000 claims abstract description 20
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 238000013329 compounding Methods 0.000 claims abstract description 19
- 239000000155 melt Substances 0.000 claims abstract description 17
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000009966 trimming Methods 0.000 claims abstract description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 52
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 52
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 52
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 36
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000004310 lactic acid Substances 0.000 claims description 18
- 235000014655 lactic acid Nutrition 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 13
- HJXABDHMKBUSNG-UHFFFAOYSA-N but-1-ene triethoxysilane Chemical compound C(C)O[SiH](OCC)OCC.CCC=C HJXABDHMKBUSNG-UHFFFAOYSA-N 0.000 claims description 12
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 238000004381 surface treatment Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005097 cold rolling Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 22
- 239000013543 active substance Substances 0.000 abstract description 10
- 239000000835 fiber Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 9
- 239000003607 modifier Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- -1 siloxane structure Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
- C22C21/04—Modified aluminium-silicon alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the technical field of battery aluminum materials, in particular to an aluminum foil and a processing technology thereof, comprising the following steps: smelting and refining raw materials to obtain a melt; casting and rolling to obtain a casting and rolling blank; rolling the cast-rolled blank for four times, carrying out primary annealing, carrying out secondary rolling, carrying out secondary annealing, and trimming to obtain a cold-rolled material; performing three-four pass finish rolling on the cold rolled material to obtain a foil rolled material; and (3) sequentially carrying out titanium sol compounding, anodic oxidation and carbonization on the foil rolled material to obtain the product aluminum foil. According to the invention, the titanium sol containing carboxymethyl fibers is coated on the surface of a foil rolled material, anodic oxidation is carried out in the electrolyte containing the carboxymethyl fibers, and a composite carbon layer with a rough porous structure is formed by carbonization, so that the corrosion resistance of an aluminum foil product, the interface resistance and the bonding strength between the aluminum foil product and active substances are improved, and the stability, the battery efficiency and the cycle service life of the lithium ion battery can be improved.
Description
Technical Field
The invention relates to the technical field of battery aluminum materials, in particular to an aluminum foil and a processing technology thereof.
Background
The lithium ion battery is widely applied to various fields such as mobile phones, electric vehicles, electric automobiles and the like as a hot spot of the secondary battery, and the development of various devices is not separated from the support of the lithium ion battery. With the expansion of consumer market scale, the increasing demands of people and the intensive research on lithium ions, there is still room for improvement in the performance of lithium ion batteries, both in terms of energy density and service life, which is also excellent and higher. Besides developing a novel battery, the comprehensive performance of the lithium ion battery can be improved from the directions of a positive electrode material, a negative electrode material, a current collector, a conductive agent, a binder, electrolyte and the like. In the lithium ion battery, a current collector bears positive and negative electrode materials, and current generated by electrochemical reaction in the battery is collected and transmitted to an external circuit, so that conversion from chemical energy to electric energy is realized. In the field of lithium ion batteries, aluminum foil is commonly used to make positive current collectors. In the industrial foil making process, oil stains on the surface of an aluminum foil cannot be cleaned completely, the bonding strength of active substances and the surface of an aluminum current collector can be influenced, the active substances are easy to fall off, and stable charge and discharge of a lithium ion battery cannot be maintained. And the presence of an aluminum oxide film layer on the surface of the aluminum foil can lead to the reduction of battery performance. Therefore, we propose an aluminum foil and a processing technique thereof.
Disclosure of Invention
The invention aims to provide an aluminum foil and a processing technology thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the processing technology of the aluminum foil comprises the following processing steps:
step 1, smelting: smelting and refining raw materials to obtain a melt; casting and rolling to obtain a casting and rolling blank;
step 2, cold rolling: performing four-pass rolling, primary annealing, secondary rolling, secondary annealing and trimming on the cast-rolled blank obtained in the step 1 to obtain a cold-rolled material;
step 3, foil rolling: performing three-four pass finish rolling on the cold rolled material obtained in the step 2 to obtain a foil rolled material;
step 4, surface treatment: and (3) sequentially carrying out titanium sol compounding, anodic oxidation and carbonization on the foil rolled material obtained in the step (3) to obtain the product aluminum foil.
Further, in the step 1, smelting process conditions are as follows: the smelting temperature is controlled to be 745-755 ℃ and the smelting time is 8-10 h.
Further, in the step 1, the refining process conditions are as follows: during refining, modifier Al-5Ti-1B is added, high-purity argon is introduced, and the addition amount of the modifier is 0.2%;
the refining temperature is 735-745 ℃ and the refining time is 15-30 min.
Further, in the step 1, the melt comprises the following components in percentage by mass: 0.10 to 0.18 percent of Si, less than or equal to 0.15 percent of Fe, 0.015 to 0.025 percent of Cu, less than or equal to 0.030 percent of Ti, less than or equal to 0.009 percent of Mn, less than or equal to 0.009 percent of Mg, less than or equal to 0.03 percent of Zn, and the balance of Al;
the raw materials comprise two or three of electrolytic aluminum, aluminum ingots and aluminum-silicon intermediate alloys.
Further, in the step 1, the casting and rolling process conditions are as follows: the casting temperature is controlled at 690-705 ℃, the casting speed is 730-810 mm/min, and the casting blank with the thickness of 6.3-6.9 mm is obtained by water cooling.
Further, in the step 2, after four passes of rolling, a cold rolled material with the thickness of 0.65-0.75 mm is obtained;
the process conditions of the primary annealing are as follows: preserving heat for 18-24 h at 560-580 ℃;
after twice rolling, obtaining a cold-rolled material with the thickness of 0.24-0.30 mm;
the process conditions of the secondary annealing are as follows: preserving heat for 14-18 h at 180-220 ℃ and cooling.
Further, in the step 3, the thickness of the foil rolled stock is 6-12 μm.
Further, in the step 4, the titanium sol compounding includes the following process steps:
soaking the foil rolled material in the step 3 in titanium sol for 2-3 min, taking out the foil rolled material and drying the foil rolled material at 90-100 ℃ for 10-60 min, and soaking the foil rolled material in the titanium sol for 1-3 times according to the steps; preserving heat for 10-30 min at 550-600 ℃ to form the composite layer.
Further, the foil rolled stock obtained in the step 3 is subjected to pretreatment before use: cleaning by using acetone to remove organic matters on the surface of the glass; then, alkali washing, namely cleaning the foil rolled material surface oxide film for 30-60 seconds by adopting a 1M sodium hydroxide solution with the temperature of 35-40 ℃, and thinning and primarily etching the foil rolled material surface oxide film; acid washing and neutralization, and cleaning for 10-15 s by adopting 0.1M nitric acid; washing with water, leaching with deionized water, and drying with nitrogen at 70-90 ℃ for 60s.
Further, the titanium sol is obtained by the following process:
mixing carboxymethyl cellulose and deionized water, heating to 40-45 ℃, stirring for dissolution, adding 3-butene triethoxysilane and an initiator, and carrying out microwave reaction for 3-5 min under 350W power to obtain a modified carboxymethyl cellulose solution;
mixing tetrabutyl titanate with lactic acid, stirring for 30-60 min, adding absolute ethyl alcohol and modified carboxymethyl cellulose solution, stirring for 30-60 min, adding acetylacetone, and stirring for 10-20 min to obtain the product;
the mass ratio of the carboxymethyl cellulose to the 3-butene triethoxysilane to the initiator is 100 (77-85) (5.6-9.2);
the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1 (5-6): 14-17): 3-4): 1;
the initiator is a mixture of potassium persulfate and potassium thiosulfate, and the mass ratio is 1:1.
In the technical scheme, in the titanium sol compounding process of the step 4, under the action of an initiator in a deionized water solution system, hydroxyl in carboxymethyl cellulose can react with carbon-carbon double bonds in 3-butene triethoxysilane, a siloxane structure is introduced into cellulose molecules to prepare modified carboxymethyl cellulose, so as to obtain an aqueous solution of the modified carboxymethyl cellulose, wherein siloxane is primarily hydrolyzed and mixed with tetrabutyl titanate to obtain titanium sol with structures and elements such as carboxymethyl cellulose, silicon and titanium, the titanium sol is coated on the surface of a foil mill base in a dipping manner, and the titanium sol is freeze-dried to form a porous structure, and then the subsequent anodic oxidation is carried out to facilitate the formation of a subsequent oxide layer porous structure.
Further, in the step 4, the anodic oxidation includes the following process steps:
and (3) adopting a stainless steel counter electrode, placing the foil rolled material compounded by the titanium sol into electrolyte at 85-90 ℃, and carrying out anodic oxidation under the voltage of 10-80V until the current is reduced to 0.01A, so as to form a composite oxide layer, and thus obtaining the aluminum oxide foil.
Further, in the step 4, the electrolyte contains 10wt.% boric acid, 0.2 to 0.5wt.% carboxymethylcellulose, and 0.09wt.% ammonium pentaborate.
Further, in the step 4, the carbonization includes the following process steps:
carrying out hydrothermal carbonization on the anodized aluminum oxide in deionized water, wherein the dosage of the deionized water is 6-7 times of the mass of the aluminum oxide, the hydrothermal temperature is 220-250 ℃, the sealing pressure is 2-10 MPa, and the reaction is carried out for 160-200 min;
taking out, placing in 1-2M sodium hydroxide solution, standing for 8-15 s, washing with water, drying at 45-48 ℃ for 8-12 h to form a composite carbon layer, and obtaining the product aluminum foil.
In the technical scheme, an anodic oxidation process is adopted, and an oxide layer is prepared on the surface of the foil rolled material in an electrochemical mode. The foil rolling material is placed in electrolyte, and under the action of electric field force, oxidation reaction is carried out to obtain an alumina coating, and the alumina coating is combined with the composite layer obtained in the previous step to form a composite oxide layer of alumina, titanium dioxide and silicon dioxide. And the rough porous structure of the composite oxide layer provides more contact area for active substances, can improve the bonding strength of the aluminum foil of the manufactured product and the active substances, and can ensure the stability of the manufactured lithium ion battery in the long-time working process.
The foil rolled material impregnated by the titanium sol contains a carboxymethyl cellulose structure in a composite layer, and carboxyl and part of hydroxyl of the foil rolled material can coordinate aluminum ions generated in the anodic oxidation process to form a cross-linked network structure, and the toughness of the foil rolled material can reduce thermal stress, inhibit the growth and development of microcracks in the crystallization and transformation process of an anodic oxidation coating, enhance the stability of the surface structure of an aluminum foil of a manufactured product, further promote the stable combination of the aluminum foil and active substances, and facilitate the comprehensive performance of the manufactured lithium ion battery. The carboxymethyl cellulose structure is positioned in the structure of the composite oxide layer, and can be subjected to electrochemical action in the anodic oxidation process to generate crosslinking and oligomerization with the carboxymethyl cellulose contained in the electrolyte, so that the carboxymethyl cellulose is grafted with the composite oxide layer, and the content of organic matters in the composite oxide layer structure is improved. Then carrying out hydrothermal carbonization, carbonizing organic matters (carboxymethyl cellulose and carboxymethyl cellulose structure) to form a porous carbon layer with a large number of oxygen-containing groups on the surface, so that the carbon layer is embedded in pores of the composite oxide layer and is loaded on the surface, the surface resistance of the aluminum foil product can be further reduced, and the bonding strength between the aluminum foil product and active substances is improved; the surface toughness of the aluminum foil of the manufactured product and the wettability of the aluminum foil to the electrolyte of the lithium ion battery can be improved, the stress brought in the charging and discharging processes of the lithium ion battery can be relieved, and the stability of the lithium ion battery can be improved. The use of ammonium pentaborate in the electrolyte can improve the surface tension and the conductivity of the ammonium pentaborate, is beneficial to the electrolyte to enter the pores of the composite oxide layer on the surface of the foil rolling material, promotes the full contact between the electrolyte and the aluminum foil, and improves the voltage resistance performance of the aluminum foil of the manufactured product. And (3) performing chemical corrosion after carbonization, removing superfluous alumina on the surface, performing etching, activating the carbon layer to a certain extent, further enhancing the rough porous structure of the prepared composite carbon layer, and improving the application performance of the product aluminum foil in the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
according to the aluminum foil and the processing technology thereof, the titanium sol containing the carboxymethyl fibers is coated on the surface of the foil rolled material, anodic oxidation is carried out in the electrolyte containing the carboxymethyl fibers, and the composite carbon layer with a rough porous structure is formed by carbonization, so that the corrosion resistance of the aluminum foil product, the interface resistance and the bonding strength between the aluminum foil and active substances are improved, and the stability, the battery efficiency and the cycle service life of the lithium ion battery can be improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Electrolytic aluminum: from Hangzhou sea Di Metal products Co., ltd;
aluminum ingot: the purity is more than or equal to 99.7 percent, and the alloy is from Yidatong (Tianjin) metal material limited company;
aluminum-silicon intermediate alloy: aluminum silicon 10% from su zhou Sichuan metallocene materials limited;
modifier Al-5Ti-1B: the mass percentages of the chemical components are as follows: 5% of Ti, 1% of B, less than or equal to 0.20% of Fe, less than or equal to 0.20% of Si and the balance of Al, and is from Liaoning Xinpeng Gao metal Co., ltd;
carboxymethyl cellulose: roen chemical reagent from Shanghai Yi En chemical technologies Inc.
Example 1: the processing technology of the aluminum foil comprises the following processing steps:
step 1, smelting: smelting raw materials: the smelting temperature is controlled at 750 ℃ and the smelting time is 9h; refining: adding modifier Al-5Ti-1B, and introducing high-purity argon, wherein the addition amount of the modifier is 0.2%, the refining temperature is 740 ℃, and the refining time is 20min, so as to obtain a melt, and the melt comprises the following components in percentage by mass: 0.13% of Si, 0.08% of Fe, 0.021% of Cu, 0.021% of Ti, 0.005% of Mn, 0.003% of Mg, 0.015% of Zn and the balance of Al; casting and rolling: the casting temperature is controlled at 705 ℃, the casting speed is 730mm/min, and the casting is water-cooled to obtain a casting blank with the thickness of 6.3 mm; the raw materials are electrolytic aluminum, aluminum ingots and aluminum-silicon intermediate alloy, and the dosage is added according to the melt components; electrolytic aluminum, aluminum ingot, aluminum-silicon intermediate alloy, the amount is added according to the melt composition.
Step 2, cold rolling: performing four-pass rolling on the cast-rolled blank obtained in the step 1 to obtain a cold-rolled material with the thickness of 0.68 mm; primary annealing: preserving heat for 24 hours at 560 ℃ and rolling twice to obtain a cold-rolled material with the thickness of 0.26 mm; secondary annealing: preserving heat for 18 hours at the temperature of 180 ℃, cooling in a furnace, and trimming to obtain a cold-rolled material;
step 3, foil rolling: performing three times of finish rolling on the cold rolled material obtained in the step 2 to obtain a foil rolled material with the thickness of 10 mu m;
step 4, surface treatment: sequentially carrying out titanium sol compounding, anodic oxidation and carbonization on the foil rolled material obtained in the step 3,
4.1, pretreatment: cleaning the foil rolled material obtained in the step 3 by using acetone to remove organic matters on the surface of the foil rolled material; then, alkali washing, namely cleaning the foil rolled material surface oxide film for 60 seconds by adopting a 1M sodium hydroxide solution at 35 ℃, and thinning and primarily etching the foil rolled material surface oxide film; acid washing and neutralization, and cleaning for 10s by adopting 0.1M nitric acid; washing with water, eluting with deionized water, and drying with nitrogen at 70deg.C for 60s;
4.2, compounding titanium sol:
mixing carboxymethyl cellulose and deionized water, heating to 40 ℃, stirring for dissolution, adding 3-butene triethoxysilane and an initiator, and carrying out microwave reaction for 3min under the power of 350W to obtain a modified carboxymethyl cellulose solution; mixing tetrabutyl titanate with lactic acid, stirring for 30min, adding absolute ethyl alcohol and modified carboxymethyl cellulose solution, stirring for 30min, adding acetylacetone, and stirring for 10min to obtain titanium sol;
the mass ratio of the carboxymethyl cellulose to the 3-butene triethoxysilane to the initiator is 100:77:5.6; the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1:5:14:3:1; the initiator is a mixture of potassium persulfate and potassium thiosulfate, and the mass ratio is 1:1; the ratio of the carboxymethyl cellulose to the deionized water is 5g to 100mL;
soaking in titanium sol for 2min, taking out, and drying at 90deg.C for 60min; preserving heat at 550 ℃ for 30min to form a composite layer;
4.3, anodic oxidation:
placing a foil rolled material compounded by titanium sol into electrolyte at 85 ℃ by adopting a stainless steel counter electrode, and performing anodic oxidation under the voltage of 10V until the current is reduced to 0.01A, so as to form a compound oxide layer, thereby obtaining an aluminum oxide foil; the electrolyte contains 10wt.% boric acid, 0.2wt.% carboxymethylcellulose and 0.09wt.% ammonium pentaborate;
4.4, carbonizing:
carrying out hydrothermal carbonization on the anodized aluminum oxide in deionized water, wherein the dosage of the deionized water is 6 times of the mass of the aluminum oxide, the hydrothermal temperature is 220 ℃, the sealing pressure is 6MPa, and the reaction is carried out for 160min; taking out, standing in 1M sodium hydroxide solution for 15s, washing with water, and drying at 45 ℃ for 8h to form a composite carbon layer, thus obtaining the product aluminum foil.
Example 2: the processing technology of the aluminum foil comprises the following processing steps:
step 1, smelting: smelting raw materials: the smelting temperature is controlled at 750 ℃ and the smelting time is 9h; refining: adding modifier Al-5Ti-1B, and introducing high-purity argon, wherein the addition amount of the modifier is 0.2%, the refining temperature is 740 ℃, and the refining time is 20min, so as to obtain a melt, and the melt comprises the following components in percentage by mass: 0.13% of Si, 0.08% of Fe, 0.021% of Cu, 0.021% of Ti, 0.005% of Mn, 0.003% of Mg, 0.015% of Zn and the balance of Al; casting and rolling: the casting temperature is controlled at 698 ℃, the casting speed is 770mm/min, and the casting blank with the thickness of 6.6mm is obtained by water cooling; the raw materials are electrolytic aluminum, aluminum ingots and aluminum-silicon intermediate alloy, and the dosage is added according to the melt components; electrolytic aluminum, aluminum ingot, aluminum-silicon intermediate alloy, the amount is added according to the melt composition.
Step 2, cold rolling: performing four-pass rolling on the cast-rolled blank obtained in the step 1 to obtain a cold-rolled material with the thickness of 0.68 mm; primary annealing: preserving heat for 21h at 570 ℃, and rolling twice to obtain a cold-rolled material with the thickness of 0.26 mm; secondary annealing: preserving heat for 16h at 200 ℃, cooling in a furnace, and trimming to obtain a cold-rolled material;
step 3, foil rolling: performing four-pass finish rolling on the cold rolled material obtained in the step 2 to obtain a foil rolled material with the thickness of 10 mu m;
step 4, surface treatment: sequentially carrying out titanium sol compounding, anodic oxidation and carbonization on the foil rolled material obtained in the step 3,
4.1, pretreatment: cleaning the foil rolled material obtained in the step 3 by using acetone to remove organic matters on the surface of the foil rolled material; then, alkali washing, namely cleaning the foil rolled material surface oxide film for 45 seconds by adopting a 1M sodium hydroxide solution at 38 ℃, and thinning and primarily etching the foil rolled material surface oxide film; acid washing and neutralization, and cleaning for 12s by adopting 0.1M nitric acid; washing with water, leaching with deionized water, and drying with nitrogen at 80deg.C for 60s;
4.2, compounding titanium sol:
mixing carboxymethyl cellulose and deionized water, heating to 42 ℃, stirring and dissolving, adding 3-butene triethoxysilane and an initiator, and carrying out microwave reaction for 4min under the power of 350W to obtain a modified carboxymethyl cellulose solution; mixing tetrabutyl titanate with lactic acid, stirring for 45min, adding absolute ethyl alcohol and modified carboxymethyl cellulose solution, stirring for 45min, adding acetylacetone, and stirring for 15min to obtain titanium sol;
the mass ratio of the carboxymethyl cellulose to the 3-butene triethoxysilane to the initiator is 100:81:7.4; the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1:5.5:15.5:3.5:1; the initiator is a mixture of potassium persulfate and potassium thiosulfate, and the mass ratio is 1:1; the ratio of the carboxymethyl cellulose to the deionized water is 5g to 100mL;
soaking in titanium sol for 2.5min, taking out, drying at 95deg.C for 35min, soaking the foil rolled material obtained in step 3 in titanium sol for 2 times according to the above steps; preserving heat at 575 ℃ for 20min to form a composite layer;
4.3, anodic oxidation:
placing a foil rolled material compounded by titanium sol into an electrolyte at 88 ℃ by adopting a stainless steel counter electrode, and performing anodic oxidation under the voltage of 50V until the current is reduced to 0.01A, so as to form a compound oxide layer, thereby obtaining an aluminum oxide foil; the electrolyte contains 10wt.% boric acid, 0.3wt.% carboxymethylcellulose and 0.09wt.% ammonium pentaborate;
4.4, carbonizing:
carrying out hydrothermal carbonization on the anodized aluminum oxide in deionized water, wherein the dosage of the deionized water is 6.5 times of the mass of the aluminum oxide, the hydrothermal temperature is 235 ℃, the sealing pressure is 6MPa, and the reaction is carried out for 180min; taking out, standing in 1.5M sodium hydroxide solution for 12s, washing with water, and drying at 46 ℃ for 10h to form a composite carbon layer, thus obtaining the product aluminum foil.
Example 3: the processing technology of the aluminum foil comprises the following processing steps:
step 1, smelting: smelting raw materials: the smelting temperature is controlled at 750 ℃ and the smelting time is 9h; refining: adding modifier Al-5Ti-1B, and introducing high-purity argon, wherein the addition amount of the modifier is 0.2%, the refining temperature is 740 ℃, and the refining time is 20min, so as to obtain a melt, and the melt comprises the following components in percentage by mass: 0.13% of Si, 0.08% of Fe, 0.021% of Cu, 0.021% of Ti, 0.005% of Mn, 0.003% of Mg, 0.015% of Zn and the balance of Al; casting and rolling: the casting temperature is controlled at 690 ℃, the casting speed is 730mm/min, and the casting is water-cooled to obtain a casting blank with the thickness of 6.9 mm; the raw materials are electrolytic aluminum, aluminum ingots and aluminum-silicon intermediate alloy, and the dosage is added according to the melt components; electrolytic aluminum, aluminum ingot, aluminum-silicon intermediate alloy, the amount is added according to the melt composition.
Step 2, cold rolling: performing four-pass rolling on the cast-rolled blank obtained in the step 1 to obtain a cold-rolled material with the thickness of 0.68 mm; primary annealing: preserving heat for 18h at 580 ℃, and rolling twice to obtain a cold-rolled material with the thickness of 0.26 mm; secondary annealing: preserving heat for 14h at 220 ℃, cooling in a furnace, and trimming to obtain a cold-rolled material;
step 3, foil rolling: performing four-pass finish rolling on the cold rolled material obtained in the step 2 to obtain a foil rolled material with the thickness of 10 mu m;
step 4, surface treatment: sequentially carrying out titanium sol compounding, anodic oxidation and carbonization on the foil rolled material obtained in the step 3,
4.1, pretreatment: cleaning the foil rolled material obtained in the step 3 by using acetone to remove organic matters on the surface of the foil rolled material; then, alkali washing, namely cleaning the foil rolled material surface oxide film for 60 seconds by adopting a 1M sodium hydroxide solution at the temperature of 40 ℃, and thinning and primarily etching the foil rolled material surface oxide film; acid washing and neutralization, and cleaning for 15s by adopting 0.1M nitric acid; washing with water, leaching with deionized water, and drying with nitrogen at 90deg.C for 60s;
4.2, compounding titanium sol:
mixing carboxymethyl cellulose and deionized water, heating to 45 ℃, stirring for dissolution, adding 3-butene triethoxysilane and an initiator, and carrying out microwave reaction for 5min under the power of 350W to obtain a modified carboxymethyl cellulose solution; mixing tetrabutyl titanate with lactic acid, stirring for 60min, adding absolute ethyl alcohol and modified carboxymethyl cellulose solution, stirring for 60min, adding acetylacetone, and stirring for 20min to obtain titanium sol;
the mass ratio of the carboxymethyl cellulose to the 3-butene triethoxysilane to the initiator is 100:85:9.2; the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1:6:17:4:1; the initiator is a mixture of potassium persulfate and potassium thiosulfate, and the mass ratio is 1:1; the ratio of the carboxymethyl cellulose to the deionized water is 5g to 100mL;
soaking in titanium sol for 3min, taking out, drying at 100deg.C for 10min, soaking the foil rolled material obtained in step 3 in titanium sol for 3 times according to the above steps; preserving heat at 600 ℃ for 10min to form a composite layer;
4.3, anodic oxidation:
placing a foil rolled material compounded by titanium sol into electrolyte at 85 ℃ by adopting a stainless steel counter electrode, and performing anodic oxidation under the voltage of 60V until the current is reduced to 0.01A, so as to form a compound oxide layer, thereby obtaining an aluminum oxide foil; the electrolyte contains 10wt.% boric acid, 0.5wt.% carboxymethylcellulose and 0.09wt.% ammonium pentaborate;
4.4, carbonizing:
carrying out hydrothermal carbonization on the anodized aluminum oxide in deionized water, wherein the dosage of the deionized water is 7 times of the mass of the aluminum oxide, the hydrothermal temperature is 250 ℃, the sealing pressure is 2MPa, and the reaction is carried out for 200min; taking out, standing in 2M sodium hydroxide solution for 8s, washing with water, and drying at 48 ℃ for 8h to form a composite carbon layer, thus obtaining the product aluminum foil.
Comparative example 1: a processing technology of an aluminum foil,
4.2, compounding titanium sol:
mixing carboxymethyl cellulose and deionized water, heating to 40 ℃ and stirring for dissolution to obtain carboxymethyl cellulose solution; mixing tetrabutyl titanate with lactic acid, stirring for 30min, adding absolute ethyl alcohol and carboxymethyl cellulose solution, stirring for 30min, adding acetylacetone, and stirring for 10min to obtain titanium sol;
the mass ratio of the carboxymethyl cellulose to the 3-butene triethoxysilane to the initiator is 100:77:5.6; the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1:5:14:3:1; the initiator is a mixture of potassium persulfate and potassium thiosulfate, and the mass ratio is 1:1; the ratio of the carboxymethyl cellulose to the deionized water is 5g to 100mL;
soaking in titanium sol for 2min, taking out, and drying at 90deg.C for 60min; preserving heat at 550 ℃ for 30min to form a composite layer;
steps 1-3, 4.1, 4.3-4.4 are the same as in example 1, and the product aluminum foil is obtained.
Comparative example 2: a processing technology of an aluminum foil,
4.2, compounding titanium sol:
mixing tetrabutyl titanate with lactic acid, stirring for 30min, adding absolute ethyl alcohol and deionized water, stirring for 30min, adding acetylacetone, and stirring for 10min to obtain titanium sol; the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1:5:14:3:1; soaking in titanium sol for 2min, taking out, and drying at 90deg.C for 60min; preserving heat at 550 ℃ for 30min to form a composite layer;
4.3, anodic oxidation:
placing a foil rolled material compounded by titanium sol into electrolyte at 85 ℃ by adopting a stainless steel counter electrode, and performing anodic oxidation under the voltage of 10V until the current is reduced to 0.01A, so as to form a compound oxide layer, thereby obtaining an aluminum oxide foil; the electrolyte contains 10wt.% boric acid, 0.2wt.% carboxymethylcellulose and 0.09wt.% ammonium pentaborate;
steps 1-3, 4.1, 4.3 are the same as in example 1, resulting in a product aluminum foil.
Comparative example 3: a processing technology of an aluminum foil,
step 4, surface treatment: sequentially carrying out titanium sol compounding and anodic oxidation on the foil rolled material obtained in the step 3,
4.2, compounding titanium sol:
mixing tetrabutyl titanate with lactic acid, stirring for 30min, adding absolute ethyl alcohol and deionized water, stirring for 30min, adding acetylacetone, and stirring for 10min to obtain titanium sol; the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1:5:14:3:1; soaking in titanium sol for 2min, taking out, and drying at 90deg.C for 60min; preserving heat at 550 ℃ for 30min to form a composite layer;
4.3, anodic oxidation:
placing a foil rolled material compounded by titanium sol into electrolyte at 85 ℃ by adopting a stainless steel counter electrode, and performing anodic oxidation under the voltage of 10V until the current is reduced to 0.01A, so as to form a compound oxide layer, thereby obtaining an aluminum oxide foil; the electrolyte contains 10wt.% boric acid, 0.2wt.% carboxymethylcellulose and 0.09wt.% ammonium pentaborate;
steps 1-3 and 4.1 were the same as in example 1 to obtain a product aluminum foil.
Comparative example 4: a processing technology of an aluminum foil,
step 4, surface treatment: sequentially carrying out titanium sol compounding, anodic oxidation and carbonization on the foil rolled material obtained in the step 3, and compounding the titanium sol with 4.2:
mixing tetrabutyl titanate with lactic acid, stirring for 30min, adding absolute ethyl alcohol and deionized water, stirring for 30min, adding acetylacetone, and stirring for 10min to obtain titanium sol; the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1:5:14:3:1; soaking in titanium sol for 2min, taking out, and drying at 90deg.C for 60min; preserving heat at 550 ℃ for 30min to form a composite layer;
4.3, anodic oxidation:
placing a foil rolled material compounded by titanium sol into electrolyte at 85 ℃ by adopting a stainless steel counter electrode, and performing anodic oxidation under the voltage of 10V until the current is reduced to 0.01A, so as to form a compound oxide layer, thereby obtaining an aluminum oxide foil; the electrolyte contains 10wt.% boric acid and 0.09wt.% ammonium pentaborate;
steps 1-3, 4.1, 4.3 are the same as in example 1, resulting in a product aluminum foil.
Comparative example 5: a processing technology of an aluminum foil,
step 4, surface treatment: anodizing the foil rolled material obtained in the step 3,
4.2, anodic oxidation:
placing a foil rolled material compounded by titanium sol into electrolyte at 85 ℃ by adopting a stainless steel counter electrode, and performing anodic oxidation under the voltage of 10V until the current is reduced to 0.01A, so as to form a compound oxide layer, thereby obtaining an aluminum oxide foil; the electrolyte contains 10wt.% boric acid and 0.09wt.% ammonium pentaborate;
steps 1-3 and 4.1 were the same as in example 1 to obtain a product aluminum foil.
Experiment: taking the aluminum foils obtained in examples 1-3 and comparative examples 1-5 as positive electrode current collector, preparing positive electrode, and mixing active material LiFePO according to the mass ratio of 92:4:4 4 Mixing a conductive agent SP, a binder PVDF and a solvent NMP to form positive electrode slurry with the solid content of 50%, coating the positive electrode slurry on an aluminum foil product, vacuum drying at 80 ℃ for 12 hours, rolling to form a positive electrode (with the diameter of 16 mm), and preparing a sample; naTi is added according to the mass ratio of 92:3:5 2 (PO 4 ) 3 Mixing the conductive agent SP, the binder PVDF and the solvent NMP to form negative electrode slurry with the solid content of 40%, coating the negative electrode slurry on carbon paper, vacuum drying for 12 hours at 80 ℃, and rolling to form a negative electrode (with the diameter of 15.4 mm); and 2M Li2SO4 is used as electrolyte, filter paper is used as a diaphragm, the lithium ion battery is formed by assembly, the performance of the lithium ion battery is detected respectively, and the detection result is recorded:
peel strength test: detecting the peeling strength of the positive pole piece by adopting an electronic tension tester, wherein the peeling rate is 300mm/min;
impedance testing: detecting alternating current impedance of the battery by adopting a battery internal resistance tester;
capacity test: the battery charging and discharging capacity and the energy are detected by adopting a 5V/6A single-core test cabinet, and the test method comprises the following steps: constant current charging to 3.65V at 0.5C, constant voltage to current 0.05C, and constant current discharging to 2.0V at 0.2C;
and (3) testing the cycle performance: the cycle performance of the battery is detected by adopting a 5V/10A single-core test cabinet, and the cycle method comprises the following steps: discharging the battery to 2.0V, standing for 30min, charging to 3.65V at 1C, constant voltage to current 0.05C, discharging to 2.0V at 1C multiplying power, standing for 30min, and circulating for 500 times; the battery capacity was again checked and the rate was calculated.
From the data in the above table, the following conclusions can be clearly drawn:
the product aluminum foils obtained in examples 1-3 were compared with the product aluminum foils obtained in comparative examples 1-5, and it was found that,
compared with the comparative examples, the aluminum foils obtained in examples 1-3 produced positive electrodes with higher peel force data; the lithium ion battery formed by assembly has lower internal resistance and higher charge-discharge efficiency and capacity retention rate data. This fully demonstrates that the invention realizes the improvement of the surface resistance, active substances and bonding strength of the aluminum foil product, and the prepared lithium ion battery has better electrochemical performance.
In comparison with example 1, the carboxymethyl cellulose in the titanium sol of comparative example 1 was not modified; comparative example 2 the titanium sol does not contain carboxymethyl cellulose or a modified substance thereof; comparative example 3 the titanium sol contained no carboxymethyl cellulose or its modified substance, and the electrolyte contained carboxymethyl cellulose, but did not undergo carbonization process; comparative example 4 neither the titanium sol nor the electrolyte was added with carboxymethyl cellulose or its modified substance; comparative example 5 was not subjected to a titanium sol compounding and carbonization process, and no carboxymethyl cellulose was added to the electrolyte;
the aluminum foils of the products obtained in comparative examples 1 to 5 gave positive electrodes having lower data on the peel force, and lithium ion batteries assembled with the same had higher internal resistance and lower data on the charge/discharge efficiency and capacity retention rate. The surface treatment process of the aluminum foil and the arrangement of the used components can promote the improvement of the surface resistance of the aluminum foil product, the active substances and the bonding strength, and the prepared lithium ion battery has better electrochemical performance.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The processing technology of the aluminum foil is characterized by comprising the following steps of: the method comprises the following process steps:
step 1, smelting: smelting and refining raw materials to obtain a melt; casting and rolling to obtain a casting and rolling blank;
step 2, cold rolling: performing four-pass rolling, primary annealing, secondary rolling, secondary annealing and trimming on the cast-rolled blank obtained in the step 1 to obtain a cold-rolled material;
step 3, foil rolling: performing three-four pass finish rolling on the cold rolled material obtained in the step 2 to obtain a foil rolled material;
step 4, surface treatment: and (3) sequentially carrying out titanium sol compounding, anodic oxidation and carbonization on the foil rolled material obtained in the step (3) to obtain the product aluminum foil.
2. A process for manufacturing an aluminum foil according to claim 1, wherein: in the step 1, the melt comprises the following components in percentage by mass: 0.10 to 0.18 percent of Si, less than or equal to 0.15 percent of Fe, 0.015 to 0.025 percent of Cu and less than or equal to Ti
0.030％，Mn:≤0.009％，Mg:≤0.009％，Zn:≤0.03％。
3. A process for manufacturing an aluminum foil according to claim 1, wherein: in the step 3, the thickness of the foil rolled material is 6-12 mu m.
4. A process for manufacturing an aluminum foil according to claim 1, wherein: in the step 4, the titanium sol compounding comprises the following process steps:
soaking the foil rolled material in the step 3 in titanium sol for 2-3 min, taking out the foil rolled material and drying the foil rolled material at 90-100 ℃ for 10-60 min, and soaking the foil rolled material in the titanium sol for 1-3 times according to the steps; preserving heat for 10-30 min at 550-600 ℃ to form the composite layer.
5. The process for manufacturing an aluminum foil according to claim 4, wherein: the titanium sol is obtained by the following process:
mixing carboxymethyl cellulose and deionized water, heating to 40-45 ℃, stirring for dissolution, adding 3-butene triethoxysilane and an initiator, and carrying out microwave reaction for 3-5 min under 350W power to obtain a modified carboxymethyl cellulose solution;
mixing tetrabutyl titanate and lactic acid, stirring for 30-60 min, adding absolute ethyl alcohol and modified carboxymethyl cellulose solution, stirring for 30-60 min, adding acetylacetone, and stirring for 10-20 min.
6. The process for manufacturing an aluminum foil according to claim 5, wherein: the mass ratio of the carboxymethyl cellulose to the 3-butene triethoxysilane to the initiator is 100 (77-85) (5.6-9.2);
the molar ratio of tetrabutyl titanate, lactic acid, absolute ethyl alcohol, deionized water and acetylacetone is 1 (5-6): 14-17): 3-4): 1.
7. The process for manufacturing an aluminum foil according to claim 5, wherein: in the step 4, the anodic oxidation comprises the following process steps:
and (3) adopting a stainless steel counter electrode, placing the foil rolled material compounded by the titanium sol into electrolyte at 85-90 ℃, and carrying out anodic oxidation under the voltage of 10-80V until the current is reduced to 0.01A, so as to form a composite oxide layer, and thus obtaining the aluminum oxide foil.
8. The process for manufacturing an aluminum foil according to claim 7, wherein: in the step 4, the electrolyte contains 10wt.% boric acid, 0.2-0.5 wt.% carboxymethyl cellulose and 0.09wt.% ammonium pentaborate.
9. The process for manufacturing an aluminum foil according to claim 7, wherein: in the step 4, the carbonization comprises the following process steps:
carrying out hydrothermal carbonization on the anodized aluminum oxide in deionized water, wherein the dosage of the deionized water is 6-7 times of the mass of the aluminum oxide, the hydrothermal temperature is 220-250 ℃, the sealing pressure is 2-10 MPa, and the reaction is carried out for 160-200 min;
taking out, placing in 1-2M sodium hydroxide solution, standing for 8-15 s, washing with water, drying at 45-48 ℃ for 8-12 h to form a composite carbon layer, and obtaining the product aluminum foil.
10. An aluminum foil produced by the process according to any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311133608.7A CN117127231B (en) | 2023-09-05 | 2023-09-05 | Aluminum foil and processing technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311133608.7A CN117127231B (en) | 2023-09-05 | 2023-09-05 | Aluminum foil and processing technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117127231A true CN117127231A (en) | 2023-11-28 |
| CN117127231B CN117127231B (en) | 2024-03-08 |
Family
ID=88852538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311133608.7A Active CN117127231B (en) | 2023-09-05 | 2023-09-05 | Aluminum foil and processing technology thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117127231B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413209A (en) * | 2008-11-12 | 2009-04-22 | 东华大学 | Method for carbon fiber surface modification of plasma coated with nano colloidal sols by plasma treatment |
| CN105063429A (en) * | 2015-07-15 | 2015-11-18 | 浙江中金铝业有限公司 | Method for preparing aluminum foil for lithium battery |
| CN105824190A (en) * | 2016-05-30 | 2016-08-03 | 中国科学院上海高等研究院 | Preparing method for nanoimprint template |
| CN111495348A (en) * | 2020-04-23 | 2020-08-07 | 王伟东 | Preparation method of porous photocatalyst filter screen |
-
2023
- 2023-09-05 CN CN202311133608.7A patent/CN117127231B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413209A (en) * | 2008-11-12 | 2009-04-22 | 东华大学 | Method for carbon fiber surface modification of plasma coated with nano colloidal sols by plasma treatment |
| CN105063429A (en) * | 2015-07-15 | 2015-11-18 | 浙江中金铝业有限公司 | Method for preparing aluminum foil for lithium battery |
| CN105824190A (en) * | 2016-05-30 | 2016-08-03 | 中国科学院上海高等研究院 | Preparing method for nanoimprint template |
| CN111495348A (en) * | 2020-04-23 | 2020-08-07 | 王伟东 | Preparation method of porous photocatalyst filter screen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117127231B (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5992016B2 (en) | Method for modifying lithium ion battery cathode material | |
| CN108346793B (en) | Preparation method and application of nano-silicon with porous structure | |
| CN108539280B (en) | Composite current collector and preparation method thereof | |
| CN113078322A (en) | Graphene-silicon negative electrode material with lithium battery cycling stability and preparation method thereof | |
| CN103811766A (en) | Preparation method of current collector | |
| CN105200509A (en) | Cleaning method of electronic energy storage materials | |
| CN111261868A (en) | Vanadium pentoxide and preparation method and application thereof | |
| CN113823781A (en) | Composite negative electrode material and preparation method thereof | |
| CN113421775A (en) | NiO @ CoMoO4Preparation method of/NF capacitance electrode | |
| CN117127231B (en) | Aluminum foil and processing technology thereof | |
| CN111584831B (en) | Polymer-coated silicon/sulfur-doped graphene negative electrode material and preparation method thereof | |
| WO2023179050A1 (en) | Graphene-based nitride negative electrode material and preparation method therefor | |
| CN109503723B (en) | Preparation method of nano CMCLi | |
| CN111540893A (en) | Preparation method of graphene modification-based lithium battery electrode material | |
| CN116002679A (en) | Negative electrode material, preparation method and application thereof | |
| KR20190060587A (en) | Process for preparing current collector for pseudo capacitor | |
| CN115172054A (en) | Medium-high voltage anodic oxidation pretreatment method, aluminum foil and aluminum electrolytic capacitor | |
| CN109994723B (en) | SiO (silicon dioxide)xPreparation method of-G/PAA-PANI/Cu composite material | |
| CN114420912A (en) | Ceramic phase silicon-nitrogen layer coated silicon negative material, preparation method and application thereof | |
| CN113113609A (en) | Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof | |
| CN112002564A (en) | Electrode material of super capacitor, preparation method and application | |
| CN114318847B (en) | Carbon fiber composite material loaded with oxygen-deficient copper oxide and preparation method and application thereof | |
| CN113823831A (en) | Sulfonic acid functionalized polyethyleneimine polymer solid electrolyte | |
| CN113753946B (en) | Preparation method of titanium dioxide @ graphene @ titanium dioxide anode material, product and application | |
| CN113991047B (en) | Preparation method and application of modified metal zinc cathode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |