CN116470066A - Composite copper current collector and application thereof in manufacturing composite lithium metal negative electrode - Google Patents
Composite copper current collector and application thereof in manufacturing composite lithium metal negative electrode Download PDFInfo
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- CN116470066A CN116470066A CN202310616392.3A CN202310616392A CN116470066A CN 116470066 A CN116470066 A CN 116470066A CN 202310616392 A CN202310616392 A CN 202310616392A CN 116470066 A CN116470066 A CN 116470066A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 89
- 239000010949 copper Substances 0.000 title claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 230000006911 nucleation Effects 0.000 claims abstract description 21
- 238000010899 nucleation Methods 0.000 claims abstract description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000011888 foil Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 5
- 239000001989 lithium alloy Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002041 carbon nanotube Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 229910017768 LaF 3 Inorganic materials 0.000 claims description 7
- 239000011858 nanopowder Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 5
- 239000002109 single walled nanotube Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 230000008021 deposition Effects 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- -1 chalcogen copper compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
-
- 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
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium battery manufacturing, and particularly relates to a composite copper current collector and application thereof in manufacturing a composite lithium metal negative electrode, wherein the composite copper current collector is obtained by coating suspension slurry L3 on the surface of a copper current collector and completely drying the suspension slurry L3; the suspension slurry L3 is prepared by sequentially adding a binder, conductive carbon and a modifying reagent into a solvent, wherein the modifying reagent is a lithium-philic reagent or a compound for regulating lithium nucleation growth; according to the invention, the lithium foil or the lithium alloy foil is pressed on the front and back sides of the copper current collector to prepare the composite lithium metal negative electrode, the prepared composite lithium metal negative electrode has higher coulomb efficiency, can control the nucleation growth of negative electrode lithium, avoid serious lithium dendrite formation, and improve the cycle life and the safety performance of a lithium metal battery.
Description
Technical Field
The invention belongs to the technical field of lithium battery manufacturing, and particularly relates to a composite copper current collector and application thereof in manufacturing a composite lithium metal negative electrode.
Background
The lithium metal battery is an energy storage battery with high energy density, and directly adopts lithium metal as a negative electrode, wherein the specific capacity of the lithium metal negative electrode is up to 3860mAh/g. However, lithium metal batteries have unpredictable cycle life and battery safety issues due to the susceptibility of lithium metal cathodes to lithium dendrite growth, "dead lithium" and loss of good electrical contact by local breakage of the lithium metal cathode during continuous lithium deposition/stripping. Although the lithium metal negative electrode can be directly compounded on the copper current collector to solve the problem that the lithium metal negative electrode is locally broken and loses good electrical contact in the continuous lithium deposition/stripping process, copper is a non-lithium-philic material, which is unfavorable for the later lithium deposition/stripping. Therefore, it is necessary to construct a layer of a lithium-philic substance on the surface of the copper current collector, specifically, to inhibit the growth of lithium dendrites and "dead lithium" by constructing a firm SEI film on the surface of the negative electrode and/or constructing a layer of a substance capable of regulating the nucleation and regular growth of lithium on the surface of the copper current collector. LiF, as a component of a robust SEI film, can be generated in situ by coating a layer of fluorine-containing species on a copper current collector. To reduce the SEI interfacial resistance, a stable lithium deposition can be promoted by pre-adhering a layer of additive species to the surface of the copper current collector to form a low resistance SEI layer, thereby reducing the interfacial resistance of the negative electrode.
The current improvement scheme for the copper current collector is as follows:
patent publication No. CN110299513B discloses LiNO 3 The lithium-philic cathode is obtained by selecting metal with lower metal activity than lithium and reacting the metal with lithium in the form of nitrate so that lithium nitrate is deposited on a cathode plate, and the aim is to optimize the preparation method of the lithium-philic matrix and realize uniform lithium deposition by adjusting lithium nucleation and homogenizing lithium ion distribution. And is reduced to LiNXOY and Li during battery cycling 3 N, the solid electrolyte layer can inhibit the growth of lithium dendrite and reduce interface impedance, so as to stabilize lithium deposition and prolong the service life of the metal lithium battery. The solution is to deposit the lithium-philic material directly on the lithium metal, so that the problem that the copper current collector is not lithium-philic cannot be improved.
The publication CN113937269a discloses the growth of silver particles on a substrate using the principle of silver mirror reaction to obtain a silver plated three-dimensional porous copper current collector. The silver particles act as lithium-philic sites to induce nucleation and growth of lithium ions in the three-dimensional pore canal, thereby confining lithium dendrites within the pore canal. However, the scheme has large control difficulty and still has unsatisfactory effect.
The patent of publication No. CN111370691A discloses that chalcogen copper compounds generated on the surface of a copper simple substance by an in-situ synthesis method are adopted as the negative electrode of a lithium ion battery, so that the problem of nonuniform deposition of lithium ions in the lithium ion battery is solved, the growth of lithium dendrites is avoided, the coulomb efficiency of the lithium ion battery is effectively improved, the cycling stability of the lithium ion battery is improved, and in addition, the nucleation overpotential of the lithium ions can be reduced by adopting the copper simple substance material containing the chalcogen copper compounds as the negative electrode of the lithium ion battery, so that the nucleation of the lithium ions is facilitated. But the scheme has high cost and high energy consumption.
Therefore, there is a need for a composite copper current collector that prevents local breakage of lithium metal negative electrodes during continuous lithium deposition/stripping, and has a lithium-philic, ability to regulate lithium nucleation growth, and ability to build a robust/low resistance SEI in situ, as well as a long cycle life and high safety composite lithium metal negative electrode. Meanwhile, the manufacturing process of the composite copper current collector and the composite lithium metal negative electrode is simple and controllable, low in cost and high in manufacturing compatibility with the prior lithium metal battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite copper current collector and application thereof in manufacturing a composite lithium metal negative electrode.
The method is realized by the following technical scheme:
a composite copper current collector is obtained by coating a suspension slurry L3 on the surface of a copper current collector and completely drying the copper current collector.
The preparation method of the suspension slurry L3 comprises the following steps:
(1) Adding a binder into a solvent, and fully dissolving the binder to obtain a solution L1;
(2) Adding conductive carbon into the solution L1, and stirring and dispersing uniformly to obtain suspension slurry L2;
(3) Adding a modifying reagent into the suspension slurry L2, and uniformly stirring to obtain suspension slurry L3; the modifying reagent is a lithium-philic reagent or a compound for regulating lithium nucleation growth.
In the step (1), the solvent is one of deionized water, N-methylpyrrolidone (NMP) and Tetrahydrofuran (THF).
In the step (1), the binder is any one of an aqueous binder and an organic binder; the water-based binder is one or more of sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR) and polyacrylic acid (PAA); the organic binder is one of polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PMMA) polymers.
Preferably, in step (1), the aqueous binder is CMC in weight ratio: sbr= (0.5 to 1.5): 1, a mixture of two or more of the above-mentioned materials; further preferably 1:1.
preferably, in step (1), the aqueous binder is CMC in weight ratio: SBR: paa= (0.5 to 1.5): (0.5-1.5): the mixture of (1-3); further preferably 1:1:2.
in the step (1), the weight ratio of the water-based binder to the deionized water is (0.01-0.1): 1, a step of; preferably 0.06:1.
preferably, in step (1), the binder is selected from PVDF, the solvent is NMP, and the weight ratio of the binder PVDF to the solvent NMP is (0.01 to 0.1): 1, a step of; further preferably 0.06:1, a step of;
preferably, in step (1), the binder is selected from PMMA polymer, the solvent is THF, and the weight ratio of the binder PMMA to the solvent THF is (0.0001 to 0.01): 1, a step of; further preferably 0.0006:1.
in the step (2), the conductive carbon is one or more of carbon black (SP), carbon Nanotubes (CNTs) and single-walled carbon nanotubes; preferably, the conductive carbon is a mixture of SP and CNTs, or a mixture of SP, CNTs and single-walled carbon nanotubes;
preferably, the weight ratio of the mixed conductive carbon of the SP and the CNTs is SP: CNTs= (0.5-1.5): (0.5-1.5); further preferably 1:1.
preferably, the weight ratio of the mixed conductive carbon of the SP, the CNTs and the single-walled carbon nanotubes is SP: CNTs: single-walled carbon nanotubes= (0.5-1.5): (0.5-1.5): (0.00025 to 0.001); further preferably 1:1:0.0005.
in the step (2), the weight ratio of the conductive carbon to the deionized water solvent in the suspension slurry L2 is (0.01-0.06): 1, a step of; preferably 0.04:1, a step of;
in the step (2), the weight ratio of the conductive carbon to the NMP solvent in the suspension slurry L2 is (0.01-0.06): 1, a step of; preferably 0.04:1, a step of;
in the step (2), the weight ratio of the conductive carbon to the THF solvent in the suspension slurry L2 is (0.0001-0.0006): 1, a step of; preferably 0.0004:1, a step of;
in the step (3), the lithium-philic reagent is Ag nano powder or LiNO 3 One or more combinations thereof.
In the step (3), the compound for regulating lithium nucleation growth is LaF 3 、CeF 3 、Cu 2 One or more combinations of Te powders.
In the step (3), the particle size of the modifying agent is 10-1000 nm; preferably 50nm.
Preferably, the lithium-philic reagent is Ag nano powder in weight ratio: liNO 3 = (0.3 to 0.9): 1, a mixture of two or more of the above-mentioned materials; further preferably 0.8:1.
preferably, the compound for regulating lithium nucleation growth is LaF 3 ；
Preferably, the compound for regulating lithium nucleation growth is Cu 2 Te powder;
preferably, the compound for regulating lithium nucleation growth is LaF in weight ratio 3 ：Cu 2 Te powder= (0.8-1.2): 1, a mixture of two or more of the above-mentioned materials; further preferably 1:1.
preferably, the compound for regulating lithium nucleation growth is LaF in weight ratio 3 ：CeF 3 Powder= (5-15): 1, a mixture of two or more of the above-mentioned materials; further preferably 10:1.
preferably, the modifying agent is a combination of a lithium-philic agent and a lithium nucleation growth regulating compound, in particular LaF 3 、Cu 2 Mixtures of Te powder and Ag nano powder, wherein LaF 3 、Cu 2 The weight ratio of Te powder to Ag nano powder is (0.8-1.2): (0.8-1.2): 1, a step of; further preferably 1:1:1.
in the step (3), the weight ratio of the addition amount of the modifying agent to the addition amount of the aqueous solvent is (0.5 to 1.2): 1, a step of; preferably 0.9:1.
in the step (3), the weight ratio of the addition amount of the modifying agent to the addition amount of the NMP solvent is (0.5 to 1.2): 1, a step of; preferably 0.9:1.
in the step (3), the weight ratio of the addition amount of the modifying agent to the addition amount of the THF solvent is (0.005 to 0.012): 1, a step of; preferably 0.009:1.
the thickness of the copper current collector is 6-15 mu m; preferably 9 μm.
The coating surface density of the suspension slurry L3 is 5-50 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 30mg/cm 2 。
The drying is to put the coated copper current collector into a blast oven, dry for 5-12 h at 60-90 ℃, then put into a vacuum oven, dry for 12-48 h at 60-150 ℃.
Preferably, the drying temperature of the blast oven is 80 ℃ and the time is 8 hours; the drying temperature of the vacuum oven is 120 ℃ and the time is 36h.
Application of a composite copper current collector in manufacturing a composite lithium metal negative electrode; the specific application method comprises the following steps: and pressing the lithium foil or the lithium alloy foil onto the front side and the back side of the composite copper current collector for the lithium battery in a rolling mode to obtain the composite lithium metal negative electrode.
The lithium alloy foil is one of lithium boron alloy and lithium magnesium alloy.
The thickness of the lithium foil or the lithium alloy foil is 5-100 mu m; preferably 30 μm.
The composite lithium metal negative electrode is used as a negative electrode of a lithium metal battery.
The beneficial effects are that:
the invention has the characteristics of simple and feasible process, low manufacturing cost, low parameter control requirement, mass production and application, and higher compatibility of lithium ion battery production and manufacturing.
The composite lithium metal negative electrode prepared by the method has higher coulomb efficiency, can control the nucleation growth of negative electrode lithium, avoid serious lithium dendrite formation, and effectively improve the cycle life and the safety performance of a lithium metal battery.
According to the invention, the lithium-philic reagent and/or the compound for regulating and controlling lithium nucleation growth are coated on the copper current collector, so that lithium nucleation can be promoted, and regular growth of lithium can be regulated and controlled, thereby inhibiting lithium dendrite and dead lithium; simultaneous selection of LaF 3 、CeF 3 And LiNO 3 Can act as an SEI film-forming additive to form a robust LiF component and a low resistance nitrogen-rich SEI component in situ. The invention combines the effect of conductive carbon, effectively improves the electronic conductivity of the electrode, thereby improving the electrical property of the lithium metal battery.
Drawings
FIG. 1 is a flow chart of a manufacturing process of a composite copper current collector and a composite lithium metal negative electrode of the invention;
FIG. 2 is a schematic view of a composite copper current collector of the present invention;
fig. 3 is a schematic view of a composite lithium metal anode according to the present invention.
Detailed Description
The following detailed description of the invention is provided in further detail, but the invention is not limited to these embodiments, any modifications or substitutions in the basic spirit of the present examples, which still fall within the scope of the invention as claimed.
Example 1
The preparation method of the composite lithium metal negative electrode comprises the following steps:
(1) According to PVDF: nmp=0.06:1, adding a binder PVDF into an NMP solvent, and fully dissolving the PVDF to prepare a solution L1;
(2) According to the mixed conductive carbon: nmp=0.04:1, adding mixed conductive carbon into the solution L1, and stirring and dispersing uniformly to obtain suspension slurry L2; the mixed conductive carbon comprises the following components in percentage by weight: CNTs: single-arm carbon nanotube=1: 1: a mixture of 0.0005;
(3) According to LaF 3 : nmp=0.9:1 weight ratio to the suspension slurry L2 was added with a lithium nucleation growth regulating compound LaF having a particle size of 50nm 3 Stirring uniformly to obtain suspension slurry L3;
(4) The suspension slurry L3 was applied to the surface of a copper current collector having a thickness of 9 μm by extrusion coating, the applied surface density being 30mg/cm 2 Drying for 8 hours at 80 ℃ in a blowing way, and then drying for 36 hours at 120 ℃ in a vacuum way to obtain the composite copper current collector;
(5) And pressing the lithium foil with the thickness of 30 mu m on the front surface and the back surface of the composite copper current collector in a rolling pressing mode to obtain the composite lithium metal electrode.
Example 2
The preparation method of the composite lithium metal negative electrode comprises the following steps:
(1) According to PMMA polymer: thf=0.0006:1 by weight, adding a binder PMMA polymer to a THF solvent, and sufficiently dissolving the PMMA polymer to prepare a solution L1;
(2) According to the mixed conductive carbon: thf=0.0004:1, adding the mixed conductive carbon into the solution L1, stirring and dispersing uniformly to obtain suspension slurry L2; the mixed conductive carbon comprises the following components in percentage by weight: CNTs: single-arm carbon nanotube=1: 1: a mixture of 0.0005;
(3) According to the lithium-philic reagent: thf=0.009: 1, adding a lithium-philic reagent with the particle size of 10nm into the suspension slurry L2, and uniformly stirring to obtain suspension slurry L3; the lithium-philic reagent is Ag nano powder according to the weight ratio: liNO 3 A mixture of =0.8:1;
(4) The suspension slurry L3 was applied to the surface of a copper current collector having a thickness of 9 μm by extrusion coating, the applied surface density being 30mg/cm 2 Drying for 8 hours at 80 ℃ in a blowing way, and then drying for 36 hours at 120 ℃ in a vacuum way to obtain the composite copper current collector;
(5) And pressing the lithium foil with the thickness of 30 mu m on the front surface and the back surface of the composite copper current collector in a rolling pressing mode to obtain the composite lithium metal electrode.
Example 3
The preparation method of the composite lithium metal negative electrode comprises the following steps:
(1) The adhesive is prepared by the following steps: deionized water = 0.06:1, adding an aqueous binder into a deionized water solvent, and fully dissolving the aqueous binder to prepare a solution L1; the water-based binder is a mixture of CMC, SBR, PAA=1:1:2 in weight ratio;
(2) According to the mixed conductive carbon: adding mixed conductive carbon into the solution L1 according to the weight ratio of deionized water=0.04:1, and stirring and dispersing uniformly to obtain suspension slurry L2; the mixed conductive carbon comprises the following components in percentage by weight: CNTs: single-arm carbon nanotube=1: 1: a mixture of 0.0005;
(3) According to Cu 2 Te: deionized water=0.9:1 by weight Cu with particle size of 1000nm was added to the suspension slurry L2 2 Te powder is uniformly stirred to obtain suspension slurry L3;
(4) The suspension slurry L3 was applied to the surface of a copper current collector having a thickness of 9 μm by extrusion coating, the applied surface density being 30mg/cm 2 Drying for 8 hours at 80 ℃ in a blowing way, and then drying for 36 hours at 120 ℃ in a vacuum way to obtain the composite copper current collector;
(5) And pressing the lithium foil with the thickness of 30 mu m on the front surface and the back surface of the composite copper current collector in a rolling pressing mode to obtain the composite lithium metal electrode.
Example 4
Based on example 3, the aqueous binder was replaced with CMC in weight ratio: sbr=1:1 mixture.
Example 5
Based on example 3, the conductive carbon was replaced with SP: CNTs = 1:1 mixture.
Example 6
Based on example 3, cu was added 2 Replacement of Te powder with LaF in weight ratio 3 ：Cu 2 Te powder = 1:1.
Example 7
Based on example 3, cu was added 2 Replacement of Te powder with LaF in weight ratio 3 ：CeF 3 Powder = 10:1.
Example 8
Based on example 3, cu was added 2 Replacement of Te powder with LaF in weight ratio 3 ：Cu 2 Te powder: ag nanopowder = 1:1:1 mixture.
Claims (9)
1. The composite copper current collector is characterized in that the composite copper current collector is obtained by coating suspension slurry L3 on the surface of a copper current collector and completely drying the copper current collector;
the preparation method of the suspension slurry L3 comprises the following steps:
(1) Adding a binder into a solvent, and fully dissolving the binder to obtain a solution L1;
(2) Adding conductive carbon into the solution L1, and stirring and dispersing uniformly to obtain suspension slurry L2;
(3) Adding a modifying reagent into the suspension slurry L2, and uniformly stirring to obtain suspension slurry L3; the modifying reagent is a lithium-philic reagent or a compound for regulating lithium nucleation growth.
2. A composite copper current collector according to claim 1, wherein in step (1), the solvent is one of deionized water, NMP, THF.
3. The composite copper current collector according to claim 1, wherein in the step (1), the binder is any one of an aqueous binder and an organic binder; the water-based binder is a mixed binder of one or more of CMC, SBR, PAA; the organic binder is one of PVDF and PMMA polymer.
4. A composite copper current collector according to claim 3 wherein the aqueous binder is CMC in weight ratio: SBR: paa= (0.5 to 1.5): (0.5-1.5): the mixture of (1-3).
5. The composite copper current collector of claim 1 wherein in step (2) said conductive carbon is one or more of carbon black (SP), carbon Nanotubes (CNTs), single-walled carbon nanotubes.
6. The composite copper current collector according to claim 1, wherein in the step (3), the lithium-philic reagent is Ag nano-powder, liNO 3 A combination of one or more of the following; the compound for regulating and controlling lithium nucleation growth is LaF 3 、CeF 3 、Cu 2 A combination of one or more of Te powders; the particle size of the modifying reagent is 10-1000 nm.
7. A composite copper current collector according to claim 1, wherein the suspension slurry L3 has a coating surface density of 5 to 50mg/cm 2 。
8. A composite copper current collector according to claim 1, wherein the drying is carried out by placing the coated copper current collector in a blast oven, drying for 5-12 hours at 60-90 ℃, then placing in a vacuum oven, and drying for 12-48 hours at 60-150 ℃.
9. The use of a composite copper current collector according to claim 1 for manufacturing a composite lithium metal negative electrode, wherein a lithium foil or a lithium alloy foil is pressed onto the front and back sides of the composite copper current collector for a lithium battery in a rolling manner, thereby obtaining the composite lithium metal negative electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117558925A (en) * | 2023-11-23 | 2024-02-13 | 河北海伟电子新材料科技股份有限公司 | Lithium battery negative electrode current collector, lithium metal negative electrode, battery and vehicle |
| CN117613283A (en) * | 2024-01-22 | 2024-02-27 | 中自环保科技股份有限公司 | Negative copper foil current collector and preparation process and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117558925A (en) * | 2023-11-23 | 2024-02-13 | 河北海伟电子新材料科技股份有限公司 | Lithium battery negative electrode current collector, lithium metal negative electrode, battery and vehicle |
| CN117613283A (en) * | 2024-01-22 | 2024-02-27 | 中自环保科技股份有限公司 | Negative copper foil current collector and preparation process and application thereof |
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