CN115472782A - Preparation method of high-performance lithium ion battery current collector anode material - Google Patents

Preparation method of high-performance lithium ion battery current collector anode material Download PDF

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CN115472782A
CN115472782A CN202211106554.0A CN202211106554A CN115472782A CN 115472782 A CN115472782 A CN 115472782A CN 202211106554 A CN202211106554 A CN 202211106554A CN 115472782 A CN115472782 A CN 115472782A
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copper foil
current collector
lithium ion
ion battery
anode
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陈守东
孙海军
魏帅
查辰宇
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Tongling University
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Tongling University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/0014—Type of force applied
    • G01N2203/0016—Tensile or compressive
    • G01N2203/0017—Tensile
    • 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

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of a high-performance lithium ion battery current collector anode material, which comprises the following steps: (1) The electrodeposited copper foil with the thickness of 8 μm is used as a raw material to carry out asynchronous rolling. (2) Combining a wafer electrode sample with a stretching clamp by adopting epoxy resin AB glue, obtaining the tensile strength of a copper foil and a copper foil/graphite anode through a uniaxial stretching experiment, carrying out peeling and stretching experiments on a sample (3), and carrying out a step of 8 on graphite, polyvinylidene fluoride (PVDF binder) and super-p-carbon: 1:1 and coating the mixture on the four different copper foil current collectors to obtain the anode. Electrochemical measurements were performed in a potential range of 0.01V to 3V using CR2032 type coin cells with lithium foil as the counter electrode. The electrolytic and re-rolled copper foil prepared by the method is used as an anode current collector of a high-performance lithium ion battery, and the mechanical property and the electrical property of the electrolytic and re-rolled copper foil are obviously improved.

Description

Preparation method of high-performance lithium ion battery current collector anode material
Technical Field
The invention relates to the technical field of energy storage, in particular to a preparation method of a high-performance lithium ion battery current collector anode material.
Background
Currently, a Lithium Ion Battery (LiB) is widely used in modern electric vehicles and portable electronic products as a promising energy storage device due to its advantages of high energy storage density, long cycle life, small self-discharge, environmental friendliness, and the like. The current collector collects current in the LIB with a non-negligible effect on the electrochemical performance. However, it has not been paid sufficient attention in the study of LIB assemblies.
In order to meet the demand for rapid development of electronic devices requiring lightweight and longer battery life, we have designed LIBS with lightweight and high energy density, copper foil (thickness range: 6-12 μm, 10wt% of battery weight) being the most common current collector in LIBS, and lighter and thinner copper foil current collector can significantly reduce the weight of LIBS and increase its energy density. The traditional copper foil can be divided into a rolled copper foil and an electrodeposited copper foil according to different preparation processes, compared with the electrodeposited copper foil, the rolled copper foil has obvious mechanical property advantages, the high-strength collector foil is not easy to deform in the circulating process, and the stability of electrochemical reaction is kept.
However, when the rolled copper foil is less than 10 μm in thickness, a complicated rolling process and high cost are required due to the limitation of the minimum achievable foil thickness. The strength of electrodeposited copper foil is affected by internal lattice defects. A side effect of electrodeposition conditions for grain refinement is an increase in the density of lattice defects in the copper foil microstructure. The pinhole rate of electrodeposited copper foil increases significantly with decreasing thickness, especially when the thickness is less than 10 μm. Therefore, there is a need for further development of a method for obtaining a thin copper foil having excellent mechanical properties at low cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a lithium ion battery current collector, which has the advantages of low cost and easy manufacture, and can be used for rolling an electrodeposited copper foil to obtain an ultrathin current collecting copper foil with excellent mechanical and electrochemical properties, and effectively improving the strength and the surface roughness of the electrodeposited copper foil through asynchronous rolling and surface morphology modification.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a high-performance lithium ion battery current collector anode material comprises the following steps:
the method comprises the following steps: carrying out asynchronous rolling and surface morphology modification to a required shape by using an electrodeposited copper foil with the thickness of 8 mu m as a raw material;
step two: measuring the peel strength between different copper foil current collectors and the active material and the tensile strength of the copper foil and the copper foil/graphite anode;
step three: mixing graphite, polyvinylidene fluoride and super p carbon in a ratio of 8:1:1, and coating the mixture on a copper foil current collector to obtain an anode;
step four: electrochemical measurements were performed in a potential range of 0.01V to 3V using CR2032 type coin cells with lithium foil as the counter electrode.
The asynchronous rolling mill in the first step adopts a 3M rolling mill, and the rolling force is 85kN.
In the first step, the electrodeposited copper foil with the thickness of 8 microns is asynchronously rolled to obtain an electrolytic re-rolled copper foil with the thickness of 6 microns, and the surface appearance is modified, so that the electrolytic re-rolled copper foil with the thickness of 6 microns passes through two rollers with rough surfaces.
The intensity measurement in the second step adopts the following steps:
(1) Combining the wafer electrode sample with a stretching clamp by adopting epoxy resin AB glue, curing at room temperature for more than 24h, and obtaining the tensile strength of the copper foil and the copper foil/graphite anode through a uniaxial stretching experiment;
(2) A tensile specimen having a gauge length of 10mm and a width of 5mm was prepared by an electrical discharge machining method, and the specimen was subjected to peeling and tensile tests.
The electrochemical measurement method in the fourth step comprises the following steps:
(1) Performing constant-current charging and discharging analysis and cyclic stability by using a Newware battery test instrument, and performing electrochemical impedance spectroscopy and cyclic voltammetry by using an electrochemical workstation;
(2) Under the open circuit voltage, an EIS diagram is collected within the frequency range of 0.01-100 kHz; the rolled electrodeposited copper foil prepared by the method is used as an anode current collector of a high-performance lithium ion battery, and the mechanical property and the electrical property of the rolled electrodeposited copper foil are obviously improved.
The rolling force of the roller is 10kN, only the surface appearance is changed, and the thickness of the copper foil is not changed.
In the second step, the stretching speed in each time in the stretching test is 0.5mm/min
The invention has the beneficial effects that: the invention solves the problems of light weight and high energy density, effectively improves the strength and the surface roughness of the electrodeposited copper foil through asynchronous rolling and surface appearance modification, obtains the electrolytic re-rolled copper foil with the thickness of 6 mu m, and can obviously reduce the weight of the LIBS.
The hilly surface morphology of the copper foil is beneficial to enhancing the interface adhesion of the current collector and the active material, reducing the charge transfer resistance and improving the specific capacity and the speed performance, the surface defects generated by multiple times of conventional rolling are effectively reduced through asynchronous rolling, the rolled copper foil with the thickness of 6 mu m is obtained, the strength of the copper foil is improved through processing and hardening after the asynchronous rolling, and the mechanical property of the rare earth copper foil is obviously improved.
Because the copper foil is processed by surface mechanical abrasion, but the steps are complex, the surface appearance modification plays a crucial role in the surface appearance modification process by using the surface roughness of two working rolls, only the surface appearance is changed, and the thickness of the copper foil is not changed.
The electrolytic re-rolled copper foil having a thickness of 6 μm has better tensile strength (503 MPa) and peel strength (2.11 MPa) than conventional electrolytic copper foil and rolled copper foil.
The excellent mechanical property of the electrolytic and re-rolled copper foil current collector can ensure that the electrode active material keeps good electrical contact integrity, the cycle service life is obviously prolonged, and the experimental result shows that the current collector has the mechanical property of 500mAg -1 At constant current rate, the discharge capacity dimension of the rare earth electrodeSupported at 329.6mAhg -1 And the capacity retention rate after 200 cycles is still 91.1%, which is far higher than that of the current collector made of the traditional copper foil.
Detailed Description
The invention provides a preparation method of a lithium ion battery current collector, which comprises the following steps.
The electrodeposited copper foil with the thickness of 8 mu M is used as a raw material and is rolled by a novel asynchronous rolling mill (3M rolling mill) with the rolling force of 85kN to obtain the electrolytic re-rolled copper foil with the thickness of 6 mu M, and the asynchronous rolling has the function of generating 25 percent of reduction rate through one-time rolling, so that the surface defects generated by multiple conventional rolling are effectively reduced.
After asynchronous rolling, the electrolytic re-rolled copper foil passes through two rollers with rough surfaces to carry out the surface appearance modification process, the rolling force is only 10kN, the surface appearance is only changed, and the thickness of the copper foil is not changed.
Graphite was coated on an electrolytic re-rolled copper foil having a thickness of 6 μm, and the current collector of the electrolytic re-rolled copper foil was used as an anode, and the surface morphology was observed with a scanning electron microscope (SEM, ultra55, zeiss, oberkochen, germany), a transmission electron microscope (TEM, JEOL2100F, usa) and a confocal laser scanning microscope (CLSM, olympusextols 4000, japan).
In order to measure the peeling strength between different copper foil current collectors and electrode active materials, a wafer electrode sample is combined with a stretching clamp by adopting epoxy resin AB glue, the wafer electrode sample is cured for more than 24 hours at room temperature, and the tensile strength of a copper foil and a copper foil/graphite anode is obtained through a uniaxial stretching experiment.
A tensile specimen having a gauge length of 10mm and a width of 5mm was prepared by an electrical discharge machining method, and the specimen was subjected to peeling and tensile tests at a tensile rate of 0.5mm/min per test to ensure reliable results.
Graphite, polyvinylidene fluoride (PVDF binder) and super p-carbon were mixed at 8:1:1 and coated on the above four different copper foil current collectors to obtain anodes, and electrochemical measurements were performed in a potential range of 0.01V to 3V using CR2032 coin cells with lithium foil as a counter electrode.
Galvanostatic charge-discharge analysis and cyclic stability were performed using a Neware battery test instrument, and Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltammetry (CV) were performed using an electrochemical workstation (iviummorphtatt, the netherlands). The EIS diagram is collected in the frequency range of 0.01-100 kHz under the open circuit voltage
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to explain the principles of the invention, and that various modifications and alterations can be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (7)

1. A preparation method of a high-performance lithium ion battery current collector anode material is characterized by comprising the following steps:
the method comprises the following steps: carrying out asynchronous rolling and surface morphology modification to a required shape by using an electrodeposited copper foil with the thickness of 8 mu m as a raw material;
step two: measuring the peel strength between different copper foil current collectors and the active material and the tensile strength of the copper foil and the copper foil/graphite anode;
step three: mixing graphite, polyvinylidene fluoride and super p carbon in a ratio of 8:1:1, and coating the mixture on a copper foil current collector to obtain an anode;
step four: electrochemical measurements were performed in a potential range of 0.01V to 3V using CR2032 type coin cells with lithium foil as the counter electrode.
2. The method for preparing the anode material of the current collector of the high-performance lithium ion battery as claimed in claim 1, wherein the asynchronous rolling mill in the first step is a 3M rolling mill, and the rolling force is 85kN.
3. The method for preparing the current collector anode material of the high-performance lithium ion battery according to claim 1, wherein in the first step, 8 μm electrodeposited copper foil is asynchronously rolled to obtain 6 μm thick electrolytic re-rolled copper foil, and the surface morphology is modified, so that the 6 μm electrolytic re-rolled copper foil passes through two rollers with rough surfaces.
4. The method for preparing the anode material of the current collector of the high-performance lithium ion battery according to claim 1, wherein the strength measurement in the second step is performed by the following steps:
(1) Combining the wafer electrode sample with a stretching clamp by adopting epoxy resin AB glue, curing at room temperature for more than 24 hours, and obtaining the tensile strength of the copper foil and the copper foil/graphite anode through a uniaxial stretching experiment;
(2) A tensile specimen having a gauge length of 10mm and a width of 5mm was prepared by an electrical discharge machining method, and the specimen was subjected to peeling and tensile tests.
5. The method for preparing the current collector anode material of the high-performance lithium ion battery according to claim 1, wherein the electrochemical measurement method in the fourth step comprises the following steps:
(1) Performing constant current charging and discharging analysis and cyclic stability by using a Neware battery test instrument, and performing electrochemical impedance spectroscopy and cyclic voltammetry by using an electrochemical workstation;
(2) Under the open circuit voltage, an EIS diagram is collected in the frequency range of 0.01-100 kHz; the rolled electrodeposited copper foil prepared by the method is used as an anode current collector of a high-performance lithium ion battery, and the mechanical property and the electrical property of the rolled electrodeposited copper foil are obviously improved.
6. The method for preparing the current collector anode material of the high-performance lithium ion battery as claimed in claim 3, wherein the rolling force of the roller is 10kN, only the surface profile is changed, and the thickness of the copper foil is not changed.
7. The method for preparing the current collector anode material of the high-performance lithium ion battery as claimed in claim 4, wherein the drawing rate in the drawing test in the second step is 0.5mm/min.
CN202211106554.0A 2022-09-12 2022-09-12 Preparation method of high-performance lithium ion battery current collector anode material Pending CN115472782A (en)

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CN202211106554.0A CN115472782A (en) 2022-09-12 2022-09-12 Preparation method of high-performance lithium ion battery current collector anode material

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Application Number Priority Date Filing Date Title
CN202211106554.0A CN115472782A (en) 2022-09-12 2022-09-12 Preparation method of high-performance lithium ion battery current collector anode material

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