CN114976037A - Aluminum-based negative electrode plate for lithium ion battery and lithium ion secondary battery - Google Patents
Aluminum-based negative electrode plate for lithium ion battery and lithium ion secondary battery Download PDFInfo
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- CN114976037A CN114976037A CN202210724026.5A CN202210724026A CN114976037A CN 114976037 A CN114976037 A CN 114976037A CN 202210724026 A CN202210724026 A CN 202210724026A CN 114976037 A CN114976037 A CN 114976037A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 154
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 72
- 239000011888 foil Substances 0.000 claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 claims abstract description 73
- 239000002184 metal Substances 0.000 claims abstract description 73
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 238000005096 rolling process Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000007769 metal material Substances 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 230000005496 eutectics Effects 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000005097 cold rolling Methods 0.000 abstract description 4
- 238000006138 lithiation reaction Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 229910000676 Si alloy Inorganic materials 0.000 description 16
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 238000004806 packaging method and process Methods 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 10
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 9
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000001989 lithium alloy Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
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- 238000005303 weighing Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000011856 silicon-based particle Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- -1 Lithium hexafluorophosphate Chemical compound 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000011572 manganese Substances 0.000 description 1
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- 229910021382 natural graphite Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- 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
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- 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
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- 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
-
- 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
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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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Abstract
The invention discloses an aluminum-based negative electrode plate for a lithium ion battery, which is characterized in that an aluminum-based metal material is melted and recast to obtain an aluminum-based metal ingot; then, carrying out cold rolling treatment on the obtained aluminum-based metal cast ingot, and rolling the aluminum-based metal cast ingot into an aluminum-based metal foil; and then carrying out heat treatment on the obtained aluminum-based metal foil to obtain the aluminum-based negative electrode material for the lithium ion battery. According to the preparation method of the aluminum-based metal foil disclosed by the embodiment of the application, the aluminum-based metal foil is used as a negative electrode material of a lithium ion secondary battery electrode after being melted and recast, then being cold-rolled and heat-treated, so that the capacity of the aluminum-based metal foil is greatly improved, and the aluminum-based metal foil has higher volumetric specific energy. After the rolled aluminum-based metal foil is subjected to proper heat treatment, the tissue structure of the aluminum-based metal foil is favorable for relieving the volume expansion of an electrode material in the lithiation process, and the stability of the electrode structure is maintained. The aluminum-based negative electrode foil is used for a negative electrode material of a lithium ion secondary battery, and not only is the capacity improved, but also the cycle performance is guaranteed.
Description
Technical Field
The invention relates to the field of lithium ion battery electrode materials, in particular to an aluminum-based negative electrode plate for a lithium ion battery and a lithium ion secondary battery.
Background
Due to global warming, environmental pollution, and exhaustion of fossil fuels, human beings are urgently required to cope with environmental and energy problems. With the development of science and technology, lithium batteries are more and more widely applied in people's life by virtue of the outstanding advantages of high voltage, high energy density, good cycle performance, low self-discharge and the like. Currently, research on lithium ion batteries mainly focuses on several aspects, such as positive electrode materials, negative electrode materials, electrolytes, and separators, wherein the negative electrode materials are considered as a key part for improving battery performance, and determine the capacity and cycle performance of the lithium ion secondary battery to some extent. Although the method of substituting carbon materials for lithium metal is successful when lithium ion batteries are initially industrialized, and lithium ion negative electrode materials undergo improvements from coke development to graphitization and then to natural graphite, carbon materials still have many disadvantages that cannot be solved by themselves, so that the search for alternative materials is particularly necessary.
From the viewpoint of energy density alone, the metal lithium has the characteristic of highest specific capacity, and is the best choice for the negative electrode material of the lithium ion battery. However, lithium metal is extremely active in chemical properties, and is very likely to cause a series of safety problems such as ignition, explosion and the like, so that pure lithium metal is not commercially used as a negative electrode material so far. In contrast, the aluminum-based negative electrode has the advantages of high mass/volume specific capacity, high electronic conductivity, good plastic processability and the like, and is expected to realize breakthrough in the field of developing low-cost and higher-specific-energy lithium ion batteries.
Disclosure of Invention
The invention aims to provide an aluminum-based negative electrode plate for a lithium ion battery, which aims to solve the problem of low energy density of a negative electrode material of the lithium ion battery in the prior art. Meanwhile, the invention also aims to provide a lithium ion secondary battery adopting the aluminum-based negative electrode plate so as to achieve the purposes of lower cost and higher energy ratio of the lithium ion battery.
One of the purposes of the invention is realized by the following technical scheme:
the aluminum-based negative electrode plate for the lithium ion battery is obtained by melting and recasting an aluminum-based metal material to obtain an aluminum-based metal ingot; then, rolling the obtained aluminum-based metal ingot into an aluminum-based metal foil; and then carrying out heat treatment on the obtained aluminum-based metal foil to obtain the aluminum-based negative electrode material for the lithium ion battery.
According to the aluminum-based negative electrode plate for the lithium ion battery, the aluminum-based metal material is pure aluminum or aluminum-based alloy; the aluminum-based alloy is pure aluminum added with eutectic components and/or doping components, and the aluminum content in the aluminum-based alloy is more than or equal to 10%.
The aluminum-based negative electrode plate for the lithium ion battery is characterized In that eutectic components are added into the aluminum-based alloy, and the eutectic components include but are not limited to Bi, Sn, In, Si and Zn.
In the aluminum-based negative electrode plate for the lithium ion battery of an embodiment of the present application, a doping component is added to the aluminum-based alloy, and the doping component includes, but is not limited to, Li, Cu, Mn, Fe, Mg, Ti, Cr, Ag, Ni, Sb, C, and Nb.
According to the aluminum-based negative electrode plate for the lithium ion battery, the melting and heat preservation time is not less than 30min in the melting and recasting process.
According to the aluminum-based negative electrode plate for the lithium ion battery, the requirement on the relative humidity of the environment in the rolling treatment process is not higher than 15%.
According to the aluminum-based negative electrode plate for the lithium ion battery, the thickness of the aluminum-based metal foil is 5-300 micrometers.
According to the aluminum-based negative electrode plate for the lithium ion battery, the heat treatment is carried out for 10min-5h at the temperature of 50-550 ℃.
The second purpose of the invention is realized by the implementation of the following technical scheme:
according to the lithium ion secondary battery of one embodiment, the negative electrode pole piece is an aluminum-based negative electrode pole piece, and aluminum-based metal material is melted and recast to obtain an aluminum-based metal ingot; then, rolling the obtained aluminum-based metal ingot into an aluminum-based metal foil; and then carrying out heat treatment on the obtained aluminum-based metal foil to obtain the aluminum-based negative electrode plate for the lithium ion battery.
According to the preparation method of the aluminum-based metal foil disclosed by the embodiment of the application, the aluminum-based metal foil is used as a negative electrode plate of a lithium ion secondary battery electrode after being melted and recast, rolled and thermally treated, so that the capacity of the aluminum-based metal foil is greatly improved, and the aluminum-based metal foil has high volumetric specific energy.
Further, we have found that by appropriately heat-treating the aluminum-based metal foil after the rolling deformation, the crystal grains can be made finer and the grain boundary (phase boundary) density can be increased. The structure is beneficial to relieving the volume expansion of the electrode material in the lithiation process and maintaining the stability of the electrode structure. The aluminum-based negative electrode foil is used as a negative electrode plate material of a lithium ion secondary battery, and not only is the capacity improved, but also the cycle performance is guaranteed.
In addition, since the relative humidity of the environment during rolling is less than 15%, the aluminum-based metal foil produced has less impurities and excellent quality.
In conclusion, after the rolled aluminum-based metal foil is subjected to proper heat treatment, the tissue structure of the aluminum-based metal foil is favorable for relieving the volume expansion of the electrode material in the lithiation process, and the stability of the electrode structure is maintained. The aluminum-based negative electrode foil is used for a negative electrode material of a lithium ion secondary battery, and not only is the capacity improved, but also the cycle performance is guaranteed. The aluminum-based metal foil is used as the negative pole piece of the lithium ion secondary battery, and the complicated processes of pulping, coating and drying of the traditional powder negative pole material are omitted. Meanwhile, due to the excellent conductivity and mechanical property of the aluminum-based metal foil, the aluminum-based metal foil can be directly used as a self-supporting electrode without a binder or a conductive agent, and the cost of the preparation process is greatly reduced.
Therefore, the lithium ion battery using the aluminum-based metal foil provided by the embodiment of the disclosure as the negative electrode has excellent cycling stability, the preparation method is simple, the required industrial technology and equipment are mature, and the popularization is easy.
Other technical effects of the present invention are further embodied by the specific embodiments.
Drawings
Fig. 1 is a graph showing the results of cycle stability test of a lithium ion half cell of comparative example 1 using only a pure aluminum foil prepared by rolling.
Fig. 2 is the results of the cycle stability test of the lithium ion half cell of example 1 using pure aluminum foil prepared by rolling + heat treatment.
Fig. 3 is a comparison of fig. 1 and fig. 2.
Fig. 4 is a graph comparing constant current charge and discharge curves of the half cells of comparative example 1 and example 1.
Fig. 5 is a constant current charge and discharge curve of the lithium ion half cell using the aluminum lithium alloy foil in example 2.
Fig. 6 is a constant current charge and discharge curve of the lithium ion half cell using the aluminum-silicon alloy foil in example 3.
Fig. 7 is a graph showing the cycle results of the lithium ion full cell using the aluminum-silicon alloy foil in example 4.
FIG. 8 is a scanning electron micrograph of the surface morphology structure of the pure aluminum foil of example 1.
FIG. 9 is an optical microscope photograph of the surface topography of the Al-Si alloy foil of example 3.
Detailed Description
In order to make the technical means and functions of the invention easy to understand, the invention is specifically described below with reference to the embodiments and the accompanying drawings.
The invention provides an aluminum-based metal foil capable of being used as a negative pole piece of a lithium ion secondary battery, which is prepared according to a specific process and specifically comprises the following steps:
step 1: preparing an aluminum-based metal ingot: under the protection of inert gas, completely melting pure aluminum, pure aluminum and eutectic metal or pure aluminum and doping metal, stirring to make the pure aluminum, the pure aluminum and the eutectic metal uniform, keeping the temperature for at least 30min to obtain molten metal, and then cooling to room temperature to obtain pure aluminum metal cast ingots or aluminum-based metal cast ingots;
step 2: rolling the obtained metal cast ingot under the condition that the relative humidity is lower than 15 percent to obtain the aluminum-based metal foil with the thickness of 5-300 mu m.
The thickness of the metal foil can be determined according to actual needs, and the thickness of the pure aluminum metal foil or the doped aluminum-based metal foil prepared in the following examples and comparative examples is 45 μm.
And 3, preserving the heat of the aluminum-based metal foil at the temperature of 50-550 ℃ for 10min-5h, polishing the surface to remove an oxide layer, wiping the aluminum-based metal foil clean by using alcohol, punching the aluminum-based metal foil into a circular foil with the diameter of 10mm, and then putting the cut foil into a vacuum drying oven to dry the surface to remove moisture, thus obtaining the lithium ion secondary battery negative electrode piece.
The electrolyte used in the following examples and comparative examples was 1mol L -1 Lithium hexafluorophosphate (LiPF) 6 ) Ethylene Carbonate (EC) -Ethyl Methyl Carbonate (EMC) -dimethyl carbonate (DMC) (1:1:1, v/v/v).
Example 1
| Composition (I) | Process for the preparation of a catalyst |
| Pure aluminium | Molten ingot → rolling → heat treatment → pure aluminum foil |
Step 1: weighing metal aluminum particles with certain mass in a glove box (in an argon protective atmosphere), placing the metal aluminum particles in a heating container, placing the heating container in a high-purity argon environment, heating until aluminum is completely molten, stirring the melt to be uniform, and keeping the temperature for 30min to obtain molten metal; and then cooled to room temperature to obtain a pure aluminum metal ingot.
Step 2: the pure aluminum metal ingot was taken out and subjected to a cold rolling treatment in a dry environment (relative humidity less than 15%) to form a foil (thickness 45 μm).
And step 3: and carrying out heat treatment on the obtained pure aluminum metal foil under the condition of keeping the temperature at 200 ℃ for 3 h.
And 4, step 4: the pure aluminum foil was then cut into 10mm diameter battery plates with a battery slicer and assembled with lithium metal into half-cells using a 12mm diameter Celgard2400 separator.
The assembly of the battery was carried out in a glove box: and sequentially stacking and assembling the positive electrode shell, the pure aluminum foil, the diaphragm, 60 mu L of electrolyte, the metal lithium sheet, the gasket, the spring piece and the negative electrode shell, and packaging the battery by using a battery packaging machine, wherein the packaging pressure is 7.5 MPa.
Fig. 2 shows the results of the cycle stability test of pure aluminum foil lithium ion half cells prepared in example 1 by rolling + heat treatment.
As shown in fig. 2, the abscissa represents the number of cycles of the pure aluminum lithium-ion half-cell, and the ordinate represents the coulombic efficiency of the pure aluminum lithium-ion half-cell. Fig. 2 shows that the pure aluminum foil lithium ion half-cell prepared by rolling and heat treatment has very good cycle stability, and the coulomb efficiency of the pure aluminum foil lithium ion half-cell does not show a reduction after 150 cycles.
Fig. 8 is a scanning electron micrograph of the surface morphology structure of the pure aluminum foil prepared in this example, which shows a complete and dense Al microstructure. The crystal boundary is regulated and controlled through rolling and heat treatment, so that the rapid lithium insertion and the cycling stability of the Al foil are facilitated.
Comparative example 1
| Composition (I) | Process for the preparation of a catalyst |
| Pure aluminium | Melting ingot → rolling → pure aluminum foil |
Comparative example 1 differs from example 1 in that there is no heat treatment step, as detailed below.
Step 1: weighing pure aluminum particles with certain mass in a glove box (in an argon protective atmosphere), placing the pure aluminum particles in a heating container, placing the heating container in a high-purity argon environment, heating the pure aluminum particles until the pure aluminum particles are completely molten, stirring the melt to be uniform, and keeping the temperature for 30min to obtain molten metal; and then cooling to room temperature to obtain a pure aluminum metal ingot.
Step 2: the pure aluminum metal ingot was taken out and subjected to a cold rolling treatment in a dry environment (relative humidity less than 15%) to form a foil (thickness 45 μm).
And step 3: pure aluminum foil was cut into 10mm diameter battery pieces with a battery slicer and then assembled with lithium metal into half cells using 12mm diameter Celgard2400 separators.
The assembly of the battery was carried out in a glove box: and sequentially stacking and assembling the positive electrode shell, the pure aluminum foil, the diaphragm, 60 mu L of electrolyte, the metal lithium sheet, the gasket, the spring piece and the negative electrode shell, and packaging the battery by using a battery packaging machine, wherein the packaging pressure is 7.5 MPa.
Fig. 1 is a result of cycle stability test of a pure aluminum foil lithium ion half cell prepared by a cold rolling manner only in comparative example 1.
As shown in fig. 1, the abscissa represents the number of cycles of the pure aluminum lithium-ion half-cell, and the ordinate represents the coulombic efficiency of the pure aluminum lithium-ion half-cell, and it can be seen from fig. 1 that the coulombic efficiency begins to decrease after several cycles of the pure aluminum foil negative electrode, and the cycle stability is poor.
Figure 3 is a comparison of half-cell cycle stability results for comparative example 1 and example 1. From fig. 3 it can be seen that the rolled and heat treated pure aluminum foil shows better cycling stability than the non-heat treated pole pieces.
Fig. 4 is a graph comparing constant current charge and discharge curves of the half cells of comparative example 1 and example 1. It can be seen from the observation of fig. 4 that the rolled and heat-treated pure aluminum foil shows higher specific capacity than the non-heat-treated pole piece.
Example 2
| Composition (I) | Process for the preparation of a catalyst |
| Pure aluminum + industrial pure lithium | Melting ingot → rolling → heat treatment → aluminum lithium alloy foil |
Step 1: weighing a certain mass of metal aluminum (978g) and industrial pure lithium (22g) in a glove box (in an argon protective atmosphere), placing the metal aluminum and the industrial pure lithium in a heating container, placing the heating container in a high-purity argon environment, heating until the aluminum and the lithium are completely molten, stirring the melt to be uniform, and keeping the temperature for 30min to obtain molten metal; and then cooling to room temperature to obtain an aluminum lithium alloy ingot.
Step 2: the aluminum lithium alloy ingot was taken out and cold rolled in a dry atmosphere (relative humidity less than 15%) to form a foil (thickness 45 μm).
And step 3: and carrying out heat treatment on the obtained aluminum lithium alloy foil under the condition of keeping the temperature at 500 ℃ for 1 h.
And 4, step 4: the aluminum lithium alloy foil was then cut into 10mm diameter battery plates with a battery slicer and assembled with lithium metal into half-cells using 12mm diameter Celgard2400 separators.
The assembly of the battery was carried out in a glove box: and sequentially stacking and assembling the battery according to the sequence of the positive electrode shell, the aluminum lithium alloy foil, the diaphragm, 60 mu L of electrolyte, the metal lithium sheet, the gasket, the spring piece and the negative electrode shell, and packaging the battery by using a battery packaging machine, wherein the packaging pressure is 7.5 MPa.
Fig. 5 is a constant current charge and discharge curve of a lithium ion half cell using an aluminum lithium alloy foil in example 2 of the present invention. From FIG. 5, it can be seen that the aluminum lithium alloy foil negative electrode is 0.1-1.0V vs. Li + The specific capacity of 780mAh/g can be provided within the voltage range of Li, which is more than 2 times of the theoretical capacity of the commercial graphite cathode material, and high quality/volume capacity characteristics are proved. Meanwhile, the voltage range can avoid the formation of lithium dendrites under the condition of high-rate charge and discharge, and has certain high-rate safety.
Example 3
| Composition (I) | Process for the preparation of a catalyst |
| Pure aluminum + silicon | Melting ingot → rolling → heat treatment → Al-Si alloy foil |
Step 1: weighing 936g of metal aluminum and 64g of silicon particles with certain mass in a glove box (in an argon protective atmosphere), placing the metal aluminum and the silicon particles in a heating container, placing the heating container in a high-purity argon environment, heating until the aluminum and the silicon are completely molten, stirring the melt to be uniform, and keeping the temperature for 30min to obtain molten metal; and then cooling to room temperature to obtain an aluminum-silicon alloy cast ingot.
Step 2: the aluminum-silicon alloy ingot was taken out and cold rolled in an atmosphere (relative humidity less than 15%) to form a foil (thickness: 45 μm).
And step 3: and carrying out heat treatment on the obtained aluminum-silicon alloy foil under the condition of keeping the temperature at 500 ℃ for 1 h.
And 4, step 4: the aluminum-silicon alloy foil was then cut into 10mm diameter battery plates with a battery slicer and assembled with lithium metal into half-cells using a 12mm diameter Celgard2400 separator.
The assembly of the battery was carried out in a glove box: and sequentially stacking and assembling the positive electrode shell, the aluminum-silicon alloy foil, the diaphragm, 60 mu L of electrolyte, the metal lithium sheet, the gasket, the spring piece and the negative electrode shell, and packaging the battery by using a battery packaging machine, wherein the packaging pressure is 7.5 MPa.
Fig. 6 is a constant current charge and discharge curve of a lithium ion half cell using an aluminum silicon alloy foil in example 3 of the present invention. From fig. 6, it can be seen that the aluminum-silicon alloy foil with the silicon content of 6.4% shows a specific mass capacity of 800mAh/g, which is more than 2 times of the theoretical capacity of the commercial graphite negative electrode material, and the charging and discharging platform is stable and has a small voltage difference, indicating good charge transfer efficiency.
Comparing fig. 4, 5 and 6, it can be seen that the grain size of the aluminum-based metal foil after cold deformation is continuously refined and the density of the grain boundary (phase boundary) is increased by performing appropriate heat treatment on the aluminum-based metal foil. The structure is beneficial to relieving the volume expansion of the electrode material in the lithiation process and maintaining the stability of the electrode structure. The aluminum-based negative electrode foil is used for a negative electrode material of a lithium ion secondary battery, and the capacity is improved, and the cycle performance is also guaranteed. The result proves the great potential of the aluminum-based metal foil negative pole piece in the aspect of preparing the high-energy-density lithium ion secondary battery.
Fig. 9 is an optical microscope photograph of the surface morphology structure of the aluminum-silicon alloy foil prepared in this example, which shows that Si and Al are uniformly distributed and Al is in a dendritic state. Si and Al provide a high density phase boundary that facilitates rapid lithium insertion. The Al is divided into small-size areas by the precipitated Si, so that the stress dispersion in the lithium intercalation and lithium deintercalation process is facilitated, and the cycling stability of the alloy foil is improved.
Example 4
| Composition (I) | Process for the preparation of a catalyst |
| Pure aluminum + silicon | Melting ingot → rolling → heat treatment → Al-Si alloy foil |
Step 1: weighing 936g of metal aluminum and 64g of silicon particles with certain mass in a glove box (in an argon protective atmosphere), placing the metal aluminum and the silicon particles in a heating container, placing the heating container in a high-purity argon environment, heating until the aluminum and the silicon are completely molten, stirring the melt to be uniform, and keeping the temperature for 30min to obtain molten metal; and then cooling to room temperature to obtain an aluminum-silicon alloy cast ingot.
And 2, step: the aluminum-silicon alloy ingot was taken out and cold rolled in a dry atmosphere (relative humidity less than 15%) to form a foil (thickness: 45 μm).
And step 3: and carrying out heat treatment on the obtained aluminum-silicon alloy foil under the condition of keeping the temperature at 500 ℃ for 1 h.
And 4, step 4: then, the aluminum-silicon alloy foil is cut into battery pole pieces with the diameter of 10mm by a battery slicer, and then the battery pole pieces are assembled into the lithium ion full battery by using a Celgard2400 diaphragm with the diameter of 12mm and a nickel-cobalt-manganese (NCM) ternary positive electrode material.
The assembly of the battery was carried out in a glove box: and sequentially stacking and assembling the positive electrode shell, the NCM positive electrode material, the diaphragm, 60 mu L electrolyte, the aluminum-silicon alloy foil, the gasket, the spring piece and the negative electrode shell, and packaging the battery by using a battery packaging machine, wherein the packaging pressure is 7.5 MPa.
In this example, the surface capacity of the NCM positive electrode was 12.4mAh cm -2 。
Fig. 7 is a schematic view showing the cycle results of the lithium ion full cell in example 4 of the present invention.
As shown in fig. 7, the abscissa is the cycle number of the battery, the ordinate is the capacity and the coulombic efficiency of the full battery, the positive electrode material is the NCM material, the negative electrode is the aluminum-silicon alloy foil with the thickness of 45 μm, the lithium ion full battery can stably circulate 150 cycles, the coulombic efficiency is kept at 100%, and the excellent electrochemical performance of the lithium ion battery is represented.
In the technical scheme of the invention, when the aluminum-based metal foil capable of being used as the negative pole piece of the lithium ion secondary battery is prepared, the content and element type of a doped or eutectic component contained in an aluminum matrix have no obvious influence on the performance of the prepared electrode foil. Other embodiments included in the scope of claims of the present application have substantially the same technical effects as the embodiments disclosed above.
The above embodiments are preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and those skilled in the art can make routine changes and modifications based on the above embodiments, and all such changes and modifications are within the scope of the present invention as claimed.
Claims (9)
1. An aluminum-based negative electrode plate for a lithium ion battery is characterized in that the negative electrode plate is obtained by melting and recasting an aluminum-based metal material to obtain an aluminum-based metal ingot; then, rolling the obtained aluminum-based metal ingot into an aluminum-based metal foil; and then carrying out heat treatment on the obtained aluminum-based metal foil to obtain the aluminum-based negative electrode plate for the lithium ion battery.
2. The aluminum-based negative electrode plate for the lithium ion battery as claimed in claim 1, wherein the aluminum-based metal material is pure aluminum or an aluminum-based alloy; the aluminum-based alloy is pure aluminum added with eutectic components and/or doping components, and the aluminum content in the aluminum-based alloy is more than or equal to 10%.
3. The aluminum-based negative electrode plate for the lithium ion battery as claimed In claim 2, wherein eutectic components are added to the aluminum-based alloy, and the eutectic components include but are not limited to Bi, Sn, In, Si, Zn.
4. The aluminum-based negative electrode plate for the lithium ion battery as claimed in claim 2, wherein the aluminum-based alloy is added with doping components, and the doping components include but are not limited to Li, Cu, Mn, Fe, Mg, Ti, Cr, Ag, Ni, Sb, C, Nb.
5. The aluminum-based negative electrode plate for the lithium ion battery as claimed in claim 1, wherein the melting and recasting process is carried out for a melting and holding time of not less than 30 min.
6. The aluminum-based negative electrode plate for the lithium ion battery as claimed in claim 1, wherein the requirement on the relative humidity of the environment in the rolling process is not higher than 15%.
7. The aluminum-based negative electrode plate for the lithium ion battery as claimed in claim 1, wherein the aluminum-based metal foil has a thickness of 5 to 300 μm.
8. The aluminum-based negative electrode plate for the lithium ion battery as claimed in claim 1, wherein the heat treatment is heat preservation at 50-550 ℃ for 10min-5 h.
9. A lithium ion secondary battery, wherein the negative electrode pole piece of the lithium ion secondary battery adopts the aluminum-based negative electrode pole piece of any one of claims 1 to 8.
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