CN112825355A - Current collector, pole piece and secondary battery - Google Patents

Current collector, pole piece and secondary battery Download PDF

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Publication number
CN112825355A
CN112825355A CN201911140845.XA CN201911140845A CN112825355A CN 112825355 A CN112825355 A CN 112825355A CN 201911140845 A CN201911140845 A CN 201911140845A CN 112825355 A CN112825355 A CN 112825355A
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aluminum
alloy
current collector
silver
copper
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洪丽
张海林
谭桂明
吴超
葛拥军
向萍
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Evergrande New Energy Technology Shenzhen Co Ltd
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Evergrande New Energy Technology Shenzhen Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention belongs to the technical field of battery materials, and particularly relates to a current collector, a pole piece and a secondary battery. The current collector is an alloy foil, and the alloy in the alloy foil is crystalline alloy or amorphous alloy. The invention improves the existing simple substance metal foil, selects the alloy foil as the current collector, thus integrating the advantages of each metal in the alloy foil, improving the electrical conductivity and the thermal conductivity of the current collector, and forming a very thin current collector, thereby improving the energy density of the battery.

Description

Current collector, pole piece and secondary battery
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a current collector, a pole piece and a secondary battery.
Background
The current collector refers to a structure or a part for collecting current, and the function of the current collector is to collect current generated by the active material of the battery so as to form larger current to be output to the outside. For lithium ion batteries, typically the positive current collector is aluminum foil and the negative current collector is copper foil, because: firstly, the copper foil and the aluminum foil have good conductivity, soft texture and low price; secondly, the copper foil and the aluminum foil are relatively stable in the air; and thirdly, in order to meet the potential requirements of the positive electrode and the negative electrode of the lithium battery, generally speaking, the positive electrode has higher potential, the copper foil is easily oxidized under the high potential, the oxidation potential of aluminum is high, and the surface layer of the aluminum foil is provided with a compact oxidation film, so that the aluminum in the aluminum foil is well protected.
Although the copper foil/aluminum foil is well used in the current collector technology, with the rapid development of the lithium ion battery industry, higher and higher requirements are provided for the cycle life and the energy density of the lithium ion battery; the performance of the metal foil as a current collector is yet to be improved. Patent CN 105470562a utilizes the low resistance property of silver and the characteristics of silver nanosheets to coat the prepared silver nanosheets on an aluminum foil to prepare a positive current collector, which is then used for preparing a lithium ion battery, can improve the conductivity of the battery and reduce the internal resistance of the battery, thereby reducing the temperature rise of the battery and improving the safety performance of the battery when the battery is charged and discharged with large current, but the improvement of the overall ductility of the positive current collector is not obvious.
Disclosure of Invention
The invention aims to provide a current collector, a pole piece and a secondary battery, and aims to solve the technical problem that the performance of the existing simple substance metal foil current collector is not ideal enough.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a current collector, which is an alloy foil, wherein alloy in the alloy foil is crystalline alloy or amorphous alloy.
The invention improves the existing simple substance metal foil, selects the alloy foil as the current collector, thus comprehensively utilizing the advantages of each metal in the alloy foil, improving the electrical conductivity and the thermal conductivity of the current collector, and forming a very thin current collector, thereby improving the energy density of the battery.
In one embodiment, the crystalline alloy is a binary alloy comprising one or more of an aluminum silver alloy, an aluminum zinc alloy, a copper aluminum alloy, and a copper silver alloy in combination. The alloy foil formed by the binary alloy can obviously improve the performance of the current collector.
In one embodiment, the crystalline alloy is an aluminum silver alloy, wherein the mass ratio of aluminum to silver is (2-9): 1, the thickness of the current collector is 4-8 μm, and the resistivity of the current collector is (1.2-1.4) x10-8Omega.m. The aluminum-silver alloy can obviously improve the performance of the aluminum foil current collector.
In one embodiment, the crystalline alloy is an aluminum zinc alloy, wherein the mass ratio of aluminum to zinc is (1.5-2.5): 1, the thickness of the current collector is 6-9 μm, and the resistivity of the current collector is (1.8-2.1) x10-8Omega.m. The aluminum-zinc alloy can obviously improve the performance of the aluminum foil current collector.
In one embodiment, the crystalline alloy is a copper aluminum alloy, wherein the mass ratio of copper to aluminum is (4-9): 1, the thickness of the current collector is 5-6 μm, and the resistivity of the current collector is (0.9-1.0) x10-8Omega.m. The copper-aluminum alloy can obviously improve the performance of the copper foil current collector.
In one embodiment, the crystalline alloy is a copper-silver alloy, wherein the mass ratio of copper to silver is (4-9): 1, the thickness of the current collector is 5-6 μm, and the resistivity of the current collector is (0.8-0.9) x10-8Omega.m. The copper-silver alloy can obviously improve the performance of the copper foil current collector.
In one embodiment, the amorphous alloy is one or more of aluminum-based amorphous alloy, copper-based amorphous alloy, zinc-based amorphous alloy and silver-based amorphous alloy; the mass percentage of aluminum element in the aluminum-based amorphous alloy is 80-95%; the mass percentage of copper element in the copper-based amorphous alloy is 50-70%; the mass percentage of zinc element in the zinc-based amorphous alloy is 45-55%; the mass percentage of the silver element in the silver-based amorphous alloy is 25-30%. The alloy foil material composed of the amorphous alloy can obviously improve the performance of the current collector.
In one embodiment, the amorphous alloy is a binary, ternary, quaternary or quinary alloy system, and the auxiliary additive elements in the amorphous alloy comprise one or more of Al, Cu, Mg, Zn, Ni, Fe, Si, V, Mn and Sc. By adding auxiliary elements, the performance of the amorphous alloy foil as a current collector is further improved.
In another aspect, the present invention provides a pole piece, including a current collector and an active material layer covering the current collector, where the current collector is the current collector described above.
The pole piece of the invention selects the current collector which is special in the invention, namely the alloy foil of crystalline alloy or amorphous alloy as the current collector, thus the advantages of each metal in the alloy foil can be integrated, the electrical conductivity and the thermal conductivity of the current collector can be improved, and a very thin current collector can be formed, thereby improving the energy density of the battery.
Finally, the invention provides a secondary battery, wherein the pole piece is used in the secondary battery.
The secondary battery of the invention uses the special pole piece of the invention, and the pole piece selects the alloy foil of crystalline alloy or amorphous alloy as the current collector, thus the advantages of each metal in the alloy foil can be integrated, the electrical conductivity and the thermal conductivity of the current collector can be improved, and a very thin current collector can be formed, thereby improving the energy density of the battery.
Drawings
Fig. 1 is a schematic structural diagram of a positive electrode current collector according to an embodiment of the present invention;
wherein the reference numerals are: 1-silver; 2-aluminum.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, an embodiment of the present invention provides a current collector, where the current collector is an alloy foil, and an alloy in the alloy foil is a crystalline alloy or an amorphous alloy.
The current collector needs to have good electrical conductivity and heat conductivity, and the embodiment of the invention improves the existing simple substance metal foil, selects the alloy foil as the current collector, so that the advantages of each metal in the alloy foil can be integrated, the electrical conductivity and the heat conductivity of the current collector can be improved, and a very thin current collector can be formed, thereby improving the energy density of a battery.
In one embodiment, the crystalline alloy is a binary alloy comprising one or more of an aluminum silver alloy, an aluminum zinc alloy, a copper aluminum alloy, and a copper silver alloy in combination. The alloy foil formed by the binary alloy can obviously improve the performance of the current collector.
The current collector is made of alloy foil, and for the crystalline alloy foil, at least one of aluminum-silver alloy foil and aluminum-zinc alloy foil is used as the positive electrode of the alloy foil; or the alloy foil material uses at least one of copper aluminum alloy foil and copper silver alloy foil as a negative electrode.
Specifically, the current collector includes a positive electrode current collector or a negative electrode current collector. When the current collector is a positive current collector, namely the alloy foil selected by the positive current collector is at least one of aluminum-silver alloy foil and aluminum-zinc alloy foil, the performance of the simple substance aluminum foil as the positive current collector can be improved. Or, when the current collector is a negative current collector, that is, the alloy foil selected for the negative current collector is at least one of copper-aluminum alloy foil and copper-silver alloy foil, the performance of the simple substance copper foil as the negative current collector can be improved.
In one embodiment, the crystalline alloy is an aluminum silver alloy, wherein the mass ratio of aluminum to silver isIs (2-9): 1, the thickness of the current collector is 4-8 μm, and the resistivity of the current collector is (1.2-1.4) x10-8Omega.m. The aluminum-silver alloy can obviously improve the performance of the aluminum foil current collector. Within the above proportion range, the comprehensive effect of silver and aluminum is optimal.
Because silver has good electrical and thermal conductivity and the resistivity of silver (1.65x 10)-8Ω. m) is much lower than the conductivity of aluminum (2.8 × 10)-8Omega.m), therefore, the aluminum silver alloy foil can overcome the defect of high resistivity of the aluminum foil current collector, and meanwhile, the silver is soft in texture and rich in ductility, so that the defect of poor ductility of the aluminum foil can be overcome, the physical and chemical properties of the silver are relatively stable, and the aluminum silver alloy foil can play a waterproof role in the positive current collector; however, the density of silver is high (10.49 g/cm)3) And is a noble metal, if only using silver foil as the current collector, is not conducive to realizing lightweight batteries, is difficult to improve the energy density per unit volume, and is costly. In addition, the potential of silver is 0.799V, the potential of aluminum is 1.663V, and the potential of copper is 0.337V, so that the silver and the aluminum can meet the positive and negative electrode potential requirements of the battery. In summary, the positive current collector of the embodiment of the invention combines the advantages of both silver and aluminum, and the alloy foil of silver and aluminum is used as the positive current collector, so that the electrical conductivity and the thermal conductivity of the positive current collector can be improved, and a thinner positive current collector can be prepared, thereby improving the energy density.
Further, the aluminum-silver alloy foil is used as a positive electrode current collector, and the thickness of the positive electrode current collector is 4-8 μm, preferably 5-7 μm; the resistivity of the aluminum-silver alloy foil is significantly reduced compared to pure aluminum foil. The density of the aluminum-silver alloy foil can be 3.479-5.037g/cm3The ductility is higher than that of pure aluminum, and the product has good impact toughness.
In one embodiment, the crystalline alloy is an aluminum zinc alloy, wherein the mass ratio of aluminum to zinc is (1.5-2.5): 1, the thickness of the current collector is 6-9 μm, and the resistivity of the current collector is (1.8-2.1) x10-8Omega.m. The aluminum-zinc alloy can obviously improve the performance of the aluminum foil current collector. Within the above proportion range, the comprehensive effect of silver and zinc is optimal.
Specifically, an aluminum-zinc alloy foil is used as a positive electrode current collector, and the thickness of the positive electrode current collector is 6-9 μm. The resistivity of the aluminum-zinc alloy foil is significantly reduced compared to pure aluminum foil. The aluminum silver alloy has better ductility, and the aluminum silver alloy foil can be thinner than the aluminum zinc alloy foil.
In one embodiment, the crystalline alloy is a copper aluminum alloy, wherein the mass ratio of copper to aluminum is (4-9): 1, the thickness of the current collector is 5-6 μm, and the resistivity of the current collector is (0.9-1.0) x10-8Omega.m. The copper-aluminum alloy can obviously improve the performance of the copper foil current collector. Within the above proportion range, the comprehensive effect of copper and aluminum is optimal. In the copper-aluminum alloy foil, the thickness can be reduced to 5-6 μm, such as 6 μm, by adding a small amount of aluminum; a small amount of aluminum can reduce its weight and the electrical conductivity is significantly enhanced. Alternatively, in one embodiment, the crystalline alloy is a copper-silver alloy, wherein the mass ratio of copper to silver is (4-9): 1, the thickness of the current collector is 5-6 μm, and the resistivity of the current collector is (0.8-0.9) x10-8Omega.m. The copper-silver alloy can obviously improve the performance of the copper foil current collector. Within the above proportion range, the comprehensive effect of copper and silver is optimal. In the copper-silver alloy foil, a small amount of silver is added to be pressed to 5-6 mu m, and the ductility of the copper-silver alloy is better, so that the thickness of the copper-silver alloy foil can be as low as 5 mu m, the conductivity is obviously enhanced, and meanwhile, the silver added into the copper-silver alloy foil can improve the wettability of a negative current collector and promote the wettability of electrolyte. Copper aluminum alloy foil and copper silver alloy foil may be used as the negative current collector.
In one embodiment, the material of the current collector is an amorphous alloy, that is, an amorphous alloy foil is used as the current collector, and the amorphous alloy is one or a combination of more of an aluminum-based amorphous alloy, a copper-based amorphous alloy, a zinc-based amorphous alloy and a silver-based amorphous alloy; the mass percentage of aluminum element in the aluminum-based amorphous alloy is 80-95%; the mass percentage of copper element in the copper-based amorphous alloy is 50-70%; the mass percentage of zinc element in the zinc-based amorphous alloy is 45-55%; the mass percentage of the silver element in the silver-based amorphous alloy is 25-30%. The alloy foil material composed of the amorphous alloy can obviously improve the performance of the current collector.
In one embodiment, the amorphous alloy is a binary, ternary, quaternary or quinary alloy system, and the auxiliary additive elements in the alloy comprise one or more of Al, Cu, Mg, Zn, Ni, Fe, Si, V, Mn and Sc. By adding auxiliary elements, the performance of the amorphous alloy foil as a current collector is further improved.
The alloy foil of the current collector in the embodiment of the invention can be prepared by melting at high temperature, fully mixing and then cooling. The crystalline alloy foil can be obtained by slow cooling, and the amorphous alloy foil can be obtained by fast cooling. Preparation of crystalline alloy: taking an aluminum-silver alloy foil as an example, pure silver and pure aluminum are melted at a high temperature (higher than the melting point of metal in the alloy) according to a certain mass ratio until being melted into silver water and aluminum water, stirred while being cooled until being in a semi-solidified state, and then rolled, rolled in a double way and cut to prepare the aluminum-silver alloy foil. Because the density of the aluminum is lower than that of the silver, the silver sinks at the bottom and the aluminum floats above if the aluminum is naturally cooled, so that the aluminum is continuously stirred in the cooling process, and the silver and the aluminum are fully mixed and are not layered. The method is characterized in that silver is added into aluminum, the aluminum and the silver are fully mixed through high-temperature melting and then cooled to prepare the aluminum-silver alloy foil, and the positive current collector with better electrical conductivity and thinner conductivity is prepared by utilizing better electrical conductivity, thermal conductivity and ductility of the silver.
In a specific embodiment, pure silver and pure aluminum with the mass ratio of 3:7 are placed at high temperature to be melted until the pure silver and the pure aluminum are melted into silver water and aluminum water, and the mixture is stirred while being cooled until the mixture is in a semi-solidification state, so that the silver and the aluminum are fully mixed and are not layered; then rolling, double rolling and cutting are carried out to prepare the aluminum silver alloy foil, the thickness of the prepared aluminum silver alloy foil is 4 mu m, the aluminum silver alloy foil is used as a positive current collector, as shown in figure 1, wherein, aluminum 2 and silver 1 are uniformly mixed to form the positive current collector. In addition, the aluminum-zinc alloy foil, the copper-aluminum alloy foil and the copper-silver alloy foil can be prepared by high-temperature melting and mixing in a similar way to the aluminum-silver alloy foil.
In another aspect, an embodiment of the present invention provides a pole piece, including a current collector and an active material layer covering the current collector, where the current collector is the current collector described above in the embodiment of the present invention.
The pole piece of the embodiment of the invention adopts the current collector which is special in the embodiment of the invention, namely the alloy foil of crystalline alloy or amorphous alloy as the current collector, so that the advantages of each metal in the alloy foil can be integrated, the electrical conductivity and the thermal conductivity of the current collector can be improved, and a very thin current collector can be formed, thereby improving the energy density of the battery.
The pole piece is prepared by coating electrode slurry on the current collector, rolling and die cutting. The pole piece may be a positive or negative pole.
Specifically, the pole piece is a positive pole, the positive pole comprises a positive pole current collector and a positive pole active layer arranged on the surface of the positive pole current collector, and the alloy foil of the positive pole current collector is at least one of aluminum-silver alloy foil and aluminum-zinc alloy foil or amorphous alloy foil (such as aluminum-based amorphous alloy foil). Or the pole piece is a negative pole, the negative pole comprises a negative pole current collector and a negative pole active layer arranged on the surface of the negative pole current collector, and the alloy foil of the negative pole current collector is at least one of copper-aluminum alloy foil and copper-silver alloy foil or amorphous alloy foil (such as copper-based amorphous alloy foil). The details of the aluminum-silver alloy foil, aluminum-zinc alloy foil, copper-aluminum alloy foil, copper-silver alloy foil, and amorphous alloy foil are described above in detail.
Specifically, the positive electrode active layer in the positive electrode includes a positive electrode active material, a conductive agent, and a binder. The positive electrode can be prepared by preparing positive electrode active slurry containing the positive electrode active substance, a conductive agent and a binder, then uniformly coating the positive electrode active slurry on the positive electrode current collector, and rolling and slitting the positive electrode current collector. The positive active material can be ternary Nickel Cobalt Manganese (NCM), lithium cobaltate, lithium iron phosphate, lithium manganate and the like, the binder can be polyvinylidene fluoride (PVDF) and the like, the conductive agent can be carbon black, Carbon Nanotubes (CNTs), carbon black Super P (SP) and the like, and the solvent of the positive active slurry can be deionized water or N-methylpyrrolidone (NMP).
Specifically, the anode active layer in the anode includes an anode active material, a conductive agent, and a binder. The negative electrode can be prepared by preparing negative electrode active slurry containing the negative electrode active material, a conductive agent and a binder, then uniformly coating the negative electrode active slurry on the negative electrode current collector, and rolling and slitting the negative electrode current collector. The negative active material may be graphite, silicon carbon, etc., the binder may be carboxylated styrene-butadiene latex (SBR), sodium carboxymethylcellulose (CMC), Polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), the conductive agent may be carbon black, carbon nanotube, SP, the solvent of the positive active slurry may be deionized water or N-methyl pyrrolidone, and the thickener CMC may be used in the negative active slurry.
Finally, the embodiment of the invention provides a secondary battery, wherein the pole piece provided by the embodiment of the invention is used in the battery.
The secondary battery of the embodiment of the invention uses the pole piece which is special for the embodiment of the invention, and the pole piece selects the alloy foil of crystalline alloy or amorphous alloy as the current collector, so that the advantages of each metal in the alloy foil can be integrated, the electrical conductivity and the thermal conductivity of the current collector can be improved, and a very thin current collector can be formed, thereby improving the energy density of the battery.
Specifically, the secondary battery comprises a positive electrode, a negative electrode and a diaphragm positioned between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive current collector and a positive active layer arranged on the surface of the positive current collector, the negative electrode comprises a negative current collector and a negative active layer arranged on the surface of the negative current collector, the positive current collector is made of crystalline alloy foil, at least one of aluminum-silver alloy foil and aluminum-zinc alloy foil, or amorphous alloy foil, and the negative current collector is made of crystalline alloy foil, at least one of copper-aluminum alloy foil and copper-silver alloy foil, or amorphous alloy foil.
The battery of the embodiment of the invention selects the special alloy foils (crystalline alloy foils and amorphous alloy foils) as the current collector, which not only can improve the electrical conductivity and the thermal conductivity of the current collector, but also can form a very thin current collector, thereby improving the energy density of the battery. The details of the aluminum-silver alloy foil, the aluminum-zinc alloy foil, the copper-aluminum alloy foil and the copper-silver alloy foil, and the amorphous alloy foil in the crystalline alloy foil are described above in detail.
The secondary battery can be a lithium ion battery, and specifically can be a cylindrical lithium ion battery, a square lithium ion battery or a soft package lithium ion battery. Use soft packet of lithium ion battery as an example, soft packet of battery includes naked electric core, holds the plastic-aluminum membrane of naked electric core, electrolyte, the positive pole and the negative pole of naked electric core are above-mentioned positive and negative pole. The preparation method comprises the following steps: and winding the prepared anode and cathode into a bare cell, filling the bare cell into an aluminum plastic film, injecting liquid, packaging, and forming into a soft package cell.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A preparation method of a lithium ion battery comprises the following steps:
(1) preparation of the positive electrode: dispersing and dissolving a lithium iron phosphate positive electrode material, 1% of SP, 1% of CNT and 3% of PVDF binder in N-methyl pyrrolidone, then coating the solution on a crystalline alloy foil (the mass ratio of aluminum to silver is 2:1) of an aluminum-silver alloy with the thickness of 8 mu m, and drying to prepare the positive electrode.
(2) Preparation of a negative electrode: graphite, 2% SBR, 1.5% CMC and 1% SP are dispersed in water, and then coated on a 10-micron copper foil, and dried to prepare a negative electrode.
(3) Winding the prepared positive electrode and negative electrode into a bare cell by taking a glass fiber film as a diaphragm, filling the bare cell into an aluminum plastic film, injecting liquid and packaging.
Example 2
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of an aluminum-silver alloy of 8 μm (aluminum to silver mass ratio: 3:1) was used for the positive electrode.
Example 3
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of an aluminum-silver alloy of 8 μm (mass ratio of aluminum to silver: 4:1) was used for the positive electrode.
Example 4
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of an aluminum-silver alloy of 8 μm (mass ratio of aluminum to silver: 5:1) was used for the positive electrode.
Example 5
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of an aluminum-silver alloy of 8 μm (mass ratio of aluminum to silver: 7:1) was used for the positive electrode.
Example 6
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of an aluminum-silver alloy of 8 μm (mass ratio of aluminum to silver: 8:1) was used for the positive electrode.
Example 7
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of an aluminum-silver alloy of 8 μm (mass ratio of aluminum to silver: 9:1) was used for the positive electrode.
Example 8
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of a 7 μm aluminum-silver alloy (aluminum to silver mass ratio 9:1) was used for the positive electrode.
Example 9
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of 6 μm aluminum-silver alloy (aluminum to silver mass ratio 9:1) was used for the positive electrode.
Example 10
A method for producing a lithium ion battery was the same as in example 1, except that a crystalline alloy foil of 4 μm aluminum-silver alloy (aluminum to silver mass ratio 9:1) was used for the positive electrode.
Example 11
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a 9 μm aluminum-zinc alloy crystalline alloy foil (aluminum/zinc mass ratio: 1.5:1) was used as a positive electrode.
Example 12
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a 9 μm aluminum-zinc alloy crystalline alloy foil (aluminum/zinc mass ratio: 1) was used for the positive electrode.
Example 13
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a 9 μm aluminum-zinc alloy crystalline alloy foil (aluminum/zinc mass ratio: 1) was used for the positive electrode.
Example 14
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a 9 μm aluminum-zinc alloy crystalline alloy foil (aluminum/zinc mass ratio: 2.0:1) was used as a positive electrode.
Example 15
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a 9 μm aluminum-zinc alloy crystalline alloy foil (aluminum/zinc mass ratio: 2.2:1) was used as a positive electrode.
Example 16
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a 9 μm aluminum-zinc alloy crystalline alloy foil (aluminum/zinc mass ratio: 2.4:1) was used as a positive electrode.
Example 17
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a 9 μm aluminum-zinc alloy crystalline alloy foil (aluminum/zinc mass ratio: 2.5:1) was used as a positive electrode.
Example 18
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a crystalline alloy foil of an aluminum-zinc alloy having a thickness of 8 μm (the mass ratio of aluminum to zinc was 2.5:1) was used as a positive electrode.
Example 19
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a crystalline alloy foil of a 7 μm aluminum-zinc alloy (aluminum/zinc mass ratio: 2.5:1) was used as a positive electrode.
Example 20
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a crystalline alloy foil of 6 μm aluminum-zinc alloy (aluminum/zinc mass ratio: 2.5:1) was used as a positive electrode.
Example 21
A preparation method of a lithium ion battery comprises the following steps:
(1) preparation of the positive electrode: dispersing and dissolving a lithium iron phosphate positive electrode material, 1% of SP, 1% of CNT and 3% of PVDF binder in N-methylpyrrolidone, then coating the mixture on a 12-micron aluminum foil, and drying to prepare the positive electrode.
(2) Preparation of a negative electrode: graphite, 2% SBR, 1.5% CMC and 1% SP are dispersed in water, then coated on a crystalline alloy foil of 5 mu m copper-aluminum alloy (the mass ratio of copper to aluminum is 4:1), and dried to prepare the negative electrode.
(3) Winding the prepared positive electrode and negative electrode into a bare cell by taking a glass fiber film as a diaphragm, filling the bare cell into an aluminum plastic film, injecting liquid and packaging.
Example 22
A method for producing a lithium ion battery, which was the same as in example 21 except that a crystalline alloy foil of 5 μm copper-aluminum alloy (mass ratio of copper to aluminum: 5:1) was used for the negative electrode.
Example 23
A method for producing a lithium ion battery, which was the same as in example 21 except that a 5 μm crystalline alloy foil of a copper-aluminum alloy (mass ratio of copper to aluminum: 7:1) was used as a negative electrode.
Example 24
A method for producing a lithium ion battery, which was the same as in example 21 except that a crystalline alloy foil of 5 μm copper-aluminum alloy (mass ratio of copper to aluminum: 8:1) was used for the negative electrode.
Example 25
A method for producing a lithium ion battery, which was the same as in example 21 except that a 5 μm crystalline alloy foil of a copper-aluminum alloy (mass ratio of copper to aluminum: 9:1) was used as a negative electrode.
Example 26
A method for producing a lithium ion battery, which was the same as in example 21 except that a crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 4:1) was used for the negative electrode.
Example 27
A method for producing a lithium ion battery, which was the same as in example 21 except that a crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 5:1) was used for the negative electrode.
Example 28
A method for producing a lithium ion battery, which was the same as in example 21 except that a crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 7:1) was used for the negative electrode.
Example 29
A method for producing a lithium ion battery, which was the same as in example 21 except that a crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 8:1) was used for the negative electrode.
Example 30
A method for producing a lithium ion battery, which was the same as in example 21 except that a crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 9:1) was used for the negative electrode.
Example 31
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of 5 μm copper-silver alloy (mass ratio of copper to silver: 4:1) was used for the negative electrode.
Example 32
A lithium ion battery was produced in the same manner as in example 21, except that a crystalline alloy foil of 5 μm copper-silver alloy (mass ratio of copper to silver: 5:1) was used for the negative electrode.
Example 33
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of 5 μm copper-silver alloy (mass ratio of copper to silver: 7:1) was used for the negative electrode.
Example 34
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of 5 μm copper-silver alloy (copper/silver mass ratio: 8:1) was used for the negative electrode.
Example 35
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of 5 μm copper-silver alloy (copper to silver mass ratio: 9:1) was used for the negative electrode.
Example 36
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of a 6 μm copper-silver alloy (copper/silver mass ratio: 4:1) was used as a negative electrode.
Example 37
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of a 6 μm copper-silver alloy (mass ratio of copper to silver: 5:1) was used as a negative electrode.
Example 38
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of a 6 μm copper-silver alloy (mass ratio of copper to silver: 7:1) was used as a negative electrode.
Example 39
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of a 6 μm copper-silver alloy (copper to silver mass ratio: 8:1) was used as a negative electrode.
Example 40
A method for producing a lithium ion battery was carried out in the same manner as in example 21 except that a crystalline alloy foil of a 6 μm copper-silver alloy (copper to silver mass ratio: 9:1) was used as a negative electrode.
EXAMPLE 41
A method for producing a lithium ion battery, which was the same as in example 1 except that an 8 μm aluminum-based amorphous alloy foil (aluminum content 80%, zinc content 20%) was used for the positive electrode.
Example 42
A method for producing a lithium ion battery, which was the same as in example 1 except that an aluminum-based amorphous alloy foil (aluminum content 80%, silver content 10%, zinc content 10%) having a thickness of 8 μm was used for the positive electrode.
Example 43
A method for producing a lithium ion battery, which was the same as in example 1 except that an aluminum-based amorphous alloy foil (aluminum content 85%, silver content 5%, zinc content 5%, copper content 5%) having a thickness of 8 μm was used for the positive electrode.
Example 44
A method for producing a lithium ion battery, which was the same as in example 1 except that an aluminum-based amorphous alloy foil (aluminum content 90%, silver content 6%, magnesium content 2%, nickel content 2%) having a thickness of 8 μm was used for the positive electrode.
Example 45
A method for producing a lithium ion battery, which was the same as in example 1 except that an 8 μm aluminum-based amorphous alloy foil (95% aluminum and 5% silver) was used for the positive electrode.
Example 46
A method for producing a lithium ion battery was the same as in example 21, except that a 6 μm copper-based amorphous alloy foil (copper content 50%, silver content 20%, aluminum content 30%) was used for the negative electrode.
Example 47
A method for producing a lithium ion battery was the same as in example 21, except that a 6 μm copper-based amorphous alloy foil (60% copper, 20% silver, 20% aluminum) was used for the negative electrode.
Example 48
A method for producing a lithium ion battery was the same as in example 21, except that a 6 μm copper-based amorphous alloy foil (65% copper, 10% silver, 15% aluminum, 10% zinc) was used for the negative electrode.
Example 49
A method for producing a lithium ion battery was the same as in example 21, except that a 6 μm copper-based amorphous alloy foil (65% copper, 15% aluminum, 5% magnesium, and 15% zinc) was used as a negative electrode.
Example 50
A method for producing a lithium ion battery was the same as in example 21, except that a 6 μm copper-based amorphous alloy foil (copper content 70%, aluminum content 10%, magnesium content 10%, nickel content 10%) was used for the negative electrode.
Example 51
A method for producing a lithium ion battery was the same as in example 1 except that crystalline alloy foil of 8 μm aluminum-silver alloy (mass ratio of aluminum to silver: 2:1) was used for the positive electrode and crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 4:1) was used for the negative electrode.
Example 52
A method for producing a lithium ion battery was the same as in example 1 except that a crystalline alloy foil of an aluminum-silver alloy of 8 μm (mass ratio of aluminum to silver: 4:1) was used for the positive electrode and a crystalline alloy foil of a copper-silver alloy of 6 μm (mass ratio of copper to silver: 5:1) was used for the negative electrode.
Example 53
A method for producing a lithium ion battery was the same as in example 1 except that crystalline alloy foil of an aluminum-silver alloy of 8 μm was used for the positive electrode (mass ratio of aluminum to silver was 8:1), and crystalline alloy foil of a copper-aluminum alloy of 6 μm was used for the negative electrode (mass ratio of copper to aluminum was 9: 1).
Example 54
A method for producing a lithium ion battery was the same as in example 1 except that a crystalline alloy foil of 9 μm aluminum-zinc alloy (mass ratio of aluminum to zinc: 1) was used for the positive electrode and a crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 4:1) was used for the negative electrode.
Example 55
A method for producing a lithium ion battery was the same as in example 1 except that a crystalline alloy foil of 9 μm aluminum-zinc alloy (aluminum to zinc mass ratio: 2:1) was used for the positive electrode, and a crystalline alloy foil of 6 μm copper-silver alloy (copper to silver mass ratio: 5:1) was used for the negative electrode.
Example 56
A method for producing a lithium ion battery was carried out in the same manner as in example 1 except that a crystalline alloy foil of 9 μm aluminum-zinc alloy (mass ratio of aluminum to zinc: 2.5:1) was used for the positive electrode and a crystalline alloy foil of 6 μm copper-aluminum alloy (mass ratio of copper to aluminum: 9:1) was used for the negative electrode.
Example 57
A method for producing a lithium ion battery, which was the same as in example 1 except that 8 μm aluminum-based amorphous alloy foil (aluminum content 80%, silver content 10%, zinc content 10%) was used for the positive electrode, and 6 μm copper-based amorphous alloy foil (copper content 60%, silver content 20%, aluminum content 20%) was used for the negative electrode.
Example 58
A method for manufacturing a lithium ion battery was the same as in example 1 except that 8 μm aluminum-based amorphous alloy foil (aluminum content 80%, silver content 10%, zinc content 10%) was used for the positive electrode, and 6 μm copper-based amorphous alloy foil (copper content 65%, silver content 10%, aluminum content 15%, zinc content 10%) was used for the negative electrode.
Example 59
A method for producing a lithium ion battery, which was the same as in example 1 except that 8 μm aluminum-based amorphous alloy foil (85% aluminum, 5% silver, 5% zinc, 5% copper) was used for the positive electrode and 6 μm copper-based amorphous alloy foil (65% copper, 15% aluminum, 5% magnesium, 15% zinc) was used for the negative electrode.
Example 60
A method for producing a lithium ion battery, which was the same as in example 1 except that 8 μm aluminum-based amorphous alloy foil (aluminum content 90%, silver content 6%, magnesium content 2%, nickel content 2%) was used for the positive electrode, and 6 μm copper-based amorphous alloy foil (copper content 65%, aluminum content 15%, magnesium content 5%, zinc content 15%) was used for the negative electrode.
Comparative example 1
A preparation method of a lithium ion battery comprises the following steps:
(1) preparation of the positive electrode: dispersing and dissolving a lithium iron phosphate positive electrode material, 1% of SP, 1% of CNT and 3% of PVDF binder in N-methylpyrrolidone, then coating the mixture on a 12-micron aluminum foil, and drying to prepare the positive electrode.
(2) Preparation of a negative electrode: graphite, 2% SBR, 1.5% CMC and 1% SP are dispersed in water, and then coated on a 10-micron copper foil, and dried to prepare a negative electrode.
(3) Winding the prepared positive electrode and negative electrode into a bare cell by taking a glass fiber film as a diaphragm, filling the bare cell into an aluminum plastic film, injecting liquid and packaging.
Comparative example 2
A method of manufacturing a lithium ion battery was the same as in comparative example 1 except that an 8 μm aluminum foil was used for the positive electrode.
Comparative example 3
A method of manufacturing a lithium ion battery was the same as in comparative example 1 except that 8 μm silver foil was used for the positive electrode.
Comparative example 4
A method of manufacturing a lithium ion battery was the same as in comparative example 1 except that 8 μm zinc foil was used for the positive electrode.
Comparative example 5
A method of manufacturing a lithium ion battery was the same as in comparative example 1 except that 8 μm silver foil was used for the negative electrode.
And (3) performance testing:
the lithium ion batteries of examples and comparative examples were subjected to discharge capacity test: and (3) testing the room-temperature rate discharge capacity under the condition of room temperature (25 +/-2 ℃), and referring to the GB/T31484-20156.1.1.4 capacity test method:
a) with 1I1(A) Discharging to cut-off voltage of 2.5V;
b) standing for 30 min;
c) with I1(A) The current constant-current charging device is used for converting 2.0V into constant-voltage charging until the charging termination current is reduced to 0.05I1(A) Stopping charging, and standing for 1 h;
d) with 1I1(A) Discharging to cut-off voltage of 2.5V;
f) calculating discharge capacity: capacity divided by weight.
The resulting energy density is shown in table 1.
TABLE 1
Figure BDA0002280884130000171
Figure BDA0002280884130000181
From table 1 above, it can be seen that: compared with the comparative example, the energy density of the lithium ion battery of the embodiment of the invention is improved.
It can be seen from the above embodiments that the secondary battery of the present invention uses the specific pole piece of the present invention, and the pole piece selects the alloy foil of the crystalline alloy or the amorphous alloy as the current collector, so that the advantages of each metal in the alloy foil can be integrated, the electrical conductivity and the thermal conductivity of the current collector can be improved, and a very thin current collector can be formed, thereby improving the energy density of the battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The current collector is characterized in that the current collector is an alloy foil, and an alloy in the alloy foil is a crystalline alloy or an amorphous alloy.
2. The current collector of claim 1, wherein the crystalline alloy is a binary alloy comprising one or more of an aluminum silver alloy, an aluminum zinc alloy, a copper aluminum alloy, and a copper silver alloy in combination.
3. The current collector of claim 2, wherein the crystalline alloy is an aluminum silver alloy, wherein the mass ratio of aluminum to silver is (2-9): 1, the thickness of the current collector is 4-8 μm, and the resistivity of the current collector is (1.2-1.4) x10-8Ω·m。
4. The current collector of claim 2, wherein the crystalline alloy is an aluminum zinc alloy, wherein the mass ratio of aluminum to zinc is (1.5-2.5): 1, the thickness of the current collector is 6-9 μm, and the resistivity of the current collector is (1.8-2.1) x10-8Ω·m。
5. The current collector of claim 2, wherein the crystalline alloy is a copper aluminum alloy, wherein the mass ratio of copper to aluminum is (4-9): 1, the thickness of the current collector is 5-6 μm, and the resistivity of the current collector is (0.9-1.0) x10-8Ω·m。
6. The current collector of claim 2, wherein the crystalline alloy is a copper-silver alloy, wherein the mass ratio of copper to silver is (4-9):1, the thickness of the current collector is 5-6 μm, and the resistivity of the current collector is (0.8-0.9) x10-8Ω·m。
7. The current collector of claim 1, wherein the amorphous alloy is one or a combination of aluminum-based amorphous alloy, copper-based amorphous alloy, zinc-based amorphous alloy, and silver-based amorphous alloy; the mass percentage of aluminum element in the aluminum-based amorphous alloy is 80-95%; the mass percentage of copper element in the copper-based amorphous alloy is 50-70%; the mass percentage of zinc element in the zinc-based amorphous alloy is 45-55%; the mass percentage of the silver element in the silver-based amorphous alloy is 25-30%.
8. The current collector of claim 7, wherein the amorphous alloy is a binary, ternary, quaternary or quinary alloy system, and the auxiliary additive elements in the amorphous alloy comprise one or more of Al, Cu, Mg, Zn, Ni, Fe, Si, V, Mn and Sc.
9. A pole piece comprising a current collector and an active material layer overlying the current collector, wherein the current collector is according to any one of claims 1 to 8.
10. A secondary battery using the pole piece according to claim 9.
CN201911140845.XA 2019-11-20 2019-11-20 Current collector, pole piece and secondary battery Pending CN112825355A (en)

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