CN116632250A - Lithium ion battery and preparation method thereof - Google Patents
Lithium ion battery and preparation method thereof Download PDFInfo
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- CN116632250A CN116632250A CN202310357760.7A CN202310357760A CN116632250A CN 116632250 A CN116632250 A CN 116632250A CN 202310357760 A CN202310357760 A CN 202310357760A CN 116632250 A CN116632250 A CN 116632250A
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- current collector
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- negative electrode
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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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/583—Devices or arrangements for the interruption of current in response to current, e.g. fuses
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
- H01M50/593—Spacers; Insulating plates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery and a preparation method thereof, wherein the lithium ion battery comprises a positive electrode composite current collector and a negative electrode composite current collector which are sequentially stacked, the positive electrode composite current collector comprises a first insulating base material positioned at the center, aluminum foils arranged on the upper surface and the lower surface of the first insulating base material, positive electrode active substances coated on the aluminum foils, a first flame-retardant oxide coating covering the surfaces of the positive electrode active substances, and the negative electrode composite current collector comprises a second insulating base material positioned at the center, copper foils arranged on the upper surface and the lower surface of the second insulating base material, a negative electrode active substance coated on the copper foils, and a second flame-retardant oxide coating covering the surfaces of the negative electrode active substances. According to the invention, the insulating base material and the oxide coating are added in the system of the battery, so that the direct contact between electrodes can be effectively prevented, and the thermal runaway of the battery is prevented; in addition, the composite current collector has a thinner conductive layer, and the local short Lewis is fused, so that the safety of the battery is effectively improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery and a preparation method thereof.
Background
The traditional lithium ion battery has the advantages that the copper foil is used as a current collector in the negative electrode, the aluminum foil is used as the current collector in the positive electrode, the current collector only has the function of conducting electrons, the heat conductivity is poor, the total mass of the positive and negative current collectors accounts for about 14-18% of the mass of the single battery, more heat is generated in the charging and discharging processes of the traditional lithium ion battery, the temperature of the battery is increased, and potential safety hazards exist.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a lithium ion battery and a preparation method thereof, which aims to solve the problems of high heat generation and easy explosion of the existing lithium ion battery.
The technical scheme of the invention is as follows:
the lithium ion battery comprises a positive electrode composite current collector and a negative electrode composite current collector which are sequentially stacked, wherein the positive electrode composite current collector comprises a first insulating substrate positioned at the center, aluminum foils arranged on the upper surface and the lower surface of the first insulating substrate, a positive electrode active substance coated on the aluminum foils, and a first flame-retardant oxide coating covering the surface of the positive electrode active substance, the negative electrode composite current collector comprises a second insulating substrate positioned at the center, copper foils arranged on the upper surface and the lower surface of the second insulating substrate, a negative electrode active substance coated on the copper foils, and a second flame-retardant oxide coating covering the surface of the negative electrode active substance.
The lithium ion battery comprises a first insulating substrate, a second insulating substrate, a lithium ion battery and a lithium ion battery, wherein the materials of the first insulating substrate and the second insulating substrate are independently selected from one or more of PET and PP.
The lithium ion battery comprises a positive electrode active material, a negative electrode active material and a negative electrode active material, wherein the positive electrode active material is one or more of ternary lithium materials and lithium cobaltate materials; the negative electrode active material is one or more of a silicon negative electrode material and a graphite negative electrode material.
The lithium ion battery comprises a first flame-retardant oxide coating and a second flame-retardant oxide coating, wherein the first flame-retardant oxide coating and the second flame-retardant oxide coating comprise the following components in percentage by mass: 70-95% of flame-retardant oxide and 5-30% of PVDF, wherein the flame-retardant oxide is LLZO, li X Al X Ti X (PO x ) X One or more of gamma-AlOOH.
The thickness of the first flame-retardant oxide coating is 1-8um, and the thickness of the second flame-retardant oxide coating is 1-8um.
A preparation method of a lithium ion battery comprises the following steps:
aluminum foil, an anode active material layer and a first flame-retardant oxide coating are sequentially arranged on the upper surface and the lower surface of a first insulating substrate to prepare an anode composite current collector;
sequentially arranging copper foil, a negative electrode active material layer and a second flame-retardant oxide coating on the upper surface and the lower surface of a second insulating substrate to prepare a negative electrode composite current collector;
respectively roll-welding transfer foil lugs on the positive composite current collector and the negative composite current collector;
sequentially stacking the negative electrode composite current collector welded with the foil tab and the positive electrode composite current collector to form a lamination;
respectively carrying out Tab welding and rubberizing treatment on foil lugs of the positive electrode composite current collector and the negative electrode composite current collector to obtain a battery cell;
and (3) packaging, baking, injecting liquid, standing, heating and pressurizing, performing two-seal molding and capacity-dividing treatment on the battery cell in sequence to obtain the lithium ion battery.
The beneficial effects are that: according to the invention, the insulating base material and the oxide coating are added in the system formula of the traditional battery, so that the direct contact between electrodes can be effectively prevented, and the thermal runaway of the battery is prevented; the positive electrode composite current collector and the negative electrode composite current collector used in the battery are thinner in conductive layers (aluminum foil and copper foil), the conductive layers are more easily fused like a fuse during short circuit, the short circuit current is greatly reduced after the local current is cut off, the temperature rise amplitude is small, the battery damage is only limited to a puncture site to form a 'point open circuit', the conductive layers are quickly fused, the current is not further conducted, and the combustion of a battery core is finally prevented; the invention solves the problem of battery combustion explosion caused by thermal runaway in the two modes.
Drawings
Fig. 1 is a schematic structural diagram of a lithium ion battery according to the present invention.
Fig. 2 is a flowchart of a method for preparing a lithium ion battery according to the present invention.
Fig. 3 is a graph showing the results of the needling test of the lithium ion battery of comparative example 1.
Fig. 4 is a graph showing the results of the needling test of the lithium ion battery of example 1.
Fig. 5 is a graph showing the short circuit test result of the lithium ion battery of comparative example 1.
Fig. 6 is a graph showing the short circuit test result of the lithium ion battery of example 1.
Fig. 7 is a graph showing the results of a high temperature furnace heat test of the lithium ion battery of comparative example 1.
Fig. 8 is a graph showing the results of the high temperature furnace heat test of the lithium ion battery of example 1.
Detailed Description
The invention provides a lithium ion battery and a preparation method thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a lithium ion battery provided by the present invention, as shown in the drawing, the lithium ion battery includes a positive electrode composite current collector 10 and a negative electrode composite current collector 20 stacked in sequence, the positive electrode composite current collector 10 includes a first insulating substrate 11 at the center, aluminum foils 12 disposed on the upper and lower surfaces of the first insulating substrate 11, a positive electrode active material 13 coated on the aluminum foils 12, and a first flame retardant oxide coating 14 covering the surface of the positive electrode active material 13, the negative electrode composite current collector 20 includes a second insulating substrate 21 at the center, copper foils 22 disposed on the upper and lower surfaces of the second insulating substrate 21, a negative electrode active material 23 coated on the copper foils 22, and a second flame retardant oxide coating 24 covering the surface of the negative electrode active material 23.
In the present invention, the lithium ion battery may include at least 32 positive electrode composite current collectors and 33 negative electrode composite current collectors. Taking the lithium ion battery shown in fig. 1 as an example, the lithium ion battery only shows a structure comprising 2 positive electrode composite current collectors and 3 negative electrode composite current collectors, and the negative electrode composite current collectors and the positive electrode composite current collectors are sequentially stacked from bottom to top in multiple layers.
The common positive and negative current collectors used in the traditional lithium ion battery structure can generate large-size burrs during puncturing to cause internal short circuit, and the current collectors are not melted yet, so that current transmission cannot be blocked, and thermal runaway is easily caused. In the invention, as the center positions of the positive electrode composite current collector and the negative electrode composite current collector are respectively provided with the insulating base material, and the outermost surfaces of the positive electrode composite current collector and the negative electrode composite current collector are respectively provided with the corresponding flame-retardant oxide coating, the composite current collectors can effectively prevent the electrodes from being in direct contact, thereby blocking the thermal runaway of the battery; the positive electrode composite current collector and the negative electrode composite current collector used in the battery are thinner in conductive layers (aluminum foil and copper foil), the conductive layers are more easily fused like a fuse during short circuit, the short circuit current is greatly reduced after the local current is cut off, the temperature rise amplitude is small, the battery damage is only limited to a puncture site to form a 'point open circuit', the conductive layers are quickly fused, the current is not further conducted, and the combustion of a battery core is finally prevented; the invention solves the problem of battery combustion explosion caused by thermal runaway in the two modes.
In some embodiments, the materials of the first and second insulating substrates are independently selected from one or more of PET, PP.
In this embodiment, compared with metals, the polymer organic materials used in the first insulating substrate and the second insulating substrate have low elastic modulus, and form a layered annular sponge structure around the active material layer in the battery, and in the charging and discharging process of the battery, the expansion-contraction stress generated by the intercalation and deintercalation of lithium ions in the active material layer of the pole piece can be absorbed, so that the long-term integrity of the pole piece interface is maintained, and the cycle life of the battery can be prolonged by more than 5%.
Further, because the density of the high molecular organic material is lower, the weight of the composite current collector can be greatly reduced by 50-80% compared with that of a pure metal current collector; in addition, the thickness of the composite current collector is reduced by 25-40% compared with that of a pure metal current collector, under the condition that the volume of the battery core is unchanged, the space in which active substances can be filled in the battery core is larger, and the volume energy density of the battery can be further improved by 5-10% by increasing the consumption of the active substances and thickening the coating thickness of the slurry.
In the invention, the composite positive current collector adopts a sandwich structure, and adopts polymer materials such as PET, PP and the like as basic materials, and metal layers are deposited on the upper surface and the lower surface by adopting an advanced process to prepare the novel lithium battery current collector material. By way of example, the weight energy density of the composite current collectors plated with 1 μm copper on the upper and lower sides of the 3 μm PP material can be improved by 3.3% compared with the 6 μm electrolytic copper foil; if the positive electrode is also replaced with a composite current collector material, the total weight energy density can be raised by 6.1%. The PET copper foil can be reduced in weight by about 56% compared to the conventional copper foil, and the PET aluminum foil can be reduced in weight by about 41%. Taking a 6 μm copper foil as an example, the traditional copper foil accounts for about 11% of the battery mass, and if the traditional copper foil is replaced by PET copper foil, the weight can be reduced by 56%, and the energy density of the corresponding battery can be expected to be improved by 5%.
In some embodiments, the positive electrode active material is one or more of a ternary lithium material, a lithium cobaltate material; the negative electrode active material is one or more of a silicon negative electrode material and a graphite negative electrode material; the first flame-retardant oxide coating and the second flame-retardant oxide coating comprise the following components in percentage by mass: 70-95% of flame-retardant oxide and 5-30% of PVDF, wherein the flame-retardant oxide is LLZO, li X Al X Ti X (PO x ) X One or more of gamma-AlOOH (hydrated alumina). Under the condition of short circuit, the flame-retardant oxide coating can effectively prevent ignition explosion caused by thermal runaway generated by contact of the anode and the cathode.
In this embodiment, the first flame retardant oxide coating layer needs to cover all positive electrode active materials when coated and 1 to 3mm beyond the positive electrode active materials, and the same second flame retardant oxide coating layer needs to cover all negative electrode active materials when coated and 1 to 3mm beyond the negative electrode active materials. In this embodiment, the excess portion can maximally reduce the contact risk of the anode and the cathode, and prevent the contact from the source of product design (especially, when the diaphragm is contracted and has no insulation protection during high temperature test such as furnace heat, the excess portion plays an insulation role).
In this embodiment, the thickness of the first flame retardant oxide coating is 1-8um, and the thickness of the second flame retardant oxide coating is 1-8um. In this embodiment, exceeding 8um lengthens the migration path of lithium ions, the coating is too thick, the grid gaps are blocked by edge coating casting during gravure coating, and the thickness of the cell product is increased and the energy density is limited.
In some embodiments, there is also provided a method for preparing a lithium ion battery, as shown in fig. 2, comprising the steps of:
s10, sequentially arranging an aluminum foil, an anode active material layer and a first flame-retardant oxide coating on the upper surface and the lower surface of a first insulating substrate to prepare an anode composite current collector;
s20, sequentially arranging copper foil, a negative electrode active material layer and a second flame-retardant oxide coating on the upper surface and the lower surface of a second insulating substrate to prepare a negative electrode composite current collector;
s30, respectively roll-welding and adapting foil lugs on the positive electrode composite current collector and the negative electrode composite current collector;
s40, sequentially stacking the negative electrode composite current collector welded with the foil tab and the positive electrode composite current collector to form a lamination;
s50, respectively performing Tab welding and rubberizing treatment on foil tabs of the positive electrode composite current collector and the negative electrode composite current collector to obtain a battery cell;
and S60, sequentially packaging, baking, injecting liquid, standing, heating and pressurizing, performing two-seal molding and capacity-separating treatment on the battery cell, and thus obtaining the lithium ion battery.
The invention is further illustrated by the following examples:
example 1
A preparation method of a lithium ion battery comprises the following steps:
aluminum foil, an anode active material layer and a first flame-retardant oxide coating are sequentially arranged on the upper surface and the lower surface of a first insulating substrate to prepare an anode composite current collector;
sequentially arranging copper foil, a negative electrode active material layer and a second flame-retardant oxide coating on the upper surface and the lower surface of a second insulating substrate to prepare a negative electrode composite current collector;
respectively roll-welding transfer foil lugs on the positive composite current collector and the negative composite current collector;
sequentially stacking 32 layers of the negative electrode composite current collector welded with the foil lugs and the positive electrode composite current collector to form a lamination, wherein the lamination comprises 33 layers of the negative electrode composite current collector and 32 layers of the positive electrode composite current collector;
respectively carrying out Tab welding and rubberizing treatment on foil lugs of the positive electrode composite current collector and the negative electrode composite current collector to obtain a battery cell;
placing the battery cell into a film shell for top side sealing, bagging, and baking to dry the moisture in the battery cell;
injecting electrolyte into the air bag, allowing the electrolyte to permeate into the battery cell, and standing to allow the electrolyte to permeate into the pole piece and the diaphragm in the battery cell for full absorption; heating and heating to charge the battery cell, completing the first activation, and forming an SEI film to ensure the electrical performance of the battery cell; and (5) vacuumizing the waste gas produced in the formation process, and finally packaging to obtain the lithium ion battery.
Comparative example 1
A preparation method of a lithium ion battery comprises the following steps:
preparing an anode active material layer on an aluminum foil to prepare an anode current collector;
preparing a negative electrode active material layer on a copper foil to prepare a negative electrode current collector;
respectively roll-welding transfer foil lugs on the positive composite current collector and the negative composite current collector;
sequentially stacking 32 layers of the negative electrode composite current collector welded with the foil lugs and the positive electrode composite current collector to form a lamination, wherein the lamination comprises 33 layers of the negative electrode composite current collector and 32 layers of the positive electrode composite current collector;
respectively carrying out Tab welding and rubberizing treatment on foil lugs of the positive electrode composite current collector and the negative electrode composite current collector to obtain a battery cell;
placing the battery cell into a film shell for top side sealing, bagging, and baking to dry the moisture in the battery cell;
injecting electrolyte into the air bag, allowing the electrolyte to permeate into the battery cell, and standing to allow the electrolyte to permeate into the pole piece and the diaphragm in the battery cell for full absorption; heating and heating to charge the battery cell, completing the first activation, and forming an SEI film to ensure the electrical performance of the battery cell; and (3) vacuumizing the waste gas produced in the formation process, and removing the waste gas from the final package to obtain the lithium ion battery.
The lithium ion batteries of example 1 and comparative example 1 were subjected to safety test, and the results are shown in fig. 3 to 8. The lithium ion batteries of example 1 and comparative example 1 were first subjected to a needling test, and as shown in fig. 3 to 4, it can be seen from the figures that the lithium ion battery of comparative example 1 was subjected to a needling treatment, and the lithium ion battery of example 1 was not subjected to a needling treatment, and was not burnt.
Next, the lithium ion batteries of example 1 and comparative example 1 were subjected to a short circuit test, and as a result, as shown in fig. 5 to 6, it can be seen from the figures that the lithium ion battery of comparative example 1 was free from fire explosion at normal temperature short circuit, but a swelling phenomenon occurred, and the lithium ion battery of example 1 was free from fire explosion nor bulging phenomenon at the same normal temperature short circuit test.
Finally, the lithium ion batteries in the example 1 and the comparative example 1 are subjected to high-temperature furnace heating test, and the results are shown in fig. 7-8, and as can be seen from the figures, the lithium ion battery in the comparative example 1 has no fire explosion under the furnace temperature condition of 130 ℃, but the battery cell has been cracked; the lithium ion battery in example 1 did not explode on fire or crack under the same furnace temperature conditions. In summary, the lithium ion battery prepared in example 1 of the present invention can safely pass needling (100% soc), and the short circuit test and the high temperature furnace heat test are also superior to those of comparative example 1.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (6)
1. The lithium ion battery is characterized by comprising a positive electrode composite current collector and a negative electrode composite current collector which are sequentially stacked, wherein the positive electrode composite current collector comprises a first insulating base material at the center, aluminum foils arranged on the upper surface and the lower surface of the first insulating base material, a positive electrode active material coated on the aluminum foils, and a first flame-retardant oxide coating covering the surface of the positive electrode active material, the negative electrode composite current collector comprises a second insulating base material at the center, copper foils arranged on the upper surface and the lower surface of the second insulating base material, a negative electrode active material coated on the copper foils, and a second flame-retardant oxide coating covering the surface of the negative electrode active material.
2. The lithium ion battery of claim 1, wherein the materials of the first and second insulating substrates are independently selected from one or more of PET, PP.
3. The lithium ion battery according to claim 1, wherein the positive electrode active material is one or more of a ternary lithium material and a lithium cobaltate material; the negative electrode active material is one or more of a silicon negative electrode material and a graphite negative electrode material.
4. The lithium ion battery of claim 1, wherein the first flame retardant oxide coating and the second flame retardant oxide coating each comprise, in mass percent: 70-95% of flame-retardant oxide and 5-30% of PVDF, wherein the flame-retardant oxide is LLZO, li X Ai X Ti X (PO x ) X One or more of gamma-AlOOH.
5. The lithium ion battery of claim 1, wherein the first flame retardant oxide coating has a thickness of 1-8um and the second flame retardant oxide coating has a thickness of 1-8um.
6. A method of manufacturing a lithium ion battery according to any one of claims 1 to 5, comprising the steps of:
aluminum foil, an anode active material layer and a first flame-retardant oxide coating are sequentially arranged on the upper surface and the lower surface of a first insulating substrate to prepare an anode composite current collector;
sequentially arranging copper foil, a negative electrode active material layer and a second flame-retardant oxide coating on the upper surface and the lower surface of a second insulating substrate to prepare a negative electrode composite current collector;
respectively roll-welding transfer foil lugs on the positive composite current collector and the negative composite current collector;
sequentially stacking the negative electrode composite current collector welded with the foil tab and the positive electrode composite current collector to form a lamination;
respectively carrying out Tab welding and rubberizing treatment on foil lugs of the positive electrode composite current collector and the negative electrode composite current collector to obtain a battery cell;
and (3) packaging, baking, injecting liquid, standing, heating and pressurizing, performing two-seal molding and capacity-dividing treatment on the battery cell in sequence to obtain the lithium ion battery.
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