CN112701254A - Lithium-sulfur soft package battery and preparation method thereof - Google Patents
Lithium-sulfur soft package battery and preparation method thereof Download PDFInfo
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- CN112701254A CN112701254A CN202011593930.4A CN202011593930A CN112701254A CN 112701254 A CN112701254 A CN 112701254A CN 202011593930 A CN202011593930 A CN 202011593930A CN 112701254 A CN112701254 A CN 112701254A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a lithium-sulfur soft package battery and a preparation method thereof, wherein the preparation method comprises the following steps: prepressing the negative pole piece, the lithium foil and the release film to obtain a composite semi-finished product; the negative pole piece is positioned between two lithium foils, and the two lithium foils are positioned between two release films; rolling the obtained composite semi-finished product to obtain a composite negative plate; and assembling the obtained composite negative plate, the positive plate, the electrolyte and the diaphragm to obtain the lithium-sulfur soft package battery. The preparation method provided by the invention improves the negative plate by providing an external lithium source, radically solves the problem of metal lithium circulation, improves the capacity of the battery and achieves the aim of prolonging the service life; the preparation method is simple to operate, environment-friendly, low in energy consumption and raw material cost, good in economic benefit, beneficial to industrial mass production and good in industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium-sulfur soft package battery and a preparation method thereof.
Background
The lithium-sulfur battery has high theoretical specific energy, so that the endurance mileage can be doubled, and the lithium-sulfur battery is widely applied in recent years. At present, the lithium-sulfur battery is applied to the unmanned aerial vehicle, but the negative electrode of the lithium-sulfur battery adopts metal lithium, which has high activity and can react with the electrolyte in a contact way, so that the irreversible consumption of the metal lithium can be caused; and during the charging and discharging process, the dissolution-deposition of the metallic lithium is not uniform, which brings about the problems of the growth of lithium dendrite and the pulverization of lithium, resulting in a low cycle life of the battery. Therefore, it has been difficult to improve the cycle life of lithium-sulfur batteries.
Currently, most researchers mainly address the problem of cycle life of lithium-sulfur batteries from the following 3 aspects: 1) developing a lithium electrode conductive protection diaphragm; 2) developing a metal lithium negative electrode film-forming electrolyte; 3) the production amplification of the lithium metal negative electrode is difficult to realize by the above 3 methods, and the lithium metal negative electrode is limited by the protection capability, and the lithium metal negative electrode cannot be comprehensively protected after the size of the lithium metal is increased, so that the cycle life of the lithium-sulfur battery is shortened.
CN102368561A discloses a chargeable and dischargeable lithium-sulfur battery, the preparation method thereof comprises: coating the silicon-carbon micro-nano composite on copper foil to obtain an electrode, and coating the electrode with 1MLiPF6Preparing a half cell by using DOL/DME as electrolyte and metal lithium as a counter electrode, and preparing a pre-lithiated silicon-carbon micro-nano composite negative electrode material through a discharging process; (2) taking the prepared pre-lithiated silicon-carbon micro-nano composite as a negative electrode; the sulfur-carbon nanotube composite is used as a positive electrode; the mass part ratio of sulfur to carbon nano tube in the sulfur-carbon nano tube compound is 2: 3; the composite material is prepared by the following method: preparing a carbon nano tube by using alumina as a template and polyacrylonitrile as a carbon source, and filling sulfur into the carbon nano tube at the temperature of 155 ℃; N-methyl-N-allyl pyrrolidine bistrifluoromethylsulfonyl imide salt as solvent and LiN (CF)3SO2)2An electrolyte is constituted of a lithium-containing electrolyte salt, and LiN (CF)3SO2)2The molar concentration of (A) is 0.5 mol/L; is composed of the electrode material and electrolyteA lithium sulfur full cell. The method has complex prelithiation process and strict requirement on operation environment, and is not suitable for mass preparation.
CN110581263A discloses a preparation method of a manganese dioxide modified lithium-sulfur battery lithium metal cathode, which comprises the following steps: transferring the metallic lithium pieces stored in the glove box to a vacuum bin; under the condition of room temperature, filling inert gas into the vacuum chamber, performing magnetron sputtering treatment, and depositing manganese dioxide with the purity of more than 99 percent on the metal lithium sheet by taking manganese dioxide as a target material to obtain MnO2MnO with deposition thickness of 2-15 nm2Coating a metal lithium composite material; MnO is added to the mixture2And carrying out pre-lithiation treatment on the coated lithium metal composite material to obtain the manganese dioxide modified lithium-sulfur battery lithium metal cathode. The method adopts a magnetron sputtering method to carry out deposition modification on the lithium metal sheet by manganese dioxide, has complex process and higher cost, and is not suitable for mass preparation.
In summary, how to provide a lithium-sulfur battery with simple preparation process and improved battery cycle life is a problem to be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a lithium sulfur soft package battery and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a preparation method of a lithium-sulfur soft package battery, which comprises the following steps:
(1) prepressing the negative pole piece, the lithium foil and the release film to obtain a composite semi-finished product;
the negative pole piece is positioned between two lithium foils, and the two lithium foils are positioned between two release films;
(2) calendering the composite semi-finished product obtained in the step (1) to obtain a composite negative plate;
(3) and (3) assembling the composite negative plate, the positive plate, the electrolyte and the diaphragm obtained in the step (2) to obtain the lithium-sulfur soft package battery.
According to the preparation method, the first effect and the cycle performance of the lithium-sulfur soft package battery are improved by improving the negative plate. The preparation method adopts a method of prepressing and then calendering, two lithium foils are attached to two sides of the negative pole piece, lithium ions are provided for the negative pole piece to form an SEI film, the lithium ions in electrolyte are prevented from being consumed in the later battery formation process, and the problems of irreversible lithium loss caused by the SEI film formed by the negative pole piece and the problems of dendritic crystal, lithium pulverization, flammability and the like when the negative pole adopts pure metal lithium are fundamentally solved; meanwhile, in the charging and discharging process, an external lithium source can provide lithium ions for the back-and-forth insertion and de-insertion between the two electrodes, so that the capacity, the first effect and the cycle performance of the whole battery are improved; the preparation method is simple and safe in process flow, the obtained composite negative plate does not need to be assembled into a battery for pre-formation, the composite negative plate can be directly used in the subsequent battery assembly application, the pre-lithiation process can be completed after the battery is injected with liquid, the production efficiency is high, and the preparation method has a good industrial application prospect.
In the invention, the preparation method adopts prepressing and then rolling, so that the dislocation of the lithium foil in the rolling process can be prevented.
In the invention, the use of the release film comprises the following steps: fixedly sleeving a rolled release film on an unwinding shaft, fixing the unwinding shaft, drawing the upper layer and the lower layer of the release film, adjusting the unwinding tension of an unwinding mechanism, and enabling the two layers of the drawn release films to pass through prepressing equipment; the use of the release film can effectively prevent the lithium foil from being bonded with equipment.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the prepressing in the step (1) is carried out by adopting prepressing equipment.
Preferably, the pre-pressing device is provided with a positioning area.
Preferably, in the positioning region, the negative electrode plate, the lithium foil and the release film are arranged according to the positional relationship in the step (1).
According to the invention, the positioning area can effectively prevent the dislocation of the negative pole piece and the lithium foil, and the product quality is ensured.
Preferably, the pre-pressing device controls the pressure of the pre-pressing through any one of an air pipe, a screw, or an oil pressure.
Preferably, the pre-pressing pressure in step (1) is 2 to 10 tons, such as 2 tons, 3 tons, 4 tons, 5 tons, 6 tons, 7 tons, 8 tons, 9 tons or 10 tons, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In the present invention, the pre-pressing pressure needs to be strictly controlled. If the pre-pressing pressure is too large, the negative pole piece can be damaged; if the pre-pressing pressure is too low, the lithium foil is not tightly attached to the negative pole piece, so that the solid-solid interface is not in good contact, a gap exists, the lithium foil and the negative pole piece are easy to misplace in the later calendering process, the pre-lithiation process is incomplete, and the pre-lithiation effect cannot reach the expected value, for example: the first effect is improved low, and the capacity is exerted low.
In the invention, the thickness of the composite semi-finished product obtained after prepressing is compared with the thickness of a corresponding standard pole piece, and prepressing is carried out again if the thickness is greater than the thickness range of the standard pole piece until the standard pole piece reaches the standard; if the thickness is smaller than the thickness range of the standard pole piece, the standard is not met, and the battery can not be applied to the assembly of the battery.
In the invention, the standard pole piece is a composite pole piece consisting of a negative pole piece and a lithium foil, and the thickness of the standard pole piece is the sum of the designed thickness of the negative pole piece and the thickness of the lithium foil minus (0.01-1 μm).
In a preferred embodiment of the present invention, the area ratio of the lithium foil to the negative electrode tab in step (1) is 1 (1 to 20), for example, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, or 1:20, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the invention, the area ratio of the lithium foil to the negative pole piece needs to be controlled. If the area of the lithium foil is too large, lithium precipitation of the negative pole piece can be caused; if the area of the lithium foil is too small, the amount of lithium source in the battery is small, and the positive electrode sheet material is wasted.
Preferably, the capacity ratio of the lithium foil to the negative electrode sheet in the step (1) is (1-10): 1, for example, 1:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but the invention is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the capacity ratio of the lithium foil to the negative pole piece needs to be controlled. If the capacity of the lithium foil is too small, the capacity of the battery becomes small; if the capacity of the lithium foil is too large, lithium precipitation of the negative electrode sheet may occur.
Preferably, the thickness of the lithium foil in step (1) is 1 to 200 μm, for example, 1 μm, 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 140 μm, 180 μm, or 200 μm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the present invention, the thickness of the lithium foil is strictly controlled. If the thickness of the lithium foil is too large, lithium precipitation of the negative pole piece can be caused, and the capacity and the cycle performance of the battery cell are greatly reduced; if the thickness of the lithium foil is too small, the pre-lithium effect is not good, and the improvement ratio of the capacity, the first effect and the like of the battery cell is small.
As a preferable technical scheme of the invention, the preparation of the negative pole piece in the step (1) comprises the following steps:
mixing a negative electrode active material, a negative electrode conductive agent, a negative electrode binder and a first solvent to obtain negative electrode slurry; and coating the obtained negative electrode slurry on a negative electrode current collector, and sequentially drying, rolling and slitting to obtain a negative electrode pole piece.
Preferably, the negative active material comprises a graphite material and/or a silicon-based negative material.
Preferably, the graphite material comprises any one of, or a combination of at least two of, artificial graphite, natural graphite, or mesocarbon microbeads, as typical but non-limiting examples: combinations of artificial graphite and natural graphite, combinations of natural graphite and mesocarbon microbeads, combinations of artificial graphite, natural graphite and mesocarbon microbeads, and the like.
Preferably, the silicon-based anode material comprises a silicon-oxygen anode material and/or a silicon-carbon anode material.
Preferably, the negative electrode conductive agent comprises any one of or a combination of at least two of conductive carbon black, conductive graphite, carbon fibers or carbon nanotubes, as typical but non-limiting examples: combinations of conductive carbon black and conductive graphite, combinations of carbon fibers and carbon nanotubes, combinations of conductive carbon black, conductive graphite and carbon fibers, and the like.
Preferably, the negative electrode binder comprises any one of cyclodextrin, polyvinyl alcohol, polyacrylic acid, styrene butadiene rubber, or sodium carboxymethyl cellulose, or a combination of at least two of them, as typical but non-limiting examples: a combination of cyclodextrin and polyvinyl alcohol, a combination of polyvinyl alcohol and sodium carboxymethylcellulose, a combination of cyclodextrin, polyvinyl alcohol and sodium carboxymethylcellulose, and the like.
Preferably, the first solvent comprises any one of water, aqueous ethanol or aqueous isopropanol, or a combination of at least two of these, typical but non-limiting examples being: combinations of aqueous ethanol and aqueous isopropanol, and the like.
Preferably, the negative electrode current collector includes any one of a copper foil, a nickel mesh or a titanium mesh.
Preferably, the content of the negative active material, the negative conductive agent and the negative binder is 90 to 98 wt%, such as 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt% or 98 wt%, respectively; 0.5 to 5 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, etc.; 1.5 to 5 wt.%, for example 1.5 wt.%, 2 wt.%, 3 wt.%, 4 wt.% or 5 wt.%, and the selection of the above-mentioned content is not limited to the recited values, and other values not recited within the respective numerical ranges are also applicable.
Preferably, the negative electrode slurry is coated on the negative electrode current collector on both sides.
Preferably, the thickness of the negative electrode sheet is 50 to 500 μm, for example, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm or 500 μm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferable technical scheme of the invention, the rolling in the step (2) is carried out by a pair roller device.
Preferably, the pressure for rolling in step (2) is 1 to 10 tons, such as 1 ton, 2 tons, 4 tons, 15 tons, 6 tons, 8 tons, or 10 tons, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In the present invention, the pressure for calendering is strictly controlled. If the pressure of calendering is too large, the negative pole piece can be damaged; if the pressure of the calendering is too low, the separation of the lithium foil from the release film at the later stage is difficult.
Preferably, the release film is peeled after the rolling in the step (2).
In a preferred embodiment of the present invention, in the composite negative electrode sheet in the step (2), the two lithium foils are embedded in the negative electrode sheet by 1 to 50 μm, for example, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the invention, the depth of the two lithium foils embedded into the negative pole piece needs to be controlled. If the embedding depth is too small, the phenomenon that the solid interface of the lithium foil and the pole piece is not tightly attached exists, and the migration of metal lithium is caused; if the embedding depth is too large, the negative pole piece is over-pressed.
In the invention, the thickness of the obtained composite negative pole piece is compared with the thickness of the corresponding standard pole piece, and if the thickness is larger than the thickness range of the standard pole piece, calendering is carried out again until the standard is reached; if the thickness is smaller than the thickness range of the standard pole piece, the standard is not met, and the battery can not be assembled.
As a preferable technical solution of the present invention, the method for preparing the positive electrode sheet in the step (3) includes the steps of:
mixing a positive electrode active material, a positive electrode conductive agent, a positive electrode binder and a second solvent to obtain positive electrode slurry; and coating the obtained positive electrode slurry on a positive electrode current collector, and sequentially drying, rolling and slitting to obtain a positive electrode sheet.
Preferably, the positive active material includes any one of or a combination of at least two of a sulfur-conductive polymer composite, a sulfur-carbon composite, a conductive organic polymer, an organic sulfide, or an oxygen-containing conjugated organic compound, which are exemplified typically but not limited to: the combination of sulfur-conductive polymer composite material and sulfur-carbon composite material, the combination of conductive organic high polymer and organic sulfide, the combination of organic sulfide and oxygen-containing conjugated organic matter, etc.
Preferably, the positive electrode conductive agent comprises any one of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube or a combination of at least two of them, as typical but non-limiting examples: combinations of conductive carbon black and conductive graphite, combinations of carbon fibers and carbon nanotubes, combinations of conductive carbon black, conductive graphite and carbon fibers, and the like.
Preferably, the positive electrode binder comprises any one or a combination of at least two of cyclodextrin, polyvinylidene fluoride, sodium alginate, polyacrylic, epoxy or acrylonitrile based copolymers, as typical but non-limiting examples: a combination of cyclodextrin and polyvinylidene fluoride, a combination of polyacrylic acids and epoxy resins, a combination of epoxy resins and acrylonitrile copolymers, and the like.
Preferably, the second solvent comprises any one of, or a combination of at least two of, water, aqueous ethanol, aqueous isopropanol, or N-methylpyrrolidone, typical but non-limiting examples of which are: a combination of an aqueous ethanol solution and an aqueous isopropanol solution, a combination of water and N-methylpyrrolidone, a combination of an aqueous ethanol solution and N-methylpyrrolidone, and the like.
Preferably, the positive electrode current collector includes any one of an aluminum foil, an aluminum mesh, a carbon-coated aluminum foil, a carbon-coated aluminum mesh, a nickel mesh, or a nickel foam.
Preferably, the content of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder is 80 to 90 wt%, such as 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt% or 90 wt%, respectively; 5 to 15 wt%, such as 5 wt%, 7 wt%, 9 wt%, 11 wt%, 13 wt%, or 15 wt%, etc.; 2 to 10 wt%, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, and the selection of the above content is not limited to the recited values, and other values not recited in the respective numerical ranges are also applicable.
Preferably, the positive electrode slurry is coated on the positive electrode current collector on both sides.
Preferably, the thickness of the positive electrode sheet is 50 to 500. mu.m, for example, 50. mu.m, 100. mu.m, 150. mu.m, 200. mu.m, 250. mu.m, 300. mu.m, 350. mu.m, 400. mu.m, 450. mu.m, or 500. mu.m, but not limited to the values listed, and other values not listed within the range of the values are also applicable.
As a preferable technical solution of the present invention, the lithium salt in the electrolyte in step (3) includes any one or a combination of at least two of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium difluorooxalato borate, lithium dioxalate borate, lithium tetrafluoroborate, and lithium nitrate, a combination of lithium hexafluorophosphate and lithium bistrifluoromethanesulfonylimide, a combination of lithium difluorosulfonimide and lithium difluorooxalato borate, a combination of lithium dioxalate borate, lithium tetrafluoroborate, and lithium nitrate, and the like.
Preferably, the solvent in the electrolyte in step (3) includes any one or a combination of at least two of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate, a combination of ethylene carbonate and ethyl methyl carbonate, a combination of dimethyl carbonate and diethyl carbonate, a combination of ethyl methyl carbonate, dimethyl carbonate and diethyl carbonate, and the like.
Preferably, the separator of step (3) comprises any one of a PE separator, a ceramic separator, a coated polyester film, a cellulose film, a polyimide film, a polyamide film, a spandex or an aramid film.
Preferably, the assembling of step (3) is performed in a dry environment.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) preparing a negative pole piece: mixing 90-98 wt% of a negative electrode active material, 0.5-5 wt% of a negative electrode conductive agent and 1.5-5 wt% of a negative electrode binder with a first solvent to obtain negative electrode slurry; coating the two sides of the obtained negative electrode slurry on a negative electrode current collector, and then sequentially drying, rolling and slitting to obtain a negative electrode piece with the thickness of 50-500 mu m;
in the location area of pre-compaction equipment, will negative pole piece, thickness are 1 ~ 200 mu m's lithium foil and arrange from the type membrane, the negative pole piece is located between two lithium foils, two lithium foils are located two-layer from type membrane between, the lithium foil with the area ratio of negative pole piece is 1: (1-20) the volume ratio is (1-10): 1; prepressing by adjusting any one of an air pipe, a screw rod or oil pressure and adopting the pressure of 2-10 tons to obtain a composite semi-finished product;
(2) rolling the composite semi-finished product obtained in the step (1) by using double-roll equipment, wherein the rolling pressure is 1-10 tons, and stripping off the release film after rolling to obtain a composite negative plate; in the composite negative plate, the two lithium foils are embedded into the negative plate by 1-50 mu m;
(3) preparing a positive plate: mixing 80-90 wt% of a positive electrode active material, 5-15 wt% of a positive electrode conductive agent, 2-10 wt% of a positive electrode binder and a second solvent to obtain positive electrode slurry; coating the two sides of the obtained anode slurry on an anode current collector, and then sequentially drying, rolling and cutting to obtain an anode sheet with the thickness of 50-500 mu m;
and (3) assembling the composite negative plate obtained in the step (2), the positive plate, the electrolyte and the diaphragm in a dry environment to obtain the lithium-sulfur soft package battery.
In another aspect, the invention provides the lithium-sulfur soft package battery prepared by the preparation method, and a battery cell of the lithium-sulfur soft package battery is a laminated battery cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method, the negative plate of the lithium-sulfur soft package battery is improved, namely a method of prepressing and then rolling is adopted, two lithium foils are attached to two sides of the negative plate, a lithium source is provided for the negative plate, the problems of dendritic crystal, lithium pulverization, flammability and the like existing when pure metal lithium is adopted as the negative electrode are fundamentally solved, and the service life of the lithium-sulfur soft package battery is prolonged; the pre-pressing pressure in the improvement process of the negative pole piece, the area ratio and the capacity ratio of the lithium foil to the negative pole piece are further controlled, so that the first-circle discharge capacity of the prepared lithium-sulfur soft package battery accounts for more than 90% of the designed capacity, and the cycle times are more than 200 times;
(2) the preparation method provided by the invention is simple and safe in process flow, the obtained composite negative plate can complete the pre-lithiation process without being assembled into a battery for pre-formation, can be directly used for the subsequent assembly application of the lithium-sulfur soft package battery, is high in production efficiency, and has a good industrial application prospect.
Drawings
Fig. 1 is a schematic structural diagram of a lithium-sulfur pouch battery provided in example 1 of the present invention;
the lithium ion battery comprises a positive electrode, a negative electrode, a lithium foil, a diaphragm, a positive electrode and an adhesive tape, wherein the positive electrode comprises 1-a negative electrode plate, 2-a lithium foil, 3-a diaphragm, 4-a positive electrode plate and 5-an adhesive tape.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides a lithium-sulfur soft package battery and a preparation method thereof, and the preparation method comprises the following steps:
(1) prepressing the negative pole piece 1, the lithium foil 2 and the release film to obtain a composite semi-finished product;
the negative pole piece 1 is positioned between two lithium foils 2, and the two lithium foils 2 are positioned between two release films;
(2) calendering the composite semi-finished product obtained in the step (1) to obtain a composite negative plate;
(3) and (3) assembling the composite negative plate obtained in the step (2), the positive plate 4, the electrolyte and the diaphragm 3 to obtain the lithium-sulfur soft package battery.
The lithium sulfur soft package battery is prepared by the preparation method.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a lithium sulfur soft package battery and a preparation method thereof, wherein the structural schematic diagram of the lithium sulfur soft package battery is shown in fig. 1, and the lithium sulfur soft package battery comprises a composite negative plate, a positive plate 4, electrolyte, a diaphragm 3 and an adhesive tape 5;
the composite negative plates and the positive plates 4 are alternately stacked; the diaphragm 3 separates the composite negative plate from the positive plate 4 in an S shape and wraps the composite negative plate from the outer side; the lithium sulfur soft package battery is packaged by an adhesive tape 5.
The preparation method comprises the following steps:
(1) preparing a negative pole piece 1: mixing artificial graphite, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber with water according to the mass ratio of 90:5:2.5:2.5 to obtain negative electrode slurry; coating the two sides of the obtained negative electrode slurry on copper foil, and then sequentially drying, rolling and slitting to obtain a negative electrode plate 1 with the thickness of 200 mu m;
arranging the negative pole piece 1, the lithium foil 2 with the thickness of 30 mu m and a release film in a positioning area of pre-pressing equipment, wherein the negative pole piece 1 is positioned between two lithium foils 2, the two lithium foils 2 are positioned between two release films, the area ratio of the lithium foils 2 to the negative pole piece 1 is 1:1, and the capacity ratio is 1: 1; prepressing by adjusting the air pipe with the pressure of 2 tons to obtain a composite semi-finished product;
(2) rolling the composite semi-finished product obtained in the step (1) by using double-roll equipment, wherein the rolling pressure is 4 tons, and stripping the release film after rolling to obtain a composite negative plate; in the composite negative plate, the two lithium foils 2 are embedded into the negative plate 1 by 5 microns;
(3) preparing a positive plate 4: mixing the sulfur-carbon composite material, the conductive carbon black and the water dispersion of the acrylonitrile multipolymer with water according to the mass ratio of 80:15:5 to obtain anode slurry; coating the two sides of the obtained anode slurry on an aluminum foil, and then sequentially drying, rolling and slitting to obtain an anode sheet 4 with the thickness of 200 um;
assembling the composite negative plate obtained in the step (2), the positive plate 4, the electrolyte and the PE diaphragm in a dry environment to obtain the lithium-sulfur soft package battery;
lithium salts in the electrolyte comprise lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide and lithium bistrifluoromethanesulfonylimide; the solvent in the electrolyte comprises ethylene carbonate and ethyl methyl carbonate.
Example 2:
the embodiment provides a lithium sulfur soft package battery and a preparation method thereof, and the structure of the lithium sulfur soft package battery is the same as that of the lithium sulfur soft package battery in embodiment 1.
The preparation method comprises the following steps:
(1) preparing a negative pole piece 1: mixing artificial graphite, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber with water according to the mass ratio of 92:5:1.5:1.5 to obtain negative electrode slurry; coating the two sides of the obtained negative electrode slurry on copper foil, and then sequentially drying, rolling and slitting to obtain a negative electrode plate 1 with the thickness of 500 microns;
arranging the negative pole piece 1, the lithium foil 2 with the thickness of 200 mu m and a release film in a positioning area of pre-pressing equipment, wherein the negative pole piece 1 is positioned between two lithium foils 2, the two lithium foils 2 are positioned between two release films, the area ratio of the lithium foils 2 to the negative pole piece 1 is 1:20, and the capacity ratio is 10: 1; prepressing by adjusting the air pipe with 10 tons of pressure to obtain a composite semi-finished product;
(2) rolling the composite semi-finished product obtained in the step (1) by using double-roll equipment, wherein the rolling pressure is 10 tons, and stripping the release film after rolling to obtain a composite negative plate; in the composite negative plate, the two lithium foils 2 are embedded into the negative plate 1 by 50 microns;
(3) preparing a positive plate 4: mixing the sulfur-conductive polymer composite material, conductive carbon black, the carbon nano tube and cyclodextrin with an ethanol water solution according to the mass ratio of 90:2.5:2.5:5 to obtain positive electrode slurry; coating the two sides of the obtained anode slurry on an aluminum foil coated with carbon, and then sequentially drying, rolling and cutting to obtain an anode sheet 4 with the thickness of 500 um;
assembling the composite negative plate obtained in the step (2), the positive plate 4, the electrolyte and the PE diaphragm in a dry environment to obtain the lithium-sulfur soft package battery;
the lithium salt in the electrolyte comprises lithium difluoro oxalate borate and lithium bis (oxalate) borate; the solvent in the electrolyte comprises dimethyl carbonate and diethyl carbonate.
Example 3:
the embodiment provides a lithium sulfur soft package battery and a preparation method thereof, and the structure of the lithium sulfur soft package battery is the same as that of the lithium sulfur soft package battery in embodiment 1.
The preparation method comprises the following steps:
(1) preparing a negative pole piece 1: mixing artificial graphite, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber with water according to the mass ratio of 98:0.5:1:0.5 to obtain negative electrode slurry; coating the two sides of the obtained negative electrode slurry on copper foil, and then sequentially drying, rolling and slitting to obtain a negative electrode plate 1 with the thickness of 50 microns;
arranging the negative pole piece 1, the lithium foil 2 with the thickness of 1 mu m and a release film in a positioning area of pre-pressing equipment, wherein the negative pole piece 1 is positioned between two lithium foils 2, the two lithium foils 2 are positioned between two release films, the area ratio of the lithium foils 2 to the negative pole piece 1 is 1:15, and the capacity ratio is 8: 1; prepressing by adopting 2 tons of pressure through an adjusting screw rod to obtain a composite semi-finished product;
(2) rolling the composite semi-finished product obtained in the step (1) by using double-roll equipment, wherein the rolling pressure is 1 ton, and stripping the release film after rolling to obtain a composite negative plate; in the composite negative plate, the two lithium foils 2 are embedded into the negative plate 1 by 1 μm;
(3) preparing a positive plate 4: mixing the sulfur-carbon anode material, the conductive carbon black and the water dispersion of the acrylonitrile multipolymer with water according to the mass ratio of 86:12:2 to obtain anode slurry; coating the two sides of the obtained anode slurry on an aluminum net, and then sequentially drying, rolling and slitting to obtain an anode sheet 4 with the thickness of 50 um;
assembling the composite negative plate obtained in the step (2), the positive plate 4, the electrolyte and the ceramic diaphragm in a dry environment to obtain the lithium-sulfur soft package battery;
the lithium salt in the electrolyte comprises lithium tetrafluoroborate and lithium nitrate; the solvent in the electrolyte comprises methyl ethyl carbonate and dimethyl carbonate.
Example 4:
the embodiment provides a lithium sulfur soft package battery and a preparation method thereof, and the structure of the lithium sulfur soft package battery is the same as that of the lithium sulfur soft package battery in embodiment 1.
The preparation method comprises the following steps:
(1) preparing a negative pole piece 1: mixing artificial graphite, conductive carbon black and polyacrylic acid with an isopropanol aqueous solution according to a mass ratio of 95:3:2 to obtain a negative electrode slurry; coating the two sides of the obtained negative electrode slurry on a nickel screen, and then sequentially drying, rolling and slitting to obtain a negative electrode plate 1 with the thickness of 150 microns;
in the locating area of pre-compaction equipment, will negative pole piece 1, thickness are 15 μm's lithium paper tinsel 2 and arrange from the type membrane, negative pole piece 1 is located between two lithium paper tinsels 2, two lithium paper tinsels 2 are located two-layer type membrane between, lithium paper tinsel 2 with the area ratio of negative pole piece 1 is 1:2, capacity ratio is 2: 1; prepressing by adjusting the air pipe with 5 tons of pressure to obtain a composite semi-finished product;
(2) rolling the composite semi-finished product obtained in the step (1) by using double-roll equipment, wherein the rolling pressure is 5 tons, and stripping the release film after rolling to obtain a composite negative plate; in the composite negative plate, the two lithium foils 2 are embedded into the negative plate 1 by 5 microns;
(3) preparing a positive plate 4: mixing organic sulfide, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 80: 10: 10 and N-methyl pyrrolidone to obtain positive electrode slurry; coating the two sides of the obtained anode slurry on an aluminum foil, and then sequentially drying, rolling and slitting to obtain an anode sheet 4 with the thickness of 150 um;
assembling the composite negative plate obtained in the step (2), the positive plate 4, the electrolyte and the ceramic diaphragm in a dry environment to obtain the lithium-sulfur soft package battery;
the lithium salt in the electrolyte comprises bis (trifluoromethane) sulfonyl imide lithium and bis (fluoro) sulfonyl imide lithium; the solvent in the electrolyte comprises ethylene carbonate and ethyl methyl carbonate.
Example 5:
this example provides a lithium sulfur pouch battery and a method of making the same, which is referenced to the method of making in example 1, except that: and (1) pre-pressing by adopting the pressure of 0.5 ton.
Example 6:
this example provides a lithium sulfur pouch battery and a method of making the same, which is referenced to the method of making in example 2, except that: and (1) pre-pressing by adopting pressure of 12 tons.
In this embodiment, the pre-pressing pressure is too large, which results in the pole piece being directly broken and the subsequent operation being unable to be performed.
Example 7:
this example provides a lithium sulfur pouch battery and a method of making the same, which is referenced to the method of making in example 2, except that: in the step (1), the area ratio of the lithium foil to the negative electrode plate is 1: 40.
example 8:
this example provides a lithium sulfur pouch battery and a method of making the same, which is referenced to the method of making in example 1, except that: in the step (1), the capacity ratio of the lithium foil to the negative electrode plate is 0.1: 1.
example 9:
this example provides a lithium sulfur pouch battery and a method of making the same, which is referenced to the method of making in example 2, except that: in the step (1), the capacity ratio of the lithium foil to the negative electrode piece is 15: 1.
comparative example 1:
this comparative example provides a lithium sulfur pouch battery and a method of manufacturing the same, which is referenced to the method of manufacturing in example 1, except that: and (2) only placing one lithium foil on one side of the negative pole piece in the step (1).
Comparative example 2:
this comparative example provides a lithium sulfur pouch battery and a method of manufacturing the same, which is referenced to the method of manufacturing in example 1, except that: the pre-pressing step in step (1) was not performed, and the negative electrode sheet, the lithium foil having a thickness of 30 μm, and the release film were assembled in their positional relationship and then directly rolled with a roll-to-roll apparatus.
The lithium foil and the negative pole piece in the composite negative pole piece prepared by the comparative example are staggered, so that the obtained composite negative pole piece does not meet the standard and cannot be applied to the subsequent battery assembly.
The lithium-sulfur pouch batteries prepared in examples 1 to 9 and comparative example 1 were subjected to a force of 700kgf, and after standing at 40 ℃ for 20 hours, a charge-discharge test was performed at a current of 0.1C rate, and the percentage of the first discharge capacity to the design capacity and the number of cycles were measured. The results are shown in Table 1.
Table 1 percentage of first-turn discharge capacity to design capacity and cycle number of lithium sulfur pouch batteries prepared in examples 1 to 9 and comparative example 1
In the lithium-sulfur soft package battery prepared in the embodiments 1 to 4, the percentage of the first-turn discharge capacity of the prepared lithium-sulfur soft package battery in the design capacity is more than 90%, and the cycle number is more than 200 by improving the negative plate and further controlling the pre-pressing pressure in the negative plate improvement process and the area ratio and the capacity ratio of the lithium foil to the negative plate; example 5 the pre-pressing pressure during the preparation of the composite negative electrode sheet is too low, which results in the lithium foil and the negative electrode sheet still being independent electrode sheets, and the lithium foil is not embedded into the negative electrode sheet, thereby affecting the improvement of the battery performance; example 7 the area of the lithium foil is too small during the preparation of the composite negative electrode sheet, which results in a reduction in the lithium source of the battery and affects the improvement of the battery performance; example 8 the capacity of the lithium foil during the preparation of the composite negative electrode sheet was too small, resulting in too small capacity of the entire battery, which did not meet the use requirements of the battery; example 9 the capacity of the lithium foil was too large during the preparation of the composite negative electrode sheet, resulting in precipitation of lithium from the negative electrode sheet and a significant reduction in cycle life.
In the process of preparing the composite negative pole piece, the lithium foil is only attached to one side of the negative pole piece, so that the improvement on the battery performance is limited.
It can be seen from the above embodiments and comparative examples that the preparation method of the invention improves the negative electrode plate of the lithium-sulfur soft package battery, namely, adopts the method of prepressing and then calendering, and attaches two lithium foils to two sides of the negative electrode plate to provide a lithium source for the negative electrode plate, so that the problems of dendritic crystal, lithium pulverization, flammability and the like existing when the negative electrode adopts pure metal lithium are fundamentally solved, and the service life of the lithium-sulfur soft package battery is prolonged; the pre-pressing pressure in the improvement process of the negative pole piece, the area ratio and the capacity ratio of the lithium foil to the negative pole piece are further controlled, so that the first-circle discharge capacity of the prepared lithium-sulfur soft package battery accounts for more than 90% of the designed capacity, and the cycle times are more than 200 times; the preparation method is simple and safe in process flow, the obtained composite negative plate can complete the pre-lithiation process without being assembled into a battery for pre-formation, can be directly used for the subsequent assembly application of the lithium-sulfur soft package battery, is high in production efficiency, and has a good industrial application prospect.
The applicants state that the present invention is illustrated by the above examples to show the detailed methods and products of the present invention, but the present invention is not limited to the above detailed methods and products, i.e. it is not meant that the present invention must rely on the above detailed methods and products to be practiced. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents thereof, additions of additional operations, selection of specific ways, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the lithium-sulfur soft package battery is characterized by comprising the following steps:
(1) prepressing the negative pole piece, the lithium foil and the release film to obtain a composite semi-finished product;
the negative pole piece is positioned between two lithium foils, and the two lithium foils are positioned between two release films;
(2) calendering the composite semi-finished product obtained in the step (1) to obtain a composite negative plate;
(3) and (3) assembling the composite negative plate, the positive plate, the electrolyte and the diaphragm obtained in the step (2) to obtain the lithium-sulfur soft package battery.
2. The production method according to claim 1, wherein the pre-pressing of step (1) is performed using a pre-pressing apparatus;
preferably, a positioning area is arranged on the pre-pressing equipment;
preferably, in the positioning region, the negative electrode plate, the lithium foil and the release film are arranged according to the positional relationship in the step (1);
preferably, the pre-pressing device controls the pre-pressing pressure through any one of an air pipe, a screw rod or oil pressure;
preferably, the pre-pressing pressure in the step (1) is 2-10 tons.
3. The preparation method according to claim 1 or 2, wherein the area ratio of the lithium foil to the negative electrode plate in the step (1) is 1 (1-20);
preferably, the capacity ratio of the lithium foil to the negative electrode plate in the step (1) is (1-10): 1;
preferably, the thickness of the lithium foil in the step (1) is 1-200 μm.
4. The preparation method according to any one of claims 1 to 3, wherein the preparation of the negative electrode sheet in the step (1) comprises the following steps:
mixing a negative electrode active material, a negative electrode conductive agent, a negative electrode binder and a first solvent to obtain negative electrode slurry; coating the obtained negative electrode slurry on a negative electrode current collector, and sequentially drying, rolling and slitting to obtain a negative electrode plate;
preferably, the negative active material comprises a graphite material and/or a silicon-based negative material;
preferably, the graphite material comprises any one or a combination of at least two of artificial graphite, natural graphite or mesocarbon microbeads;
preferably, the silicon-based anode material comprises a silicon-oxygen anode material and/or a silicon-carbon anode material;
preferably, the negative electrode conductive agent comprises any one or a combination of at least two of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube;
preferably, the negative electrode binder comprises any one or a combination of at least two of cyclodextrin, polyvinyl alcohol, polyacrylic acid, styrene butadiene rubber or sodium carboxymethyl cellulose;
preferably, the first solvent comprises any one of water, ethanol aqueous solution or isopropanol aqueous solution or a combination of at least two of the above;
preferably, the negative electrode current collector comprises any one of a copper foil, a nickel mesh or a titanium mesh;
preferably, the content of the negative active material, the content of the negative conductive agent and the content of the negative binder are respectively 90-98 wt%, 0.5-5 wt% and 1.5-5 wt%;
preferably, the negative electrode slurry is coated on the negative electrode current collector on both sides;
preferably, the thickness of the negative pole piece is 50-500 μm.
5. The production method according to any one of claims 1 to 4, wherein the calendering of step (2) is carried out using a pair-roll apparatus;
preferably, the pressure of the calendering in the step (2) is 1-10 tons;
preferably, the release film is peeled after the rolling in the step (2).
6. The preparation method according to any one of claims 1 to 5, wherein in the composite negative electrode sheet in the step (2), the two lithium foils are embedded in the negative electrode sheet by 1-50 μm.
7. The production method according to any one of claims 1 to 6, characterized in that the production method of the positive electrode sheet of step (3) includes the steps of:
mixing a positive electrode active material, a positive electrode conductive agent, a positive electrode binder and a second solvent to obtain positive electrode slurry; coating the obtained positive electrode slurry on a positive electrode current collector, and sequentially drying, rolling and slitting to obtain a positive electrode sheet;
preferably, the positive active material comprises any one or a combination of at least two of a sulfur-conductive polymer composite material, a sulfur-carbon composite material, a conductive organic macromolecule, an organic sulfide or an oxygen-containing conjugated organic matter;
preferably, the positive electrode conductive agent comprises any one or a combination of at least two of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube;
preferably, the positive binder comprises any one or a combination of at least two of cyclodextrin, polyvinylidene fluoride, sodium alginate, polyacrylic acids, epoxy resins or acrylonitrile copolymers;
preferably, the second solvent comprises any one of water, ethanol aqueous solution, isopropanol aqueous solution or N-methylpyrrolidone or a combination of at least two of the above;
preferably, the positive current collector comprises any one of an aluminum foil, an aluminum mesh, a carbon-coated aluminum foil, a carbon-coated aluminum mesh, a nickel mesh or a nickel foam;
preferably, the content of the positive active material, the content of the positive conductive agent and the content of the positive binder are respectively 80-90 wt%, 5-15 wt% and 2-10 wt%;
preferably, the positive electrode slurry is coated on the positive electrode current collector on both sides;
preferably, the thickness of the positive electrode sheet is 50 to 500 μm.
8. The production method according to any one of claims 1 to 7, wherein the lithium salt in the electrolyte of step (3) includes any one of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium bistrifluorosulfonylimide, lithium difluorooxalatoborate, lithium dioxalate borate, lithium tetrafluoroborate, or lithium nitrate, or a combination of at least two thereof;
preferably, the solvent in the electrolyte in step (3) includes any one or a combination of at least two of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate;
preferably, the separator of step (3) comprises any one of a PE separator, a ceramic separator, a coated polyester film, a cellulose film, a polyimide film, a polyamide film, a spandex or an aramid film;
preferably, the assembling of step (3) is performed in a dry environment.
9. The method of any one of claims 1 to 8, comprising the steps of:
(1) preparing a negative pole piece: mixing 90-98 wt% of a negative electrode active material, 0.5-5 wt% of a negative electrode conductive agent and 1.5-5 wt% of a negative electrode binder with a first solvent to obtain negative electrode slurry; coating the two sides of the obtained negative electrode slurry on a negative electrode current collector, and then sequentially drying, rolling and slitting to obtain a negative electrode piece with the thickness of 50-500 mu m;
in the location area of pre-compaction equipment, will negative pole piece, thickness are 1 ~ 200 mu m's lithium foil and arrange from the type membrane, the negative pole piece is located between two lithium foils, two lithium foils are located two-layer from type membrane between, the lithium foil with the area ratio of negative pole piece is 1: (1-20) the volume ratio is (1-10): 1; prepressing by adjusting any one of an air pipe, a screw rod or oil pressure and adopting the pressure of 2-10 tons to obtain a composite semi-finished product;
(2) rolling the composite semi-finished product obtained in the step (1) by using double-roll equipment, wherein the rolling pressure is 1-10 tons, and stripping off the release film after rolling to obtain a composite negative plate; in the composite negative plate, the two lithium foils are embedded into the negative plate by 1-50 mu m;
(3) preparing a positive plate: mixing 80-90 wt% of a positive electrode active material, 5-15 wt% of a positive electrode conductive agent, 2-10 wt% of a positive electrode binder and a second solvent to obtain positive electrode slurry; coating the two sides of the obtained anode slurry on an anode current collector, and then sequentially drying, rolling and cutting to obtain an anode sheet with the thickness of 50-500 mu m;
and (3) assembling the composite negative plate obtained in the step (2), the positive plate, the electrolyte and the diaphragm in a dry environment to obtain the lithium-sulfur soft package battery.
10. The lithium-sulfur soft package battery prepared according to the preparation method of any one of claims 1 to 9, wherein the battery cell of the lithium-sulfur soft package battery is a laminated battery cell.
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