WO2023216240A1 - 二次电池及其制备方法、电池模块、电池包和用电装置 - Google Patents
二次电池及其制备方法、电池模块、电池包和用电装置 Download PDFInfo
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- WO2023216240A1 WO2023216240A1 PCT/CN2022/092737 CN2022092737W WO2023216240A1 WO 2023216240 A1 WO2023216240 A1 WO 2023216240A1 CN 2022092737 W CN2022092737 W CN 2022092737W WO 2023216240 A1 WO2023216240 A1 WO 2023216240A1
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- Prior art keywords
- lithium
- negative electrode
- layer
- secondary battery
- positive electrode
- Prior art date
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- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- XLDXZSVHMLAQMY-UHFFFAOYSA-N lithium;dioxalooxyborinate Chemical compound [Li+].OC(=O)C(=O)OB([O-])OC(=O)C(O)=O XLDXZSVHMLAQMY-UHFFFAOYSA-N 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
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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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
-
- 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
- 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
Definitions
- the present application relates to the technical field of lithium batteries, and in particular to a secondary battery and its preparation method, battery module, battery pack and electrical device.
- lithium-ion batteries are widely used in energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields. Due to the great development of lithium-ion batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance.
- the lithium ions in the positive electrode plate are preferentially embedded in the reaction area of the negative electrode plate, causing the potential of the reaction area to drop, forming a voltage difference with the non-reaction area, and the lithium ions in the reaction area diffuse to the non-reaction area at a slow rate. It is difficult for the lithium ions embedded in the non-reactive area to return to the positive electrode during the discharge process, which causes irreversible lithium loss of the positive electrode and deteriorates the first efficiency, cycle performance and storage performance of the battery cell. Therefore, existing lithium-ion batteries still need to be improved in terms of first efficiency, cycle performance and storage performance.
- This application was made in view of the above-mentioned problems, and its object is to provide a secondary battery which has improved first efficiency, cycle performance, and storage performance.
- the present application provides a secondary battery and its preparation method, battery module, battery pack and electrical device.
- a first aspect of the present application provides a secondary battery, including a positive electrode piece and a negative electrode piece.
- the positive electrode piece includes a positive electrode current collector and positive electrode film layers on both surfaces of the positive electrode current collector.
- the negative electrode sheet includes a negative electrode current collector and negative electrode film layers on both surfaces of the negative electrode current collector.
- the negative electrode film layer includes a reaction zone that is opposite to the positive electrode film layer and a reaction zone that is not opposite to the positive electrode film layer.
- a non-reactive zone wherein a lithium supplement layer and a barrier layer are provided on the non-reactive zone.
- this application provides a lithium replenishing layer and a barrier layer on the non-reactive area of the negative electrode sheet.
- the lithium replenishing layer effectively prevents the lithium ions in the reaction area from diffusing and intercalating into the non-reactive area.
- the lithium in the lithium supplement layer will diffuse to the reaction zone at a slow speed; while the barrier layer completely isolates the non-reactive zone outside the lithium supplement layer, and the electrolyte cannot infiltrate it, completely blocking the lithium in the reaction zone and the lithium supplement layer. Diffusion path to the non-reaction zone, thus reducing the loss of lithium source and further improving the first efficiency, cycle performance and storage performance of the secondary battery.
- the lithium replenishing layer is disposed at one end of the non-reactive zone close to the reaction zone, and the barrier layer starts from the lithium replenishing layer and is disposed away from the reaction zone.
- the distance between the side of the lithium supplement layer close to the reaction zone and the reaction zone is 2 mm to 5 mm.
- the first efficiency and cycle performance of the secondary battery can be further improved.
- the lithium supplement layer includes a substance capable of providing active lithium; optionally including one or more of metal lithium foil, lithium powder and lithium alloy; further optionally including metal lithium foil, lithium alloy powder, one or more of silicon-lithium alloy, aluminum-lithium alloy, magnesium-lithium alloy and tin-lithium alloy.
- the theoretical capacity C Li of lithium in the lithium supplement layer satisfies 20% C 1 ⁇ C Li ⁇ 120% C 1 , optionally 90% C 1 ⁇ C Li ⁇ 120% C 1 , where C 1 is the capacity of the negative electrode film layer corresponding to the lithium supplement layer.
- the theoretical capacity C Li of lithium in the lithium supplement layer meets the given conditions, it can improve the first efficiency, cycle performance and storage performance of the secondary battery without affecting the safety performance of the secondary battery.
- the barrier layer is selected from a film or coating that cannot be wetted by the electrolyte;
- the film includes one or more of polypropylene, polyethylene, polyester fiber, and polyvinyl chloride, optionally
- the coating includes one or more of cast polypropylene, uniaxially stretched polypropylene, biaxially stretched polypropylene, polyethylene, polyester fiber and polyvinyl chloride, and further optionally includes polyethylene; the coating Including polyvinylidene fluoride, polytetrafluoroethylene, polyamide, polyimide, polymethylmethacrylate, polyurethane, polystyrene, polyacrylic acid, polyacrylamide, polyacrylonitrile and copolymers of the above substances One or several.
- the thickness of the barrier layer ranges from 6 ⁇ m to 40 ⁇ m, optionally from 10 ⁇ m to 20 ⁇ m. When the thickness of the barrier layer is within the given range, it can ensure that the pole piece does not undergo major deformation and is fully compatible with the battery core.
- the film is adhesive and has an adhesive force greater than 20 N/m.
- the adhesive force of the film is within the given range, the film can be effectively applied to the surface of the non-reactive area.
- a spacer is provided on the negative electrode sheet on the side of the lithium supplement layer away from the reaction zone and along the width direction of the negative electrode sheet, and the barrier layer starts from the spacer area , set away from the reaction zone.
- the width of the spacer zone is between 5 mm and 50 mm, optionally between 10 mm and 15 mm.
- the width of the spacer area is within the given range, it can better assist in setting the barrier layer, more effectively isolate the electrolyte without affecting the processing of the pole piece.
- the depth of the spacer region is equal to the thickness of the negative electrode film layer.
- the depth of the spacer area is equal to the thickness of the negative electrode film layer, it will prevent the electrolyte from infiltrating along the bottom negative electrode film layer into the non-reactive area, thereby preventing lithium ions from diffusing to the non-reactive area, thereby improving the first efficiency and cycle of the secondary battery. performance and storage performance.
- a second aspect of the application also provides a method for preparing a secondary battery, including the following steps:
- step (2) includes the step of providing a lithium replenishing layer and a barrier layer on the negative electrode piece;
- the secondary battery includes a positive electrode piece and a negative electrode piece.
- the positive electrode piece includes a positive electrode current collector and positive electrode film layers on both surfaces of the positive electrode current collector.
- the negative electrode piece includes a negative electrode current collector and a positive electrode film layer on both surfaces of the positive electrode current collector.
- Negative electrode film layers on both surfaces of the negative electrode current collector, the negative electrode film layer includes a reaction area arranged opposite to the positive electrode film layer and a non-reactive area not arranged opposite to the positive electrode film layer, in the non-reactive area
- the reaction zone is provided with a lithium supplement layer and a barrier layer.
- the barrier layer is provided by a coating or pasting process, optionally, the barrier layer is provided by a pasting process.
- a third aspect of the present application provides a battery module, including the secondary battery of the first aspect of the present application or a secondary battery prepared by the method of the second aspect of the present application.
- a fourth aspect of the present application provides a battery pack, including the battery module of the third aspect of the present application.
- a fifth aspect of the present application provides an electrical device, including a secondary battery selected from the first aspect of the present application or a secondary battery prepared by the method of the second aspect of the present application, a battery module of the third aspect of the present application, or a secondary battery of the present application. At least one of the battery packs of the fourth aspect is applied.
- the battery modules, battery packs and electrical devices of the present application include the secondary battery of the present application, and thus have at least the same advantages as the secondary battery.
- FIG. 1 is a schematic structural diagram of a wound cell of a secondary battery according to an embodiment of the present application.
- FIG. 2 is a schematic structural diagram of a laminated battery cell of a secondary battery according to an embodiment of the present application.
- FIG. 3 is an expanded schematic view of the negative electrode tab of the wound cell of the secondary battery according to one embodiment of the present application shown in FIG. 1 .
- FIG. 4 is a schematic structural diagram of a cell of a secondary battery according to an embodiment of the present application.
- FIG. 5 is a schematic diagram of a secondary battery according to an embodiment of the present application.
- FIG. 6 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 5 .
- FIG. 7 is a schematic diagram of a battery module according to an embodiment of the present application.
- Figure 8 is a schematic diagram of a battery pack according to an embodiment of the present application.
- FIG. 9 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 8 .
- Fig. 10 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
- Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
- the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
- the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
- a certain parameter is an integer ⁇ 2
- the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
- steps (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), also It may include steps (a), (c) and (b), or may also include steps (c), (a) and (b), etc.
- condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
- the negative electrode piece In a wound or laminated battery cell, since the negative electrode piece must completely cover the positive electrode piece, the negative electrode piece includes a reaction area that is opposite to the positive electrode piece and a non-reactive area that is not opposite to the positive electrode piece.
- the lithium ions in the positive electrode are preferentially embedded in the reaction area of the negative electrode.
- the potential in the reaction area of the negative electrode decreases, forming a voltage difference with the non-reactive area.
- the lithium ions in the reaction area It diffuses and embeds into the non-reactive area at a slow speed, and the lithium ions embedded in the non-reactive area are difficult to return to the positive electrode piece during the discharge process. This causes irreversible lithium loss of the positive electrode piece and ultimately deteriorates the first performance of the battery cell. efficiency, cycle performance and storage performance.
- This application can improve the first efficiency, cycle performance and storage performance of the secondary battery by arranging a lithium replenishing layer in the non-reactive area of the negative electrode sheet; arranging a barrier layer in the non-reactive area of the negative electrode sheet can prevent the penetration of electrolyte, It blocks the diffusion path of lithium ions in the lithium replenishment layer and the reaction zone to the non-reaction zone, improves the lithium replenishment efficiency, and further improves the first efficiency, cycle performance and storage performance of the secondary battery.
- the present application proposes a secondary battery, including a positive electrode piece and a negative electrode piece.
- the positive electrode piece includes a positive electrode current collector and positive electrode film layers on both surfaces of the positive electrode current collector.
- the negative electrode electrode The sheet includes a negative electrode current collector and negative electrode film layers on both surfaces of the negative electrode current collector.
- the negative electrode film layer includes a reaction area arranged opposite to the positive electrode film layer and a non-reactive area not arranged opposite to the positive electrode film layer, wherein in the non-reactive area A lithium replenishing layer and a barrier layer are provided on the area.
- the lithium replenishing layer effectively prevents lithium ions in the reaction area from flowing into the non-reactive area. Diffusion embedding.
- the lithium ions in the lithium replenishing layer will diffuse to the reaction area at a slow speed; while the barrier layer completely isolates the non-reactive area outside the lithium replenishing layer, and the electrolyte cannot infiltrate it. It completely blocks the diffusion path of lithium ions in the reaction zone and lithium supplement layer to the non-reaction zone, thereby reducing the loss of lithium source and further improving the first efficiency, cycle performance and storage performance of the secondary battery.
- the secondary battery further includes a separator film.
- the positive electrode piece, the negative electrode piece and the isolation film are made into a battery core using a winding or lamination process.
- the outermost layer of the negative electrode piece is the non-reactive area.
- FIG. 3 is an unfolded schematic view of the negative electrode piece in the wound battery core shown in FIG. 1 .
- a lithium supplement layer and a barrier layer are respectively provided in the empty roll non-reactive area on the A side and the closing non-reactive area on the B side.
- the optional battery core is a wound battery core.
- FIG. 4 is a schematic structural diagram of a secondary battery according to an embodiment of the present application.
- the lithium source is placed on the surface of the negative electrode film in the non-reactive zone before liquid injection to form a lithium replenishing layer.
- the standard electrode potential of lithium versus hydrogen is -3.05V.
- the negative electrode active material without embedded lithium is as follows:
- the standard electrode potential of graphite or silicon carbon materials for hydrogen is about 0V, so lithium has a voltage difference of about 3V for negative electrode active materials such as graphite or silicon carbon materials.
- an electrical circuit is formed, which is equivalent to a direct short-circuit state (in this state, the lithium source is the negative electrode and the negative electrode film is the positive electrode). Under the action of their voltage difference, the lithium in the lithium source loses electrons and becomes free.
- the mobile lithium ions are embedded in the negative electrode film layer, forming for example LiC x (x ⁇ 6) or/and Li x Si y (x>0, y>0), etc.
- the original lithium source, LiC x or/and Li forms a new stable lithium supplement layer. Since the potential of the lithium supplement layer is reduced, it can effectively prevent the lithium ions in the reaction area from diffusing and embedding into the non-reactive area.
- the lithium supplement layer is always at a relatively low potential.
- the potential of the reaction area of the negative electrode plate Gradually increases.
- the potential of the reaction zone is much higher than that of the non-reaction zone.
- the lithium in the lithium supplement layer will diffuse to the reaction zone at a slow speed, thereby improving the first efficiency and cycle performance of the secondary battery. and storage performance.
- the lithium ions in the lithium supplement layer will not only diffuse to the reaction zone under the action of the voltage difference, but will also be embedded in the non-reaction zone outside the lithium supplement layer under the action of the voltage difference.
- This application sets a barrier layer in the non-reaction zone.
- the non-reactive area outside the lithium replenishing layer is completely isolated, and the electrolyte cannot infiltrate it, completely blocking the diffusion path of lithium ions in the lithium replenishing layer and the reaction area to the non-reactive area, thereby reducing the loss of lithium source and further improving First efficiency, cycle performance and storage performance of secondary batteries.
- the lithium replenishing layer is disposed at one end of the non-reactive zone close to the reaction zone, and the barrier layer starts from the edge of the lithium replenishing layer and is disposed away from the reaction zone. If the lithium replenishment layer is placed far away from the reaction zone and in the center of the non-reaction zone, the relative diffusion path of lithium ions will become longer, reducing the lithium replenishment efficiency. At the same time, it is inconvenient to set up a barrier layer that affects production capacity.
- the distance between the side of the lithium supplement layer close to the reaction zone and the reaction zone is 2 mm to 5 mm.
- the lithium replenishment layer must be kept at a certain distance from the reaction zone to prevent slight misalignment of the positive and negative electrode sheets during the winding process, causing part of the lithium replenishment layer to enter the reaction zone and causing serious safety risks.
- the lithium in the lithium replenishment layer is being injected into the liquid. After that, it will spread to the surroundings. If it is too close to the reaction area, it may cause lithium in the reaction area close to the lithium supplement layer to over-intercalate and cause lithium precipitation, resulting in the risk of battery short circuit. Keeping a distance of more than 2mm can avoid the above risk. At the same time, the distance cannot Too far, too far will consume more lithium sources and reduce the effect of lithium supplementation. The best effect is within 5mm.
- the lithium supplement layer includes a substance capable of providing active lithium; optionally including one or more of metal lithium foil, lithium powder and lithium alloy; further optionally including metal lithium foil, lithium powder, One or more of silicon-lithium alloy, aluminum-lithium alloy, magnesium-lithium alloy and tin-lithium alloy.
- the gram capacity of lithium alloy is relatively low, and metal impurities will be formed after delithiation; the gram capacity of metallic lithium is high, and no impurities are produced after the reaction.
- the processing performance of lithium foil in metallic lithium is better than that of lithium powder, so the optional lithium supplement layer includes metallic lithium foil.
- the theoretical capacity C Li of lithium in the lithium supplement layer satisfies 20% C 1 ⁇ C Li ⁇ 120% C 1 , optionally 90% C 1 ⁇ C Li ⁇ 120% C 1 , where C 1 is The capacity of the negative electrode film layer corresponding to the lithium replenishment layer.
- V Li is the potential of the lithium supplement layer
- V negative is the lithium embedding platform voltage of the negative electrode piece
- the lithium in the lithium replenishment layer cannot be embedded in the lithium embedding area, and the lithium in the lithium intercalation area cannot be prevented from diffusing to the lithium replenishment layer.
- the theoretical capacity of lithium in the lithium replenishing layer set in the empty coil non-reactive area on side A, C B is the theoretical capacity of lithium in the lithium replenishing layer set in the ending non-reactive area on side B of the battery cell.
- Weight of the lithium replenishing layer per unit area (coating weight of the negative electrode film layer ⁇ weight ratio of the negative electrode active material ⁇ gram capacity of the negative electrode active material) ⁇ (C Li /C 1 )/theoretical capacity of lithium in the lithium replenishing layer.
- the coating weight of the negative electrode film layer is 9.4 mg/cm 2
- the negative electrode active material is artificial graphite
- the weight ratio of the negative electrode active material to the negative electrode film layer is 96%
- C Li 100% C 1
- the gram capacity of artificial graphite is 360mAh/g
- the theoretical capacity of lithium metal 3860mAh/ g.
- Calendering equipment can be used to produce different lithium supplement layer weights per unit area.
- the barrier layer is selected from a film or coating that cannot be wetted by the electrolyte;
- the film includes one or more of polypropylene, polyethylene, polyester fiber, and polyvinyl chloride, optionally including cast One or more of polypropylene, uniaxially oriented polypropylene, biaxially oriented polypropylene, polyethylene, polyester fiber and polyvinyl chloride, further optionally including polyethylene;
- the coating includes polyvinylidene fluoride, One or more of polytetrafluoroethylene, polyamide, polyimide, polymethyl methacrylate, polyurethane, polystyrene, polyacrylic acid, polyacrylamide, polyacrylonitrile and copolymers of the above substances.
- PE film Since polyethylene (PE) film has the advantages of being odorless, non-toxic, stable within -90°C to 100°C, resistant to acids and alkalis, organic solvents, low water absorption, and excellent electrical insulation properties, the film optionally contains PE film .
- polyester fibers include polyethylene terephthalate and polybutylene terephthalate.
- the thickness of the barrier layer ranges from 6 ⁇ m to 40 ⁇ m, optionally from 10 ⁇ m to 20 ⁇ m.
- the thickness of the barrier layer needs to be controlled. A barrier layer that is too thin will be easily damaged, while a barrier layer that is too thick will cause greater deformation of the pole piece. When the thickness of the barrier layer is within the given range, it can ensure that the pole piece does not undergo major deformation and is fully compatible with the battery core.
- the film is tacky with an adhesion force greater than 20 N/m, optionally greater than 200 N/m, further optionally greater than 400 N/m.
- the film has a certain viscosity, and the adhesive force is too small to closely adhere the film to the negative electrode film layer on the negative electrode piece, and is easy to tear.
- the adhesive force of the film is greater than 20N/m to effectively Apply it to the surface of the non-reactive area.
- the adhesive force of the film is greater than the cohesion between particles in the negative electrode film layer.
- a spacer is provided on the negative electrode sheet on the side of the lithium supplement layer away from the reaction area and along the width direction of the negative electrode sheet, and the barrier layer is provided starting from the spacer area and away from the reaction area. More specifically, the barrier layer is disposed on the bottom surface of the spacer region, the side of the spacer region close to the non-reactive region, and the non-reactive region away from the reaction region.
- the electrolyte can be prevented from infiltrating into the non-reaction area after liquid injection, thereby preventing the lithium ions in the lithium replenishment layer and the reaction area from diffusing to the non-reaction area, thereby preventing Further improve the first efficiency, cycle performance and storage performance of secondary batteries.
- the width of the spacer region is 5mm-50mm, optionally 10mm-15mm.
- the width of the interval area is too wide, which affects the processing performance of the pole piece, especially during the cold pressing stage, resulting in uneven compaction of the pole piece. If the width is too narrow, it will affect the non-reaction area film application process in the later stage, causing the film to be not tight and the electrolyte to penetrate from the bottom. When the width of the spacer area is within the given range, it can better assist the setting of the barrier layer, more effectively isolate the electrolyte without affecting the processing of the pole piece.
- the depth of the spacer region is equal to the thickness of the negative electrode film layer.
- the depth of the separation area is less than the thickness of the negative electrode film, that is, there is a negative electrode film layer at the bottom of the separation area, then after injection, the electrolyte will infiltrate along the negative electrode film layer at the bottom into the non-reaction area, unable to prevent the lithium replenishment layer and the reaction area.
- the lithium ions diffuse to the non-reactive area. Therefore, the depth of the spacer region is equal to the thickness of the negative electrode film layer, that is, the bottom of the spacer region is the current collector of the negative electrode plate.
- a method for preparing a secondary battery including the following steps:
- step (2) includes the step of providing a lithium replenishing layer and a barrier layer on the negative electrode piece;
- the secondary battery includes a positive electrode piece and a negative electrode piece.
- the positive electrode piece includes a positive electrode current collector and positive electrode film layers on both surfaces of the positive electrode current collector.
- the negative electrode piece includes a negative electrode current collector and two layers of positive electrode film on both surfaces of the negative electrode current collector.
- the negative electrode film layer includes a reaction area opposite to the positive electrode film layer and a non-reactive area not opposite to the positive electrode film layer. A lithium supplement layer and a barrier layer are provided on the non-reaction area.
- the barrier layer is provided by a coating or pasting process.
- the barrier layer is provided by a pasting process.
- the barrier layer to prevent electrolyte infiltration is very important and can be provided by two processes: coating or pasting. Since the coating process requires equipment for mixing, coating, baking and other steps, the process is more complicated than the pasting process. Therefore, optionally, the barrier layer is set through the pasting process.
- the lithium replenishing layer can be set by applying, rolling, coating and other processes.
- the method further includes arranging a spacer on the negative electrode sheet on the side of the lithium replenishment layer away from the reaction area and along the width direction of the negative electrode sheet, and the spacer area is cleaned by solvent, polished, or intermittent coating way to set.
- a secondary battery typically includes a positive electrode plate, a negative electrode plate, an electrolyte and a separator.
- active ions are inserted and detached back and forth between the positive and negative electrodes.
- the electrolyte plays a role in conducting ions between the positive and negative electrodes.
- the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows ions to pass through.
- the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
- the positive electrode film layer includes a positive electrode active material.
- the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
- the positive electrode current collector may be a metal foil or a composite current collector.
- the metal foil aluminum foil can be used.
- the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
- the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the cathode active material may be a cathode active material known in the art for batteries.
- the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
- the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
- lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 )), lithium nickel cobalt aluminum oxide (such as Li
- lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), phosphoric acid At least one of a composite material of lithium manganese and carbon, a composite material of lithium manganese iron phosphate, or a composite material of lithium manganese iron phosphate and carbon.
- lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
- composites of lithium iron phosphate and carbon such as LiMnPO 4
- LiMnPO 4 lithium manganese phosphate
- phosphoric acid At least one of a composite material of lithium manganese and carbon, a composite material of lithium manganese iron phosphate, or a composite material of lithium manganese iron phosphate and carbon.
- the positive electrode film layer optionally further includes a binder.
- the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
- the positive electrode film layer optionally further includes a conductive agent.
- the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
- the positive electrode sheet can be prepared by dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
- a solvent such as N -methylpyrrolidone
- the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, where the negative electrode film layer includes a negative electrode active material.
- the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
- the negative electrode current collector may be a metal foil or a composite current collector.
- the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
- the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the negative active material may be a negative active material known in the art for batteries.
- the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like.
- the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
- the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
- the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
- the negative electrode film layer optionally further includes a binder.
- the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polysodium acrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
- the negative electrode film layer optionally further includes a conductive agent.
- the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
- the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
- thickeners such as sodium carboxymethylcellulose (CMC-Na)
- the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
- a solvent such as deionized water
- the electrolyte plays a role in conducting ions between the positive and negative electrodes.
- the type of electrolyte in this application can be selected according to needs.
- the electrolyte can be liquid, gel, or completely solid.
- the electrolyte is an electrolyte solution.
- the electrolyte solution includes electrolyte salts and solvents.
- the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
- the solvent may be selected from ethylene carbonate (ethylene carbonate), propylene carbonate (propylene carbonate), ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, Methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate At least one of ester, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
- ethylene carbonate ethylene carbonate
- propylene carbonate propylene carbonate
- ethyl methyl carbonate diethyl carbonate
- dimethyl carbonate diprop
- the electrolyte optionally further includes additives.
- additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
- the secondary battery further includes a separator film.
- a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
- the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
- the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
- the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly (battery core) through a winding process or a lamination process.
- the secondary battery may include an outer packaging.
- the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
- the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
- the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
- the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
- Fig. 5 shows a square-structured secondary battery 5 as an example.
- the outer package may include a housing 51 and a cover 53 .
- the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
- the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
- the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
- the electrode assembly 52 is packaged in the containing cavity.
- the electrolyte soaks into the electrode assembly 52 .
- the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
- secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.
- FIG. 7 shows the battery module 4 as an example.
- a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
- the plurality of secondary batteries 5 can be fixed by fasteners.
- the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
- the above-mentioned battery modules can also be assembled into a battery pack.
- the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
- the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
- the battery box includes an upper box 2 and a lower box 3 .
- the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
- Multiple battery modules 4 can be arranged in the battery box in any manner.
- the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
- the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
- the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
- a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
- Figure 10 is an electrical device as an example.
- the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
- a battery pack or battery module can be used.
- the device may be a mobile phone, a tablet, a laptop, etc.
- the device is usually required to be thin and light, and a secondary battery can be used as a power source.
- the negative electrode film layer is 61 ⁇ m, and is cut into negative electrode pieces with a length of 735 mm and a film width of 93 mm.
- the coating weight of the negative electrode piece is 9.4 mg/cm 2 and the compacted density is 1.55 g/cm 3 .
- a single-sided sticky polyethylene film is pasted as a barrier layer.
- the adhesive force of the polyethylene film is 470N/ m, with a thickness of 20 ⁇ m.
- ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) in a volume ratio of 1:1:1 to obtain an organic solvent.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- LiPF 6 fully dried lithium salt LiPF 6 in the above organic solvent.
- the concentration of lithium salt is 1mol/L, and the electrolyte is obtained by mixing evenly.
- a polyethylene film with a thickness of 12 ⁇ m was selected as the isolation film.
- the secondary battery is generally prepared with reference to Example 1. The difference is that in the preparation of the negative electrode sheet, a lithium aluminum alloy is applied to the empty roll non-reactive area and the finishing non-reactive area of the negative electrode sheet, and its gram delithiation capacity is 1980mAh/g.
- the secondary battery is generally prepared as in Example 1, except that in the preparation of the negative electrode sheet, the distances between the side of the lithium foil close to the reaction zone and the reaction zone are 0 mm, 2 mm, 5 mm and 6 mm respectively.
- the secondary battery is generally prepared with reference to Example 1. The difference is that in the preparation of the negative electrode sheet, lithium foil with the same specifications is applied to the empty roll non-reactive area and the finishing non-reactive area of the negative electrode sheet, wherein the lithium foil
- the secondary battery was generally prepared as in Example 1, except that the thicknesses of the polyethylene films were 6 ⁇ m and 40 ⁇ m respectively.
- the secondary battery is generally prepared with reference to Example 1. The difference is that in the preparation of the negative electrode sheet, the single-sided adhesive polyethylene film is replaced with a single-sided adhesive polyethylene terephthalate film and a polyethylene film. Vinyl chloride film.
- the secondary battery was generally prepared as in Example 1, except that the non-reactive area of the negative electrode plate was coated with polytetrafluoroethylene as a barrier layer with a thickness of 20 ⁇ m.
- the secondary battery was generally prepared as in Example 1, except that the non-reactive area of the negative electrode plate was coated with polymethylmethacrylate as a barrier layer with a thickness of 20 ⁇ m.
- the secondary battery is generally prepared with reference to Example 1. The difference is that in the preparation of the negative electrode sheet, a spacer is provided on the negative electrode sheet on the side of the lithium supplement layer away from the reaction area and along the width direction of the negative electrode sheet.
- the spacer area is formed by removing the negative electrode film layer by polishing. Its width is 15mm and its depth is equal to the thickness of the negative electrode film layer, which is 61 ⁇ m.
- the barrier layer starts from the spacer area and is placed away from the reaction zone.
- the preparation of the secondary battery is generally similar to that of Example 18, except that the widths of the separation regions are 5 mm and 50 mm respectively.
- the secondary battery was generally prepared as in Example 18, except that the depth of the spacer region was 20 ⁇ m, that is, the negative electrode film layer in the spacer region was not completely removed.
- the secondary battery is generally prepared as in Example 1, except that in the preparation of the negative electrode sheet, a barrier layer is not provided in the non-reactive region.
- the secondary battery is generally prepared as in Example 1. The difference is that in the preparation of the negative electrode sheet, a lithium replenishing layer is not provided in the non-reactive area, and the barrier layer is provided in the entire non-reactive area.
- the secondary battery is generally prepared as in Example 1, except that in the preparation of the negative electrode sheet, a lithium replenishing layer and a barrier layer are not provided in the non-reaction area.
- the capacity measured by charging at 45°C for 10 hours at a rate of 0.02C is marked as C0, then charged at 25°C at a rate of 0.33C to 3.65V, and the capacity measured at a constant voltage of 3.65V to 0.05C is marked as C1.
- the capacity measured at the last 0.33C discharge to 2.5V is marked as D0, and D0/(C0+C1) ⁇ 100% is the first-week Coulombic efficiency (first effect) of the secondary battery.
- SOC state of charge
- Comparing Example 1 with Comparative Examples 1 to 3 by arranging a lithium replenishing layer and a barrier layer in the non-reactive area of the negative electrode plate, the first efficiency, storage performance and cycle performance of the secondary battery can be significantly improved.
- Example 1 and Example 3 to Example 6 shows that when the distance between the side of the lithium supplement layer close to the reaction zone and the reaction zone is 2mm-5mm, the first efficiency of the secondary battery can be further improved and the capacity is 80%. Storage days and number of cycles when capacity retention rate is 80%.
- the first effect of the secondary battery is good when the distance between the side of the lithium supplement layer close to the reaction zone and the reaction zone is 0 mm, if the side of the lithium supplement layer close to the reaction zone is completely close to the edge of the reaction zone, the reaction zone may Lithium precipitation occurs, which affects the safety of the battery core. Therefore, the side of the lithium replenishment layer close to the reaction zone is larger than 0mm.
- Example 1 and Example 7 to Example 11 shows that when the theoretical capacity C Li of lithium in the lithium supplement layer and the capacity C 1 of the negative electrode film layer corresponding to the lithium supplement layer satisfy 20% C 1 ⁇ C Li ⁇ 120% C 1 , which can further improve the first efficiency, storage performance and cycle performance of secondary batteries.
- Example 1 Comparing Example 1 and Examples 18 to 21, when a spacer is provided on the negative electrode sheet on the side of the lithium supplement layer away from the reaction area, the first efficiency, storage performance and cycle performance of the secondary battery can be further improved.
- Example 18 shows that when the depth of the separation area is equal to the thickness of the negative electrode film layer, the first efficiency, storage performance and cycle performance of the secondary battery can be further improved.
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Abstract
Description
Claims (16)
- 一种二次电池,包括正极极片和负极极片,所述正极极片包括正极集流体和在所述正极集流体两个表面上的正极膜层,所述负极极片包括负极集流体和在所述负极集流体两个表面上的负极膜层,所述负极膜层包括与所述正极膜层相对设置的反应区和不与所述正极膜层相对设置的非反应区,其中,在所述非反应区上设置有补锂层和阻隔层。
- 根据权利要求1所述的二次电池,其中,所述补锂层设置在所述非反应区靠近所述反应区的一端,所述阻隔层自所述补锂层开始、远离所述反应区设置。
- 根据权利要求1或2所述的二次电池,其中,所述补锂层靠近所述反应区的一侧与所述反应区的距离为2mm-5mm。
- 根据权利要求1至3中任一项所述的二次电池,其中,所述补锂层包括能够提供活性锂的物质;可选地包括金属锂箔、锂粉和锂合金中的一种或多种;进一步可选地包括金属锂箔、锂粉、硅锂合金、铝锂合金、镁锂合金和锡锂合金中的一种或几种。
- 根据权利要求1至4中任一项所述的二次电池,其中,所述补锂层中锂的理论容量C Li满足20%C 1≤C Li≤120%C 1,可选地90%C 1≤C Li≤120%C 1,其中C 1为所述补锂层对应的所述负极膜层的容量。
- 根据权利要求1至5中任一项所述的二次电池,其中,所述阻隔层选自不能被电解液浸润的薄膜或涂层;所述薄膜包括聚丙烯、聚乙烯、聚酯纤维和聚氯乙烯中的一种或几种,可选地包括流延聚丙 烯、单向拉伸聚丙烯、双向拉伸聚丙烯、聚乙烯、聚酯纤维和聚氯乙烯中的一种或几种,进一步可选地包括聚乙烯;所述涂层包括聚偏氟乙烯、聚四氟乙烯、聚酰胺、聚酰亚胺、聚甲基丙烯酸甲酯、聚氨酯、聚苯乙烯、聚丙烯酸、聚丙烯酰胺、聚丙烯腈以及上述物质的共聚物中的一种或几种。
- 根据权利要求1至6中任一项所述的二次电池,其中,所述阻隔层的厚度为6μm-40μm,可选地为10μm-20μm。
- 根据权利要求6或7所述的二次电池,其中,所述薄膜具有粘性,粘结力大于20N/m。
- 根据权利要求1至8中任一项所述的二次电池,其中,在所述负极极片上在所述补锂层远离所述反应区的一侧、沿着所述负极极片的宽度方向设置间隔区,并且所述阻隔层自间隔区开始、远离所述反应区设置。
- 根据权利要求9所述的二次电池,其中,所述间隔区的宽度为5mm-50mm,可选地为10mm-15mm。
- 根据权利要求9或10所述的二次电池,其中,所述间隔区的深度等于所述负极膜层的厚度。
- 一种制备二次电池的方法,包括以下步骤:(1)制备正极极片;(2)制备负极极片;(3)制备隔离膜;(4)制备电解液;(5)制备二次电池;其中,步骤(2)包括在所述负极极片上设置补锂层和阻隔层的步骤;所述二次电池包括正极极片和负极极片,所述正极极片包括正极集流体和在所述正极集流体两个表面上的正极膜层,所述负极极片包括负极集流体和在所述负极集流体两个表面上的负极膜层,所述负极膜层包括与所述正极膜层相对设置的反应区和不与所述正极膜层相对设置的非反应区,在所述非反应区上设置有补锂层和阻隔层。
- 根据权利要求12所述的方法,其中,所述阻隔层通过涂覆或粘贴工艺设置,可选地,所述阻隔层通过粘贴工艺设置。
- 一种电池模块,其中,包括权利要求1至11中任一项所述的二次电池或通过权利要求12或13所述的方法制备的二次电池。
- 一种电池包,其中,包括权利要求14所述的电池模块。
- 一种用电装置,其中,包括选自权利要求1至11中任一项所述的二次电池或通过权利要求12或13所述的方法制备的二次电池、权利要求14所述的电池模块或权利要求15所述的电池包中的至少一种。
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EP22938727.9A EP4318637A1 (en) | 2022-05-13 | 2022-05-13 | Secondary battery and preparation method therefor, battery module, battery pack, and electric device |
CN202280037457.2A CN117413376A (zh) | 2022-05-13 | 2022-05-13 | 二次电池及其制备方法、电池模块、电池包和用电装置 |
KR1020247000758A KR20240021222A (ko) | 2022-05-13 | 2022-05-13 | 이차전지 및 이의 제조 방법, 배터리모듈, 배터리팩과 전기기기 |
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CN216084938U (zh) * | 2021-10-28 | 2022-03-18 | 蜂巢能源科技有限公司 | 一种固态电池 |
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CN102055011A (zh) * | 2009-10-29 | 2011-05-11 | 比亚迪股份有限公司 | 一种锂离子二次电池及其制造方法 |
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CN101894937A (zh) * | 2010-07-02 | 2010-11-24 | 东莞新能源科技有限公司 | 锂离子电池及其正极片 |
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CN216084938U (zh) * | 2021-10-28 | 2022-03-18 | 蜂巢能源科技有限公司 | 一种固态电池 |
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