CN118053981A - Large cylindrical battery for improving high-nickel ternary power battery cycle, preparation method thereof and battery module containing cylindrical battery - Google Patents
Large cylindrical battery for improving high-nickel ternary power battery cycle, preparation method thereof and battery module containing cylindrical battery Download PDFInfo
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- CN118053981A CN118053981A CN202410451781.XA CN202410451781A CN118053981A CN 118053981 A CN118053981 A CN 118053981A CN 202410451781 A CN202410451781 A CN 202410451781A CN 118053981 A CN118053981 A CN 118053981A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 981
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 653
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 591
- 239000011248 coating agent Substances 0.000 claims abstract description 564
- 238000004804 winding Methods 0.000 claims abstract description 112
- 238000007755 gap coating Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005520 cutting process Methods 0.000 claims description 41
- 239000006258 conductive agent Substances 0.000 claims description 28
- 239000011267 electrode slurry Substances 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011800 void material Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000003475 lamination Methods 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 52
- 239000003792 electrolyte Substances 0.000 abstract description 42
- 230000009286 beneficial effect Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011247 coating layer Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 238000003825 pressing Methods 0.000 description 21
- 238000009472 formulation Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000011149 active material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910004764 HSV900 Inorganic materials 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910004761 HSV 900 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000004308 accommodation Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ASUTZQLVASHGKV-JDFRZJQESA-N galanthamine Chemical compound O1C(=C23)C(OC)=CC=C2CN(C)CC[C@]23[C@@H]1C[C@@H](O)C=C2 ASUTZQLVASHGKV-JDFRZJQESA-N 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- SQFSKOYWJBQGKQ-UHFFFAOYSA-N kaempferide Chemical compound C1=CC(OC)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 SQFSKOYWJBQGKQ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
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- HPOIPOPJGBKXIR-UHFFFAOYSA-N 3,6-dimethoxy-10-methyl-galantham-1-ene Natural products O1C(C(=CC=2)OC)=C3C=2CN(C)CCC23C1CC(OC)C=C2 HPOIPOPJGBKXIR-UHFFFAOYSA-N 0.000 description 1
- LPCKPBWOSNVCEL-UHFFFAOYSA-N Chlidanthine Natural products O1C(C(=CC=2)O)=C3C=2CN(C)CCC23C1CC(OC)C=C2 LPCKPBWOSNVCEL-UHFFFAOYSA-N 0.000 description 1
- 244000062250 Kaempferia rotunda Species 0.000 description 1
- 235000013422 Kaempferia rotunda Nutrition 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
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- 229960003980 galantamine Drugs 0.000 description 1
- BGLNUNCBNALFOZ-WMLDXEAASA-N galanthamine Natural products COc1ccc2CCCC[C@@]34C=CCC[C@@H]3Oc1c24 BGLNUNCBNALFOZ-WMLDXEAASA-N 0.000 description 1
- ASUTZQLVASHGKV-UHFFFAOYSA-N galanthamine hydrochloride Natural products O1C(=C23)C(OC)=CC=C2CN(C)CCC23C1CC(O)C=C2 ASUTZQLVASHGKV-UHFFFAOYSA-N 0.000 description 1
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- IYVSXSLYJLAZAT-NOLJZWGESA-N lycoramine Natural products CN1CC[C@@]23CC[C@H](O)C[C@@H]2Oc4cccc(C1)c34 IYVSXSLYJLAZAT-NOLJZWGESA-N 0.000 description 1
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Classifications
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
-
- 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
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The disclosure provides a large cylindrical battery for improving the cycle of a high-nickel ternary power battery, a preparation method thereof and a battery module containing the cylindrical battery. In the battery, the first high-nickel active coating is arranged on the inner side surface of the winding of the positive current collector, and the second high-nickel active coating is arranged on the outer side surface of the winding of the positive current collector; the inner ring high nickel active coating and the middle outer ring high nickel active coating of the second high nickel active coating are arranged at intervals along the length direction of the positive current collector, a preset gap is formed between the inner ring high nickel active coating and the middle outer ring high nickel active coating, the surface capacity of the inner ring high nickel active coating is 2.0% -6.0% larger than that of the middle outer ring high nickel active coating, the battery not only reduces the CB value of the positive electrode material of the inner ring of the positive electrode towards the outer side, improves the circulation performance, is beneficial to electrolyte circulation, also improves the problem that the internal stress of the inner ring is difficult to release, but also plays a certain role in positioning for gap coating, is beneficial to rapid water emission in the baking process, and improves the baking efficiency.
Description
Technical Field
The disclosure relates to the technical field of high-nickel ternary power batteries, in particular to a large cylindrical battery for improving the cycle of a high-nickel ternary power battery, a preparation method thereof and a battery module containing the cylindrical battery.
Background
Because the ternary material has the characteristics of high energy density, long cycle life, low cost, high safety and the like, the ternary material becomes the first choice material of the current high-performance lithium ion battery. The lithium ion battery prepared by adopting the ternary material is generally called as a ternary power battery, and in order to better adapt to the high-speed development of the new energy industry, a high-nickel ternary power battery is also appeared on the market. Because Ni in the ternary material of the high-nickel ternary power battery is more than 90%, the energy density of the ternary power battery is greatly improved, and the increasingly-changing market demands are better met.
Although ternary materials with high nickel content have the advantages of high specific capacity and low cost, there is also poor cycle performance. Especially for a large cylindrical battery, due to the special structure of the large cylindrical battery, the CB value of the positive electrode material of the positive electrode inner ring which faces to the outer side is larger because of the arc effect at the position close to the center of the large cylindrical battery, so that the positive electrode material of the region is easy to be overdischarged in the circulating process of the high-nickel ternary power battery, and the material structure of the high-nickel ternary power battery collapses in advance, namely, the capacity attenuation and electrolyte decomposition of the high-nickel ternary power battery are accelerated, so that the high-nickel ternary power battery is in circulating acceleration failure.
In order to solve the above technical problems, as disclosed in chinese patent document CN111934027a, a cylindrical lithium battery winding core and a cylindrical lithium battery are disclosed, in which the difference between the surface density of the positive electrode sheet and the surface density of the negative electrode sheet dynamically changes, that is, the surface densities of the positive electrode sheet and the negative electrode sheet synchronously change along with the change of the curvatures of the positive electrode sheet and the negative electrode sheet, so as to counteract the influence of the curvature change on the actual CB of the winding body, so that the actual CB values at different positions of the winding body are always greater than the designed CB value, thereby ensuring that the negative electrode capacity at each position of the winding body is always in an excessive state, and avoiding that the actual CB value at a certain position cannot meet the requirement of excessive negative electrode, thereby causing the short circuit of the cylindrical lithium battery winding core of the invention.
However, the above-mentioned cylindrical lithium battery is mainly improved against the phenomenon of insufficient CB value, and for the high-nickel ternary power battery, if the above-mentioned design method is adopted, the CB value of the positive electrode material with the inner ring of the positive electrode facing to the outer side deviates from the CB design value greatly, and there is still the problem of long-cycle failure of the high-nickel ternary power battery.
Disclosure of Invention
The aim of the present disclosure is to overcome the shortcomings in the prior art, and provide a large cylindrical battery which can reduce the CB value of a positive electrode material with an inner ring of the positive electrode facing to the outer side, is beneficial to electrolyte circulation, improves the problem that the internal stress of the inner ring is difficult to release, and can play a certain role in positioning for gap coating, effectively avoid the phenomenon that an overlapping area is easy to appear between an inner ring high-nickel active coating and a middle outer ring high-nickel active coating during gap coating, is beneficial to the rapid dissipation of moisture in the subsequent baking process of a positive electrode plate, improves the baking efficiency of the positive electrode plate, improves the cycle of a high-nickel ternary power battery, a preparation method thereof, and a battery module containing the cylindrical battery. .
The aim of the disclosure is achieved by the following technical scheme:
The large cylindrical battery with high nickel ternary power battery circulation comprises a winding core and a shell, wherein the winding core is arranged in the shell, the winding core is formed by sequentially laminating and winding a negative plate, a diaphragm and a positive plate, the positive plate comprises a positive current collector, a first high nickel active coating and a second high nickel active coating,
The positive current collector is provided with a winding inner side surface and a winding outer side surface which are oppositely arranged, the first high-nickel active coating is arranged on the winding inner side surface, and the second high-nickel active coating is arranged on the winding outer side surface; the second high-nickel active coating comprises an inner ring high-nickel active coating and a middle outer ring high-nickel active coating, the inner ring high-nickel active coating and the middle outer ring high-nickel active coating are arranged at intervals along the length direction of the positive current collector, and a preset gap is formed between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating;
Wherein the surface capacity of the inner ring high-nickel active coating is 2.0% -6.0% greater than that of the middle outer ring high-nickel active coating.
In one embodiment, the surface capacity of the inner ring high nickel active coating is 4% -6% greater than the surface capacity of the middle outer ring high nickel active coating.
In one embodiment, the length of the inner ring high nickel active coating is equal to the difference obtained by subtracting the width of the preset gap from the sum of the circumferences of all turns of the position, which is less than or equal to 9.0mm from the center of the winding core, of the winding start position of the positive current collector.
In one embodiment, the inner ring high nickel active coating is formed with a preset cut void adjacent to the winding start position of the positive current collector.
In one embodiment, the high-nickel ternary power battery cycle large cylindrical battery further comprises a first middle-nickel active coating and a second middle-nickel active coating, wherein the first middle-nickel active coating is arranged on one surface of the first high-nickel active coating, which is opposite to the positive current collector, and the second middle-nickel active coating is arranged on one surface of the second high-nickel active coating, which is opposite to the positive current collector.
In one embodiment, the first high nickel active coating has a Ni content of 90% or more, and/or,
The Ni content of the second high-nickel active coating is more than or equal to 90%; and/or the number of the groups of groups,
Ni content of the first middle nickel active coating is 50% -80%; and/or the number of the groups of groups,
Ni content of the second middle nickel active coating is 50% -80%; and/or the number of the groups of groups,
The number of the first high-nickel active coatings is at least two, and the first high-nickel active coatings are sequentially stacked; and/or the number of the groups of groups,
The number of the second high-nickel active coatings is at least two, and the second high-nickel active coatings are sequentially stacked.
In one embodiment, the first midnickel active coating has a lower level of conductive agent than the first high nickel active coating; and/or the number of the groups of groups,
The content of the conductive agent of the second middle nickel active coating is less than the content of the conductive agent of the second high nickel active coating.
The preparation method of the large cylindrical battery for improving the high-nickel ternary power battery circulation comprises the following steps of:
Acquiring a positive current collector roll;
Performing continuous coating operation on the winding inner side surface of the positive current collector roll by adopting high-nickel positive electrode slurry so as to form a first high-nickel active coating on the winding inner side surface of the positive current collector roll;
Performing gap coating operation on the winding outer side surface of the positive current collector roll by adopting high-nickel positive electrode slurry to obtain an inner ring high-nickel active coating and a middle outer ring high-nickel active coating which are arranged at intervals on the winding outer side surface of the positive current collector roll, so as to obtain a positive plate A, wherein the surface capacity of the inner ring high-nickel active coating is 2% -6% greater than that of the middle outer ring high-nickel active coating;
Rolling the positive plate A;
Baking the positive plate A after the rolling operation to obtain a positive plate B;
Cutting the positive plate B to obtain a positive plate;
Sequentially stacking a negative plate, a diaphragm and the positive plate to obtain a to-be-rolled body;
and (3) winding the body to be wound to obtain the large cylindrical battery with the high-nickel ternary power battery circulation according to any embodiment.
In one embodiment, the step of performing a gap coating operation on the winding outer side surface of the positive current collector roll by using high nickel positive electrode slurry comprises the following specific steps:
The coating machine carries out a first coating operation according to the set conditions of the middle-outer-ring high-nickel active coating;
closing a discharge port of the coating machine after the first coating operation is completed;
the coater moves the positive current collector roll according to a preset gap;
After the positive current collector roll moves to the preset gap position, opening a discharge hole of the coating machine;
and the coating machine performs a second coating operation according to the set conditions of the inner ring high-nickel active coating.
A battery module comprises the large cylindrical battery with the high-nickel ternary power battery circulation prepared by the method for preparing the large cylindrical battery with the high-nickel ternary power battery circulation improved in any embodiment.
Compared with the prior art, the method has at least the following advantages:
1) The second high-nickel active coating is divided into the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating, a preset gap is formed between the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating, so that the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating can be arranged separately, independent coating operation of the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating is realized, namely the independent surface capacity of the inner ring high-nickel active coating and the independent surface capacity of the middle and outer ring high-nickel active coating are well controlled, the capacity of the large cylindrical battery of the high-nickel ternary power battery cycle is effectively controlled by changing the surface capacity of the inner ring high-nickel active coating, the suitability of an anode material CB value of the large cylindrical battery of the anode with the inner ring facing the outer side is reduced, the cycle performance of the large cylindrical battery of the high-nickel ternary power battery cycle with different specifications is improved, and the utilization rate of the middle and outer ring high-nickel active coating is improved.
2) The surface capacity of the inner ring high-nickel active coating is 2.0% -6.0% larger than that of the middle and outer rings, and the surface capacity of the inner ring high-nickel active coating is only partially changed, so that the surface capacity of the inner ring high-nickel active coating can be ensured to be in a proper range, and the problem that the CB value of the positive electrode material CB of the positive electrode inner ring facing to the outer side is large, so that the long-cycle failure of the high-nickel ternary power battery is effectively avoided.
3) Because the preset gap is additionally arranged between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating, on one hand, the preset gap is beneficial to the circulation of electrolyte; on the other hand, the preset gap can reserve an expansion space for the high-nickel active coating of the inner ring so as to ensure that the structural shape of the inner ring of the infiltrated winding core is not easy to deform, thereby solving the problem that the internal stress of the inner ring is difficult to release to cause the deformation of the structural shape; on the other hand, the preset gap plays a certain role in positioning for gap coating so as to realize automatic batch production, and effectively avoid the problems that the circulating performance and cost of a large cylindrical battery of a high-nickel ternary power battery are increased due to the fact that the connecting part of the inner-ring high-nickel active coating and the middle-outer-ring high-nickel active coating is thickened due to the fact that an overlapping area is easy to appear between the inner-ring high-nickel active coating and the middle-outer-ring high-nickel active coating during gap coating, and CB difference fluctuation on two sides of the connecting part is increased; on the other hand, the preset gap improves the contact areas of the inner ring high-nickel active coating, the middle outer ring high-nickel active coating and air, is favorable for rapid water emission of the positive plate in the subsequent baking process, and improves the baking efficiency of the positive plate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present disclosure and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a flow chart of a method of preparing a large cylindrical battery for improved cycling of a high nickel ternary power battery in accordance with an embodiment of the present invention;
FIG. 2 is a schematic illustration of the structure of the coating of comparative example 1 of the present invention;
FIG. 3 is a schematic illustration of the structure of the coating of embodiment 1 of the present invention;
FIG. 4 is a schematic illustration of the structure of the coating of example 4 of the present invention;
FIG. 5 is a schematic illustration of the structure of the coating of example 5 of the present invention;
FIG. 6 is a schematic illustration of the coating structure of embodiments 5-8 of the present invention;
FIG. 7 is a chart showing comparison of CB values on both the inner and outer sides of the positive electrode in example 4 of the present invention.
Reference numerals: 10. a positive current collector roll; 20. a first high nickel active coating; 30. a first nickel-in-nickel active coating; 41. the inner ring is provided with a high nickel active coating; 42. a high nickel active coating of the middle outer ring; 51. a nickel active coating in the inner ring; 52. a nickel active coating in the middle outer ring; 60. presetting a gap; 70. presetting a cutting gap.
Detailed Description
In order that the disclosure may be understood, a more complete description of the disclosure will be rendered by reference to the appended drawings. Preferred embodiments of the present disclosure are shown in the drawings. This disclosure may, however, be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "fixed to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In order to better understand the technical scheme and beneficial effects of the present disclosure, the following further details are described in conjunction with specific embodiments:
The large cylindrical battery with the circulating high-nickel ternary power battery comprises a winding core and a shell, wherein the winding core is arranged in the shell, the winding core is formed by sequentially laminating and winding a negative plate, a diaphragm and a positive plate, the positive plate comprises a positive current collector, a first high-nickel active coating and a second high-nickel active coating, the positive current collector is provided with a winding inner side surface and a winding outer side surface which are oppositely arranged, the first high-nickel active coating is arranged on the winding inner side surface, and the second high-nickel active coating is arranged on the winding outer side surface; the second high-nickel active coating comprises an inner ring high-nickel active coating and a middle outer ring high-nickel active coating, the inner ring high-nickel active coating and the middle outer ring high-nickel active coating are arranged at intervals along the length direction of the positive current collector, and a preset gap is formed between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating; wherein the surface capacity of the inner ring high-nickel active coating is 2.0% -6.0% greater than that of the middle outer ring high-nickel active coating.
It can be appreciated that since the capacity fade sequence of the emerging high nickel ternary power cell cycle large cylindrical cell is positive ternary material > graphite, the capacity fade sequence is different from that of a conventional general lithium iron phosphate large cylindrical cell (lithium iron phosphate < graphite). Therefore, if the method of improving the CB value is adopted as in the background art, there is a positive electrode material CB with the inner ring of the positive electrode facing outward, and when the CB value increases, the lithium intercalation ratio of the negative electrode decreases, and the potential of the negative electrode is relatively high at this time, and under the condition that the charging voltage is unchanged, the potential of the positive electrode is simultaneously high, so that the reaction between the positive electrode and the electrolyte is aggravated, and the cycle acceleration fails. Therefore, the conventional method of improving CB value is not well embodied in large cylindrical batteries of high nickel ternary power battery cycles.
In order to find a positive electrode material CB with a larger value, which can effectively solve the problem that the positive electrode inner ring of a large cylindrical battery with a high-nickel ternary power battery cycle is towards the outer side, some scholars propose: the method can be deduced according to a calculation formula of CB value (the ratio of the product of the surface density of the cathode and the gram capacity of the cathode to the product of the surface density of the anode and the gram capacity of the anode), namely the problem that the CB value of the anode material of which the inner ring of the anode is towards the outer side is larger can be reduced by only reducing the surface density or the gram capacity of the cathode or by increasing the surface density or the gram capacity of the anode.
Although the problem of larger CB value of the positive electrode material of the positive electrode with the inner ring facing to the outer side can be solved by reducing the surface density or gram capacity of the negative electrode or by increasing the surface density or gram capacity of the positive electrode, when the surface density or gram capacity of the negative electrode is reduced, the overall high performance of the large cylindrical battery of the high-nickel ternary power battery cycle is affected, and the large cylindrical battery of the high-performance high-nickel ternary power battery cycle cannot be ensured, so that the development trend of the market cannot be better satisfied; the surface density or gram capacity of the positive electrode is improved by mainly integrally improving the surface capacity of the whole layer of the second high-nickel active coating, so that the surface density or gram capacity of the positive electrode is improved, the CB value requirement of the positive electrode material with the inner ring facing to the outer side is reduced, and the problem of larger CB value is solved.
However, in practical applications, the closer the second high-nickel active coating layer is to the starting position of the positive current collector winding, the larger the fluctuation range of the positive electrode material CB value of the positive electrode inner ring toward the outer side from the CB design value, while the fluctuation range of the positive electrode material CB value of the starting position of the positive current collector winding is not substantially changed, and the details can be seen from fig. 7. Therefore, if the surface capacity of the entire second high-nickel active coating layer is increased, the CB value of the second high-nickel active coating layer distant from the start position of winding of the positive current collector is not significantly improved, and thus, there is a problem that the utilization rate of the second high-nickel active coating layer distant from the start position of winding of the positive current collector is lowered.
Therefore, in the present disclosure, the second high-nickel active coating is divided into the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating, and a preset gap is formed between the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating, so that the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating can be separately arranged, so that separate coating operations of the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating are realized, that is, the independent surface capacities of the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating are better controlled, the capacity of the large cylindrical battery circulated by the high-nickel ternary power battery and the positive electrode material CB value of the positive electrode inner ring facing the outer side are effectively controlled by changing the surface capacity of the inner ring high-nickel active coating, the suitability of the large cylindrical battery circulated by the high-nickel ternary power battery with different specifications is improved, the circulating performance of the large cylindrical battery circulated by the high-nickel ternary power battery is improved, the utilization rate of the middle and the outer ring high-nickel active coating is improved, that is the problem that the surface capacity of the large-nickel active coating is obviously improved due to the whole improvement of the whole surface capacity of the second high-nickel active coating is reduced.
It can also be understood that if the surface capacity of the inner ring high nickel active coating is less than 2% of the surface capacity of the middle and outer ring high nickel active coating, the CB value of the inner and outer sides of the inner ring of the positive electrode cannot be reduced well; or when the surface capacity of the high-nickel active coating of the inner ring is higher than that of the high-nickel active coating of the middle outer ring by 6%, the CB value of the inner side and the outer side of the inner ring of the positive electrode cannot be ensured to meet the design requirement, namely, the two can influence the cycle performance of the large cylindrical battery of the high-nickel ternary power battery cycle. Therefore, the surface capacity of the inner ring high-nickel active coating is set to be 2.0% -6.0% larger than that of the middle and outer rings, and thus the problem that the positive electrode material CB value of the inner ring facing the outer side of the high-nickel ternary power battery is large and long-cycle failure of the high-nickel ternary power battery is caused by the fact that the positive electrode material CB value of the inner ring facing the outer side of the positive electrode is effectively reduced only by locally changing the surface capacity of the inner ring high-nickel active coating under the condition that the surface capacity of the negative electrode plate, the surface capacity of the first high-nickel active coating and the surface capacity of the middle and outer rings are not changed is effectively avoided.
Specifically, in one embodiment, the surface area of the inner-ring high-nickel active coating layer is greater than that of the middle-outer-ring high-nickel active coating layer, and the surface area of the inner-ring high-nickel active coating layer can be 2%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5% and 6.0%, which can be selected by those skilled in the art according to actual needs.
In order to realize that the surface capacity of the inner ring high nickel active coating is greater than 2.0% -6.0% of the surface capacity of the middle and outer ring high nickel active coating, the thickness of the inner ring high nickel active coating is required to be larger than that of the middle and outer ring high nickel active coating in the coating process, and when the inner ring high nickel active coating and the middle and outer ring high nickel active coating are subjected to cold pressing and roller pair operation under the same conditions, the inner ring high nickel active coating and the middle and outer ring high nickel active coating can be rolled to be consistent in thickness, so that the surface density of the inner ring high nickel active coating is higher than that of the middle and outer ring high nickel active coating, and the problems that the inner ring high nickel active coating is difficult to infiltrate in a subsequent electrolyte and the inner ring internal stress is difficult to release are easily caused. Therefore, the added preset gap can effectively solve the problems that electrolyte is difficult to infiltrate and internal stress of the inner ring is difficult to release; that is, the preset gap is on the one hand beneficial to the circulation of the electrolyte; on the other hand, an expansion space reserved for the high-nickel active coating of the inner ring can be reserved so as to ensure that the structural shape of the inner ring of the infiltrated winding core is not easy to deform, thereby solving the problem that the internal stress of the inner ring is difficult to release so as to cause the deformation of the structural shape; on the other hand, the high-nickel active coating plays a certain role in positioning for gap coating so as to realize automatic batch production, and effectively avoid the problems that the circulating performance and the cost of a large cylindrical battery of which the circulating performance is influenced by the CB difference fluctuation on two sides of the high-nickel ternary power battery become high because the connecting part of the high-nickel active coating of the inner ring and the high-nickel active coating of the middle and outer rings is thickened due to the fact that an overlapping area is easy to appear between the high-nickel active coating of the inner ring and the high-nickel active coating of the middle and outer rings during gap coating; on the other hand, the contact area of the inner-ring high-nickel active coating and the middle-outer-ring high-nickel active coating with air is also improved, the rapid water emission of the positive plate in the subsequent baking process is facilitated, and the baking efficiency of the positive plate is improved.
It is worth mentioning that, at present, in order to better improve the high performance of the large cylindrical battery of the high-nickel ternary power battery cycle, a full tab structure is generally adopted, and the large cylindrical battery of the full tab structure further causes the problems that the internal stress release of the inner ring of the large cylindrical battery of the high-nickel ternary power battery cycle is difficult and the electrolyte infiltration is difficult. Therefore, the preset gap additionally arranged in the method can better solve the problems that the internal stress release of the large cylindrical battery of the high-nickel ternary power battery circulation of the full tab is difficult and the electrolyte infiltration is difficult, so as to ensure that the large cylindrical battery of the high-nickel ternary power battery circulation with high performance and good structural shape is prepared and obtained, and the market demand is better met.
In the present disclosure, the initial position of the first high-nickel active coating near the positive current collector winding is the positive electrode material with the inner ring of the positive electrode facing inwards, and the initial position of the second high-nickel active coating near the positive current collector winding is the positive electrode material with the inner ring of the positive electrode facing outwards, namely the inner ring high-nickel active coating.
In the present disclosure, the surface area refers to the total capacity (product of surface density and gram capacity) that the active material contained can exert per unit area.
In a preferred embodiment, the CB value of the positive electrode material of the inner ring high-nickel active coating can be effectively reduced by setting the surface capacity of the inner ring high-nickel active coating to be 4% -6% larger than that of the middle outer ring high-nickel active coating, so that the full charge potential of the positive electrode material of the positive electrode inner ring towards the outer side is well reduced, and the capacity attenuation of the positive electrode material of the positive electrode inner ring towards the outer side is well reduced.
It can be understood that, at present, chinese patent document CN114824508 a discloses an electrochemical device, and specifically discloses that by changing the thickness and gram capacity between the positive and negative electrode corner regions and the positive and negative electrode flat regions, the interface problem of purple spots and lithium precipitation in the positive and/or negative electrode corner regions is improved, the safety performance of the electrochemical device is improved, and a certain gap is reserved in the positive and/or negative electrode corner regions, so that the positive and/or negative electrode sheets have sufficient space expansion during the charge and discharge cycle of the electrochemical device, and the risk of extrusion deformation of the positive and/or negative electrode corner regions due to expansion is reduced. However, since the gram capacity of the anode and cathode corner regions is higher than that of the anode and cathode straight regions, and the thickness of the anode and cathode corner regions is smaller than that of the anode and cathode straight regions, the surface density of the anode and cathode corner regions is higher than that of the anode and cathode straight regions, and as can be seen in conjunction with fig. 1, a reserved gap is arranged between the anode and cathode corner regions, so that there is enough space expansion for the anode and cathode electrode sheets 10 and 20 to a certain extent, but the compacted porosity is reduced due to the high surface densities of the anode and cathode corner regions, so that the electrolyte cannot quickly and comprehensively infiltrate the active material of the bottom layer (the active material close to the anode current collector). Therefore, in the present disclosure, the preset gap is extended along the width direction of the positive current collector, so as to ensure that the electrolyte can quickly and more comprehensively infiltrate the positive electrode active material at the bottom of the high-nickel active coating of the inner ring, thereby effectively avoiding the problem of slower infiltration of the traditional electrolyte.
In one embodiment, the ends of the preset gap are flush with the ends of the width of the positive current collector to ensure that electrolyte can enter the preset gap more quickly.
In one embodiment, the accommodating amount of the preset gap is at least greater than the expansion amount of the inner ring high nickel active coating and less than 5mm.
It can be understood that if the accommodation amount (i.e., the total volume) of the preset gap is equal to the expansion amount of the inner-ring high-nickel active coating, the infiltrated inner-ring high-nickel active coating is just abutted against the middle-outer-ring high-nickel active coating, and the porosity of the compacted inner-ring high-nickel active coating is reduced due to the relatively high surface capacity of the inner-ring high-nickel active coating, which is not beneficial to the backflow and circulation of the long-cycle electrolyte of the large-cylinder battery of the infiltrated high-nickel ternary power battery cycle. If the containing amount of the preset gap is larger than 5mm, the unit area capacity of the middle-outer-ring high-nickel active coating or the inner-ring high-nickel active coating is reduced, so that the utilization rate of the unit coating area of the second high-nickel active coating is influenced, and a large cylindrical battery with high energy performance and good structural shape and high nickel ternary power battery circulation cannot be prepared. Therefore, in the present disclosure, by setting the accommodation amount of the preset gap to be at least greater than the expansion amount of the inner ring high nickel active coating and less than 5mm, the distribution of the preset gap in the positive current collector is more suitable, so that the utilization rate of the unit coating area of the second high nickel active coating is ensured to the greatest extent, and the circulation channel of the electrolyte is still maintained between the infiltrated inner ring high nickel active coating and the middle outer ring high nickel active coating, which is beneficial to the backflow and circulation of the electrolyte of the large cylindrical battery of the high nickel ternary power battery circulation after long circulation, thereby improving the circulation performance of the large cylindrical battery of the high nickel ternary power battery circulation.
In one of the embodiments, the preset gap may be 2mm, 3mm, 4mm or 5mm. In a preferred embodiment, the predetermined gap is 2mm.
In one embodiment, the areal density of the inner ring high nickel active coating remains uniform along the length of the positive current collector.
It can be understood that compared with the traditional mode of sequential gradient, the problem of poor consistency of CB values is caused by the fact that the surface density of positive and negative electrode plates of the traditional cylindrical lithium battery is continuously changed, so that the connection change surface density is difficult to control in the actual coating process. Therefore, the surface density of the inner ring high-nickel active coating is set to be consistent in the length direction of the positive current collector, so that the coating difficulty is reduced, and the consistency of the overall CB value of the inner ring high-nickel active coating is ensured to be better, thereby more effectively reducing the capacity fading of the positive electrode material.
In one embodiment, the length of the inner ring high nickel active coating is equal to the difference obtained by subtracting the width of the preset gap from the sum of the circumferences of all turns of the position, which is less than or equal to 9.0mm from the center of the winding core, of the winding start position of the positive current collector.
It can be understood that in practical application, the phenomenon that the CB value of the positive electrode material of the positive electrode inner ring is larger towards the outer side is most likely to occur at the position of the circle center of the winding core which is less than or equal to 9.0mm distance. Therefore, in the present disclosure, the difference obtained by subtracting the width of the preset gap from the sum of the circumferences of all the turns of the inner ring high-nickel active coating, where the length of the inner ring high-nickel active coating is equal to the position where the winding start position of the positive current collector is less than or equal to 9.0mm from the center of the winding core, is set to ensure that the inner ring high-nickel active coating can be just located at the position where the center of the winding core is less than or equal to 9.0mm after winding, so that the overall CB value of the inner ring high-nickel active coating is reduced more comprehensively, that is, the fluctuation range of the overall CB value of the inner ring high-nickel active coating is ensured to be between 0.04 and 0.06, which means that the utilization rate of the anode material is increased by about 5%, the capacity of the inner ring high-nickel active coating in a local area is improved by about 5%, the utilization rate of the inner ring high-nickel active coating is not only improved, and the cycle capacity retention rate of a large cylindrical battery of the whole high-nickel ternary power battery cycle is improved.
Specifically, in one embodiment, the inner ring high nickel active coating length calculation formula l=pi of positive electrode turns (winding needle diameter+positive electrode turns (separator thickness×2+positive electrode sheet thickness+negative electrode sheet thickness)) -width of preset gap, wherein the positive electrode turns are positive electrode sheet turns at positions ranging from winding start position to positions less than or equal to 9.0mm from the center of the winding core; positive electrode circle number= (9*2-winding needle diameter)/(separator thickness. Times.2+positive electrode thickness+negative electrode thickness) to ensure that the inner ring high nickel active coating can be just positioned at the position of the circle center <9.0mm of the winding core after winding, so as to comprehensively reduce the overall CB value of the inner ring high nickel active coating.
In one embodiment, the inner ring high nickel active coating is formed with a preset cut void adjacent to the winding start position of the positive current collector. It can be understood that, in order to realize continuous production of the inner-ring high-nickel active coating and the middle-outer-ring high-nickel active coating, a preset cutting gap is formed at the winding starting position of the inner-ring high-nickel active coating adjacent to the positive current collector, so that the preset cutting gap is additionally arranged to provide a cutting position for each adjacent positive plate on one hand, and rapid cutting of each adjacent positive plate is realized; on the other hand, the preset cutting gap can further improve the circulation of electrolyte and release of internal stress of the inner ring, so that the large cylindrical battery with good structural shape and high performance and high nickel ternary power battery circulation is ensured to be prepared.
It is worth mentioning that if only the preset gap is added between the inner-ring high-nickel active coating and the middle-outer-ring high-nickel active coating, the circulation of the electrolyte in the radial plane of the winding core is poor, and the problem of structural deformation still exists because the internal stress of the inner ring cannot be released rapidly. Therefore, in the present disclosure, since the preset cutting gap is disposed at one end of the inner ring high nickel active coating adjacent to the winding start position of the positive current collector, the preset gap is disposed between the inner ring high nickel active coating and the middle and outer ring high nickel active coatings, that is, the preset gap is located at the end of the inner ring high nickel active coating, so that the inner ring high nickel active coating after winding can be ensured to release internal stress to the preset gap and the preset cutting gap on both sides well, and the circulation of electrolyte in the radial plane of the winding core is improved, so that the electrolyte circulates more comprehensively in the inner ring high nickel active coating, thereby ensuring that a large cylindrical battery with better structural shape and higher circulation performance and high nickel ternary power battery circulation is obtained.
Likewise, the preset cutting gap also has a structure similar to the preset gap, that is, the preset cutting gap is at least larger than the expansion amount of the inner ring high nickel active coating and smaller than 5mm. In a preferred embodiment, the preset cut gap is 2mm.
In one embodiment, when the preset cutting gap and the preset gap are added at the same time, the length of the inner ring high nickel active coating is equal to the difference value obtained by subtracting the width of the preset gap and the preset cutting gap from the sum of the circumferences of all the circles of the position, where the winding starting position of the positive current collector is less than or equal to 9.0mm away from the circle center of the winding core.
In one embodiment, the number of the first high-nickel active coatings is at least two, and each first high-nickel active coating is sequentially stacked, so as to ensure that a high-performance high-nickel ternary power battery circulating large cylindrical battery is obtained. Meanwhile, in one embodiment, the number of the second high-nickel active coatings is at least two, and each second high-nickel active coating is sequentially stacked, so as to ensure that a high-performance high-nickel ternary power battery circulating large cylindrical battery is obtained.
It should be noted that, since Ni of the first high nickel active coating layer and the second high nickel active coating layer is generally greater than 90%, they are extremely reactive with the electrolyte. Therefore, the person skilled in the art generally will not add the preset gap and the preset cutting gap on the second high nickel active coating at the same time, mainly because if the preset gap and the preset cutting gap are added on the second high nickel active coating at the same time, the surface area of the second high nickel active coating is further increased, the contact area between the second high nickel active coating and the electrolyte is increased, the migration amount of the conductive agent in the baking process of the second high nickel active coating and the first high nickel active coating is increased, the specific surface area of the conductive agent of the second high nickel active coating and the first high nickel active coating is increased, and the decomposition reaction between the surface layers of the first high nickel active coating and the second high nickel active coating and the electrolyte is aggravated, so that the capacity attenuation of the positive electrode materials on the surface layers of the first high nickel active coating and the second high nickel active coating is aggravated, and the cycle performance of the large cylindrical battery of the high nickel ternary power battery is seriously affected.
In order to solve the above technical problems, in one embodiment, the circulating large cylindrical battery of the high-nickel ternary power battery further includes a first middle nickel active coating and a second middle nickel active coating, the first middle nickel active coating is disposed on a surface of the first high nickel active coating facing away from the positive current collector, the second middle nickel active coating is disposed on a surface of the second high nickel active coating facing away from the positive current collector, so that the added first middle nickel active coating and the first high nickel active coating can form a gradient difference in formulation, and the second middle nickel active coating and the second high nickel active coating can form a gradient difference in formulation, and as the Ni content of the first middle nickel active coating and the second middle nickel active coating is small and is located at the outermost side, the reaction of the first middle nickel active coating and the second middle nickel active coating with the electrolyte is reduced, and the content of the conductive agent on the surface of the first middle nickel active coating and the second middle nickel active coating is also reduced, and the phenomena of the first high nickel active coating and the second high nickel active coating directly located at the outer side are further reduced, and the phenomena of the high nickel active material of the first high nickel active coating and the second positive active coating are reduced.
Specifically, in one embodiment, the Ni content of the first high nickel active coating is greater than or equal to 90% to ensure that the first high nickel active coating has a higher energy density. Likewise, in one embodiment, the second high nickel active coating has a Ni content of 90% or more; to ensure a higher energy density of the second high nickel active coating.
In one embodiment, the Ni content of the first middle nickel active coating is 50% -80% to ensure that the Ni content of the first middle nickel active coating is less than the Ni content of the first high nickel active coating; likewise, in one embodiment, the Ni content of the second middle nickel active coating is 50% -80%, so as to ensure that the Ni content of the first middle nickel active coating is less than that of the first high nickel active coating, and especially, the Ni content of the first high nickel active coating is greater than or equal to 90% and the Ni content of the second high nickel active coating is greater than or equal to 90%, so that the formation of a formulation gradient difference between the first high nickel active coating and the first middle nickel active coating is more suitable, the formation of a formulation gradient difference between the second high nickel active coating and the second middle nickel active coating is more suitable, the reaction of the first high nickel active coating and the second high nickel active coating with an electrolyte is well reduced, and the capacity fading phenomenon of the cathode materials on the surface layers of the first high nickel active coating and the second high nickel active coating is well reduced.
In a preferred embodiment, the Ni content of both the first and second mid-nickel active coatings is 60% and the Ni content of both the first and second high-nickel active coatings is 90%. It can be understood that, since the stability of the positive electrode material of the first middle nickel active coating and the second middle nickel active coating is better when the Ni content is 60%, the reaction of HF in the electrolyte with the first high nickel active coating and the second high nickel active coating is effectively blocked, and particularly, the use of the first high nickel active coating and the second high nickel active coating with the Ni content of 90% is matched, under the condition of meeting high performance, the phenomenon of capacity fading of the positive electrode material is also more effectively reduced.
It is understood that the conductive agent is easily migrated to the outer surface layers of the first and second high nickel active coatings by the solvent during baking process, so that the content of the conductive agent in the outer surface layers of the first and second high nickel active coatings is high to aggravate the capacity fade of the positive electrode material. Thus, in one embodiment, the first midnickel active coating has a lower level of conductive agent than the first high nickel active coating; meanwhile, the content of the conductive agent matched with the second middle nickel active coating is smaller than that of the conductive agent of the second high nickel active coating, so that the content of the conductive agent finally migrated to the first middle nickel active coating and the second middle nickel active coating is reduced, and the capacity fading phenomenon of the anode material is effectively reduced. Specifically, in one embodiment, the content of the conductive agent of the first middle nickel active coating is less than 0.3% -0.5% of the content of the conductive agent of the first high nickel active coating, and the content of the conductive agent of the second middle nickel active coating is less than 0.3% -0.5% of the content of the conductive agent of the second high nickel active coating.
In one embodiment, the second middle-nickel active coating comprises a middle-nickel active coating in the inner ring and a middle-outer ring, the middle-nickel active coating in the inner ring is arranged on the inner-ring high-nickel active coating, the middle-nickel active coating in the inner ring is flush with the peripheral edge of the inner-ring high-nickel active coating, the middle-outer ring middle-nickel active coating is arranged on the middle-outer ring high-nickel active coating, and the middle-outer ring middle-nickel active coating is flush with the peripheral edge of the middle-outer ring high-nickel active coating, so that the inner-ring middle-nickel active coating and the middle-outer ring middle-nickel active coating can be ensured to comprehensively block the reaction of electrolyte with the inner-ring high-nickel active coating and the inner-ring high-nickel active coating.
In one embodiment, the surface capacity of the nickel active coating in the inner ring is set to be 2% -6% greater than the surface capacity of the nickel active coating in the inner ring under the condition that the surface capacities of the first high nickel active coating, the inner ring high nickel active coating, the middle outer ring high nickel active coating and the middle outer ring medium nickel active coating are kept unchanged. It can be understood that the overall CB value of the nickel active coating in the inner ring is reduced only by locally changing the surface capacity of the nickel active coating in the inner ring, so that the problem that the CB value of the positive electrode material of the positive electrode inner ring towards the outer side is larger is effectively avoided, the capacity attenuation of the positive electrode material of the positive electrode inner ring towards the outer side is effectively reduced, and the utilization rate of the nickel active coating in the middle and outer rings is also improved under the condition that the reaction between electrolyte and the inner ring high nickel active coating is reduced; the full charge potential of the positive electrode material of the positive electrode with the inner ring facing to the outer side is effectively reduced, and the preparation of the high-performance large cylindrical battery with the high-nickel ternary power battery circulation is ensured.
The present disclosure also provides a method for manufacturing a large cylindrical battery for improving the cycle of a high-nickel ternary power battery, the method for manufacturing a large cylindrical battery for improving the cycle of a high-nickel ternary power battery comprising the steps of: acquiring a positive current collector roll; performing continuous coating operation on the winding inner side surface of the positive current collector roll by adopting high-nickel positive electrode slurry so as to form a first high-nickel active coating on the winding inner side surface of the positive current collector roll; performing gap coating operation on the winding outer side surface of the positive current collector roll by adopting high-nickel positive electrode slurry to obtain an inner ring high-nickel active coating and a middle outer ring high-nickel active coating which are arranged at intervals on the winding outer side surface of the positive current collector roll, so as to obtain a positive plate A, wherein the surface capacity of the inner ring high-nickel active coating is 2% -6% greater than that of the middle outer ring high-nickel active coating; rolling the positive plate A; baking the positive plate A after the rolling operation to obtain a positive plate B; cutting the positive plate B to obtain a positive plate; sequentially stacking a negative plate, a diaphragm and the positive plate to obtain a to-be-rolled body; and (3) winding the body to be wound to obtain the large cylindrical battery with the high-nickel ternary power battery circulation according to any embodiment.
According to the preparation method of the large cylindrical battery for improving the circulation of the high-nickel ternary power battery, the high-nickel positive electrode slurry is adopted to carry out gap coating operation on the winding outer side surface of the positive current collector roll, so that the problem of long-cycle failure of the high-nickel ternary power battery caused by the fact that the positive electrode material value of the positive electrode inner ring is larger than that of the positive electrode material of the positive electrode inner ring, namely a preset gap is formed between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating, the surface capacity of the inner ring high-nickel active coating is 2% -6% larger than that of the middle outer ring high-nickel active coating, and therefore the surface capacity of the inner ring high-nickel active coating is only partially changed, the problem that the inner ring high-nickel active coating is difficult to release the inner ring is difficult to infiltrate is solved, and the problem that the inner ring structure is difficult to deform after the inner ring is ensured is avoided; on the other hand, the preset gap plays a certain role in positioning for gap coating, so that the problems that the circulating performance and the cost of a large cylindrical battery of a high-nickel ternary power battery are increased due to the fact that the CB difference value fluctuation on two sides of the connecting part between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating is increased due to the fact that the overlapping area is easily formed between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating during gap coating are effectively avoided; on the other hand, the preset gap improves the contact areas of the inner ring high-nickel active coating and the middle outer ring high-nickel active coating with air, so that the rapid dissipation of moisture in the subsequent baking process of the positive plate is facilitated, the baking efficiency of the positive plate is improved, the production process is simple, and the coating difficulty is low.
Referring to fig. 1, in order to better understand the technical scheme and the beneficial effects of the present disclosure, the following describes the present disclosure in further detail with reference to specific embodiments, and the preparation method of a large cylindrical battery for improving the cycle of a high-nickel ternary power battery according to an embodiment includes some or all of the following steps:
And S101, acquiring a positive current collector roll to provide support for the first high-nickel active coating and the second high-nickel active coating. Specifically, the positive current collector roll has a winding inner side and a winding outer side to ensure that the subsequent continuous coating operation is performed on the winding inner side and the gap coating operation is performed on the winding outer side.
S102, continuously coating the winding inner side surface of the positive current collector roll by adopting high-nickel positive electrode slurry so as to form a first high-nickel active coating on the winding inner side surface of the positive current collector roll.
S103, performing gap coating operation on the winding outer side surface of the positive current collector roll by adopting high-nickel positive electrode slurry so as to form an inner ring high-nickel active coating and a middle outer ring high-nickel active coating which are arranged at intervals on the winding outer side surface of the positive current collector roll to obtain a positive plate A, wherein the surface capacity of the inner ring high-nickel active coating is 2% -6% greater than that of the middle outer ring high-nickel active coating.
It can be understood that, because the gap coating operation is performed on the winding outer side surface, the winding outer side surface can form an inner ring high nickel active coating and a middle outer ring high nickel active coating which are arranged at intervals, and the surface capacity of the inner ring high nickel active coating is 2% -6% greater than that of the middle outer ring high nickel active coating, so that the surface capacity of the inner ring high nickel active coating can be in a proper range only by locally changing the surface capacity of the inner ring high nickel active coating, the problem that the CB value of the positive electrode material of the positive electrode towards the outer side is larger to cause long-cycle failure of the high nickel ternary power battery is effectively avoided, the additionally arranged preset gap is beneficial to the circulation of electrolyte, and the preset gap can reserve an expansion space for the inner ring high nickel active coating, so that the problem that the inner ring stress is difficult to release is solved, and the inner ring structural shape of the impregnated winding core is difficult to deform is solved; on the other hand, the preset gap plays a certain role in positioning for gap coating, so that the problems that the circulating performance and the cost of a large cylindrical battery of a high-nickel ternary power battery are increased due to the fact that the CB difference value fluctuation on two sides of the connecting part between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating is increased due to the fact that the overlapping area is easily formed between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating during gap coating are effectively avoided; on the other hand, the preset gap improves the contact areas of the inner ring high-nickel active coating and the middle and outer rings high-nickel active coating with air, so that the rapid water emission of the positive plate in the subsequent baking process is facilitated, the baking efficiency of the positive plate is improved, the production process is simple, the coating difficulty is low, and the utilization rate of the middle and outer rings high-nickel active coating is improved.
And S104, carrying out rolling operation on the positive plate A to obtain the coating surface density required by production.
And S105, baking the positive plate A after the rolling operation to obtain a positive plate B.
It can be understood that the contact area between the inner ring high nickel active coating and the middle and outer rings high nickel active coating and air is increased due to the additionally arranged preset gap, so that the rapid dissipation of moisture of the positive plate in the subsequent baking process is improved, and the baking efficiency of the positive plate is further improved.
S106, cutting the positive plate B to obtain the positive plate required by production.
And S107, sequentially stacking the negative plate, the diaphragm and the positive plate to obtain a to-be-rolled body.
S108, winding the to-be-wound body to obtain the large cylindrical battery with the high-nickel ternary power battery circulation in any embodiment.
According to the preparation method, the surface capacity of the high-nickel active coating of the inner ring can be ensured to be in a proper range only by locally changing the surface capacity of the high-nickel active coating of the inner ring, the problem that the CB value of the positive electrode material of the outer ring of the positive electrode is larger to cause long-cycle failure of the high-nickel ternary power battery is effectively avoided, the additionally arranged preset gap is beneficial to circulation of electrolyte on one hand, and the expansion space reserved for the high-nickel active coating of the inner ring can be reserved for the preset gap on the other hand, so that the problem that the internal stress of the inner ring is difficult to release is solved, and the structural shape of the inner ring of the impregnated winding core is difficult to deform is ensured; on the other hand, the preset gap plays a certain role in positioning for gap coating, so that the problems that the circulating performance and the cost of a large cylindrical battery of a high-nickel ternary power battery are increased due to the fact that the CB difference value fluctuation on two sides of the connecting part between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating is increased due to the fact that the overlapping area is easily formed between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating during gap coating are effectively avoided; on the other hand, the preset gap improves the contact areas of the inner ring high-nickel active coating and the middle and outer rings high-nickel active coating with air, so that the rapid water emission of the positive plate in the subsequent baking process is facilitated, the baking efficiency of the positive plate is improved, the production process is simple, the coating difficulty is low, and the utilization rate of the middle and outer rings high-nickel active coating is improved.
In one embodiment, the step of performing a gap coating operation on the winding outer side surface of the positive current collector roll by using high nickel positive electrode slurry comprises the following specific steps: the coating machine carries out a first coating operation according to the set conditions of the middle-outer-ring high-nickel active coating; closing a discharge port of the coating machine after the first coating operation is completed; the coater moves the positive current collector roll according to a preset gap; and after the positive current collector roll moves to the preset gap position, opening a discharge hole of the coating machine, and performing a second coating operation by the coating machine according to the set conditions of the inner ring high-nickel active coating.
It can be appreciated that, first, the coater performs a first coating operation according to the set conditions of the middle-outer-ring high-nickel active coating layer to form the middle-outer-ring high-nickel active coating layer on the wound outer side of the positive current collector roll; then, after the first coating operation is finished, closing a discharge port of the coating machine to ensure that high-nickel anode slurry at the discharge port cannot leak into a preset gap to cause a waste phenomenon; and then, after the positive current collector roll moves to the preset gap position, opening a discharge hole of the coating machine to perform a second coating operation, so that the coating machine performs the second coating operation according to the set conditions of the inner ring high nickel active coating, and the inner ring high nickel active coating is formed on the outer side surface of the winding at intervals, thereby realizing the gap coating of the inner ring high nickel active coating and the middle outer ring high nickel active coating.
In one embodiment, the first coating operation, the second coating operation and the continuous coating operation are all constant coating, so that the consistency of the inner ring high-nickel active coating, the middle outer ring high-nickel active coating and the first high-nickel active coating is better ensured, and compared with the traditional continuously-changing coating mode, the consistency of the constant coating surface density is better, so that the fluctuation range of CB of the whole inner ring high-nickel active coating is ensured to be smaller, the capacity exertion of the local area of the inner ring high-nickel active coating is improved, and the capacity of a large cylindrical battery of the whole high-nickel ternary power battery cycle is improved; the use amount of the high-nickel active coating of the middle and outer rings is reduced, and the CB value of the position (2.3 mm) which is closer to the center of the coil core is ensured to be closer to the lower limit value.
In one embodiment, after the step of performing the second coating operation by the coating machine according to the setting conditions of the inner ring high nickel active coating layer and before the step of performing the rolling operation on the positive electrode sheet a, the method further comprises the following specific steps: closing a discharge hole of the coating machine, moving the positive current collector roll by the coating machine according to a preset cutting gap, opening the discharge hole of the coating machine to enter the next round of coating operation after the positive current collector roll moves to the preset cutting gap so as to ensure that the preset cutting gap is formed between every two adjacent positive plates, and enabling the additionally arranged preset cutting gap to provide a better cutting position for every adjacent positive plate so as to realize quick cutting of every adjacent positive plate; and the additionally arranged preset cutting gap can further improve the circulation of electrolyte and release of internal stress of the inner ring, so as to ensure that the large cylindrical battery with good structural shape and high performance and high nickel ternary power battery circulation is prepared.
It can be further understood that during gap coating, the coating operation of the middle-outer-ring high-nickel active coating is performed first, and then the coating operation of the inner-ring high-nickel active coating is performed, so that the middle-outer-ring high-nickel active coating is ensured to be in contact with a roller press first during subsequent passing operation, so that the middle-outer-ring high-nickel active coating can realize good buffering of the rolling pressure with larger fluctuation, the rolling pressure entering the inner-ring high-nickel active coating is ensured to be relatively stable, further, the preset gap and the preset cutting gap are ensured not to be changed greatly during the passing operation, the preset gap and the preset cutting gap are ensured to meet the expansion amount of the inner-ring high-nickel active coating, and meanwhile, a circulation channel of electrolyte is ensured to be maintained after infiltration, and the backflow and circulation of electrolyte of a large-cylindrical battery of a high-nickel ternary power battery after long circulation are facilitated, so that the problem that the rolling pressure of the inner-ring high-nickel active coating after rolling is poor in surface density due to large rolling pressure fluctuation is effectively avoided, and the preset gap and the starting phenomenon of the high-nickel active coating after rolling is occupied by the preset gap after rolling is caused in severe conditions is also.
In one embodiment, the positive electrode sheet a is subjected to a roll passing operation by using a cold press pair roll, so as to compact and roll the inner ring high nickel active coating, the middle outer ring high nickel active coating and the first high nickel active coating, so that after the cold press pair roll operation under the same conditions, the inner ring high nickel active coating and the middle outer ring high nickel active coating can be rolled into the same thickness, and the wound winding core can maintain a better structural shape (cylindrical shape). Specifically, the cold press twin roll conditions are: under normal temperature, the cold pressing speed is 10-40 m/s, and the cold pressing pressure is 5-8 tons.
It can be understood that the high nickel ternary material of the positive plate A after cold pressing and roller pairing is easy to be excessively brittle, so that the phenomenon that powder is easily dropped on the rolled positive plate due to the influence of the arc rate is easy to occur, and the problem of increasing the K value is caused. Therefore, in the present disclosure, before the step of cold pressing the positive electrode sheet a into a pair of rollers, preheating the positive electrode sheet a, wherein the preheating is performed at 20 ℃ to 40 ℃ for 1min to 5min; therefore, the high-nickel active coating adhesive ensures that the first high-nickel active coating and the second high-nickel active coating adhesive have better viscosity, can effectively avoid the phenomenon that the inner ring high-nickel active coating and the middle and outer ring high-nickel active coating are easy to extend outwards in the rolling process, and can improve the connection firmness of active substances in the first high-nickel active coating and the second high-nickel active coating, and can effectively avoid the phenomenon that the coiled positive plate is easy to fall off powder.
It can also be understood that if the preheating temperature is higher than 40 ℃, normal operation of cold-pressing pair roller operation cannot be ensured, and if the preheating temperature is lower than 20 ℃, the phenomenon that the high nickel ternary material after cold-pressing pair roller is too brittle still exists. Therefore, when the preheating operation is carried out at 20-40 ℃ for 1-5 min, the viscosity of the adhesive is improved during the cold pressing operation on the rollers, and meanwhile, the phenomenon that the large cylindrical battery of the high-nickel ternary power battery is easy to fall off is avoided.
It can be understood that although the phenomenon that the large cylindrical battery of the high-nickel ternary power battery cycle is easy to fall off can be improved by a preheating mode, the improvement effect needs to be further improved. Thus, in one embodiment, the binder used for the first and second high nickel active coatings is one of suv 5130 or alcma HSV 900. Because the adhesive property of the Suwei 5130 or the Acomax HSV900 is better, the adhesive property of the first high-nickel active coating and the second high-nickel active coating can be further improved, and the phenomenon that the large cylindrical battery of the high-nickel ternary power battery is easy to fall off is more effectively avoided.
It will be appreciated that since Ni of the first and second high nickel active coatings 20 and 20 is typically greater than 90%, they are extremely reactive with the electrolyte, and the addition of the preset gap 60 and preset cut gap 70 of the present disclosure further increases the surface area of the second high nickel active coating, resulting in a faster decay of the positive electrode material capacity of the second high nickel active coating surface layer. Thus, in one embodiment, as shown in fig. 6, the first high nickel active coating 20 is continuously coated with the intermediate nickel positive electrode slurry to form a stable first intermediate nickel active coating 30 on the outer side of the first high nickel active coating 20, so that the first intermediate nickel active coating 30 can form a gradient difference with the first high nickel active coating 20, thereby reducing the reaction of the first high nickel active coating 20 directly on the outer side with the electrolyte; and performing gap coating operation on the second high-nickel active coating by adopting the middle-nickel positive electrode slurry to form a stable inner-ring middle-nickel active coating 51 and a stable middle-outer-ring middle-nickel active coating 52 on the outer side of the second high-nickel active coating, so that the inner-ring middle-nickel active coating 51 and the middle-outer-ring middle-nickel active coating 52 can form a formula gradient difference with the second high-nickel active coating, and the reaction of the second high-nickel active coating directly positioned on the outer side with electrolyte is lightened.
In one embodiment, when the intermediate nickel anode slurry is used to perform a gap coating operation on the second high nickel active coating, under the condition that the surface capacities of the first high nickel active coating 20, the inner ring high nickel active coating 41, the intermediate outer ring high nickel active coating 42 and the intermediate outer ring intermediate nickel active coating 52 are kept unchanged, the surface capacity of the inner ring intermediate nickel active coating 51 is controlled to be 2% -6% greater than the surface capacity of the inner ring high nickel active coating 41, so that the surface capacity of the inner ring intermediate nickel active coating 51 is set to be 2% -6% greater than the surface capacity of the inner ring high nickel active coating 41, and thus, under the condition that the reaction between the electrolyte and the inner ring high nickel active coating 41 is reduced, the full charge potential of the positive electrode material of the positive electrode inner ring facing to the outer side is effectively reduced, the positive electrode material capacity attenuation of the positive electrode inner ring facing the outer side is effectively reduced, and the utilization rate of the intermediate outer ring intermediate nickel active coating 52 is also improved; and the preparation of the high-performance high-nickel ternary power battery circulating large cylindrical battery is ensured.
Specifically, the surface capacity ratio of the nickel active coating layer 51 in the inner ring to the surface capacity ratio of the nickel active coating layer 52 in the outer ring is (2 to 6): (94-98), and the surface capacity ratio of the middle-outer ring middle-nickel active coating 52 to the first high-nickel active coating 20, the inner-ring high-nickel active coating 41 and the middle-outer ring high-nickel active coating 42 is consistent, so that the surface capacity of the inner-ring middle-nickel active coating 51 is set to be 2% -6% greater than the surface capacity of the inner-ring high-nickel active coating 41 under the condition that the surface capacities of the first high-nickel active coating 20, the inner-ring high-nickel active coating 41, the middle-outer ring high-nickel active coating 42 and the middle-outer ring middle-nickel active coating 52 are kept unchanged. Further, in some preferred embodiments, the surface area of the nickel active coating in the inner ring is 4% -6% greater than the surface area of the high nickel active coating in the inner ring.
In one embodiment, the binder of the first and second middle nickel active coatings is a mixture of suwei 5130 and alcima HSV 900. It can be appreciated that the first middle nickel active coating and the second middle nickel active coating are positioned at the outermost side, so that the powder falling phenomenon is more likely to occur in the winding process. Therefore, in the present disclosure, by setting the binder of the first middle nickel active coating layer and the second middle nickel active coating layer to be a mixture of suwei 5130 and alcomax HSV900, the phenomenon that the first middle nickel active coating layer and the second middle nickel active coating layer are not easy to fall off during winding can be better ensured.
It can be further understood that when the surface capacity of the nickel active coating in the inner ring is greater than 2% -6% of the surface capacity of the high nickel active coating in the inner ring, the coating thickness of the nickel active coating in the inner ring is higher than that of the nickel active coating in the outer ring under the same coating condition, and the preset gaps and the preset cutting gaps are located at two sides of the nickel active coating in the inner ring, so that the nickel active coating in the inner ring is easy to extend towards the preset gaps and the preset cutting gaps in the two sides in the rolling process, and the phenomenon that the rolled high nickel active coating in the inner ring occupies the positions of the preset gaps and the preset cutting gaps is caused. Therefore, the bonding agent of the second middle nickel active coating is controlled to be the mixture of the Suwei 5130 and the Acomat HSV900, so that the bonding property of the nickel active coating in the inner ring is obviously larger than that of the inner ring high nickel active coating, the nickel active coating in the inner ring is not easy to extend to preset gaps and preset cutting gaps on two sides in the rolling process due to strong bonding property, and the connection firmness of the nickel active coating in the middle inner ring and the inner ring high nickel active coating can be improved by using one of the Suwei 5130 or the Acomat HSV900, so that the connection firmness of the nickel active coating in the inner ring and the inner ring high nickel active coating is also improved on the premise that the preset gaps and the preset cutting gaps are not changed greatly in the passing operation.
In one embodiment, the mass ratio of suwei 5130 to alcima HSV900 is 1:1 to ensure that the threw 5130 and the alcomax HSV900 can exert better synergistic effect. Further, suwei 5130 is provided by suwei manufacturer and alcomax HSV900 is provided by alcomax.
In order to increase the coating efficiency, in one embodiment, the winding inner side of the positive current collector roll is coated in a continuous double layer manner, and the winding outer side of the positive current collector roll is coated in a gap double layer manner. It can be understood that the continuous double-layer coating is to continuously coat the inner side surface of the winding with the high nickel positive electrode slurry first and then continuously coat with the medium nickel positive electrode slurry to realize continuous double-layer coating on the inner side surface of the winding; the gap double-layer coating is to use high nickel positive electrode slurry to coat the outer side surface of the winding in a gap mode, and then use medium nickel positive electrode slurry to coat the outer side surface of the winding in a gap mode, so that the gap double-layer coating on the outer side surface of the winding is achieved, and coating efficiency is improved.
It is understood that the positive electrode material capacity fade is exacerbated by the greater content of the conductive agent in the outer layers of the first and second high nickel active coatings due to the ease with which the conductive agent is transferred by the solvent to the outer layers of the first and second high nickel active coatings. Therefore, in one embodiment, the content of the conductive agent in the middle nickel positive electrode slurry is less than 0.3% -0.5% of that in the high nickel positive electrode slurry, and especially, the nickel active coating in the inner ring is matched with the use that the surface capacity of the nickel active coating in the inner ring is more than 2% -6% of that of the high nickel active coating in the inner ring, and on the premise of meeting the requirement of preparing the high-performance high nickel ternary power battery circulation, the nickel active coating in the inner ring can better block the reaction of the high nickel active coating in the inner ring and the electrolyte, so that the capacity attenuation of the positive electrode material is effectively reduced, the use amount of the conductive agent is reduced, and the use cost of the conductive agent is reduced.
In one embodiment, the conductive agent is a conventionally used conductive agent, for example, the conductive agent may be a super dense manufacturer SP conductive carbon black.
The disclosure also provides a battery module, which comprises the large cylindrical battery with the high-nickel ternary power battery circulation prepared by the method for preparing the large cylindrical battery with the high-nickel ternary power battery circulation improved in any embodiment.
It can be understood that the large cylindrical battery with high nickel ternary power battery circulation prepared by the preparation method of the large cylindrical battery with high nickel ternary power battery circulation is applied to a battery module, namely the battery module comprises a plurality of large cylindrical batteries with high nickel ternary power battery circulation, and the large cylindrical batteries with high nickel ternary power battery circulation are electrically connected in parallel or in series to realize the circulation of the plurality of high nickel ternary power batteries. Because the preset gap and the preset cutting gap are formed in the large cylindrical battery of each high-nickel ternary power battery cycle, on one hand, the circulation of electrolyte of the large cylindrical battery of a single high-nickel ternary power battery cycle in the battery module after long cycle is ensured, and on the other hand, the CB value of the positive electrode material of the large cylindrical battery of the single high-nickel ternary power battery cycle is effectively reduced, and the capacity attenuation of the positive electrode material of the large cylindrical battery of the single high-nickel ternary power battery cycle is reduced; on the other hand, the heat dissipation of the large cylindrical battery of the single high-nickel ternary power battery cycle is improved, so that the heat dissipation of the high-performance battery module is ensured.
Specific examples are set forth below, and all references to percentages are by weight. It should be noted that the following examples are not exhaustive of all possible scenarios, and that the materials used in the examples described below are commercially available unless otherwise specified.
Comparative example 1
The positive electrode uses a formula with 96.3% of ternary NCM (Ni content ratio is more than or equal to 90%) in mass ratio, and the other 3.7% of materials are respectively 1.0% of sp conductive carbon black (Temi high manufacturer), 0.5% of CNT (kaempferia galanthamine manufacturer) and 2.2% of binder Suwei 5130;
The positive electrode sheet A (shown in FIG. 2) was obtained by coating using a continuous coating method, and then successively subjected to cold pressing twin-roll operation (cold pressing speed of 20m/s at room temperature, cold pressing pressure of 6 tons), baking operation and cutting to obtain a positive electrode sheet.
The positive electrode formula 1 (high-nickel positive electrode slurry, a first high-nickel active coating and a second high-nickel active coating close to two sides of a positive current collector) adopts a formula with a ternary NCM (Ni content ratio is more than or equal to 90%) in mass ratio of 96.3%, other 3.7% of materials are respectively 1.0% sp conductive carbon black (high density manufacturer), 0.5% CNT (kaneter manufacturer) and 2.2% adhesive Suwei 5130;
The cathode formula 2 (middle nickel cathode slurry, a first middle nickel active coating and a second middle nickel active coating respectively positioned on the two outermost sides of a positive current collector) adopts a formula with a ternary NCM (Ni content ratio of 60%) in a mass ratio of 96.3%, other 3.7% of materials in mass ratio are respectively 1.0% sp conductive carbon black (termi high manufacturer), 0.5% CNT (kaempferide manufacturer) and 2.2% adhesive Suwei 5130;
Wherein the total surface capacity is unchanged, the surface capacity ratio of the double-layer active material=positive electrode formulation 2: the positive electrode formulation 1=5:95 was coated by using a continuous double-layer coating method to obtain a positive electrode sheet a (as shown in fig. 3), and then cold-pressing twin-roll operation (cold-pressing speed is 20m/s at normal temperature, cold-pressing pressure is 6 tons), baking operation and cutting were sequentially performed to obtain a positive electrode sheet.
The difference from example 1 is that 2.2% of the binder threw 5130 in example 1 is replaced by 1.1% of the binder threw 5130 and 1.1% of the binder alcima HSV900; the rest is unchanged.
The difference from example 2 is that 1% sp conductive carbon black (termi manufacturer) in the positive electrode formulation of example 2 is replaced with 0.5% sp conductive carbon black (termi manufacturer), the remainder being unchanged.
The difference from example 3 is that the coating mode of example 4 was changed (as shown in fig. 4), and the rest was unchanged.
Coating mode of example 4: wherein the total surface capacity is unchanged, the double-layer active material surface capacity ratio of the positive electrode active material facing the inside = positive electrode formulation 2: positive electrode formulation 1=5:95 was coated using a continuous double coating method, and the double active material surface capacity ratio of positive electrode active material toward the outside=positive electrode formulation 2: the positive electrode formula 1=5:95 is coated by using a gap double-layer coating mode to form an inner ring high nickel active coating, a preset gap, a middle outer ring high nickel active coating, an inner ring middle nickel active coating, a middle outer ring middle nickel active coating and a preset cutting gap, wherein the preset gap and the preset cutting gap are both 2mm, the lengths of the inner ring high nickel active coating and the inner ring middle nickel active coating are equal to the difference obtained by subtracting the width of the preset gap and the preset cutting gap from the sum of the circumferences of all the circles at the position where the winding starting position of the positive current collector is less than or equal to 9.0mm from the center of the coil core, the rolled inner ring high nickel active coating and the rolled inner ring middle nickel active coating can be located in the range of 2.3 mm-9.0 mm of the center of the coil core, so as to obtain a positive electrode plate A (as shown in figure 4), and then cold pressing operation (cold pressing speed is 20m/s under normal temperature condition, cold pressing pressure is 6 tons), baking operation and cutting are sequentially carried out, so as to obtain the positive electrode plate.
The difference from example 4 is that: the coated surface area of example 5 was changed (as shown in fig. 5) and the rest was unchanged.
Coating mode of example 5: wherein the total surface area is changed, the double-layer active material surface area ratio of the positive electrode active material toward the inside = positive electrode formulation 2: the positive electrode formulation 1=5:95 was coated using a continuous bilayer coating; positive electrode active material with tail wound toward the outside, double-layer active material surface capacity ratio=positive electrode formulation 2: gap coating was performed using a bilayer coating method in a positive electrode formulation 1=5:95; namely, the surface volume ratio of the positive electrode active material which faces to the outside and winds the head part is changed under the condition that the surface volumes of the first high nickel active coating, the inner ring high nickel active coating, the middle outer ring high nickel active coating and the middle outer ring middle nickel active coating are unchanged, and the double-layer active material surface volume ratio = positive electrode formula 2: gap coating is carried out in a double-layer coating mode of positive electrode formula 1=9:95; the surface capacity of the nickel active coating in the inner ring is made to be more than 4% of the surface capacity of the high nickel active coating in the inner ring.
The difference from example 5 is that: the surface-to-volume ratio of the positive electrode active material wound around the head and facing outward in example 5 was changed, and a double-layer active material surface-to-volume ratio=positive electrode formulation 2: positive electrode formulation 1 = 9:95 double layer coated gap coated "9:95 was replaced with 11:95, even though the surface area of the nickel active coating in the inner ring is more than 6% of the surface area of the high nickel active coating in the inner ring, the rest is unchanged.
The difference from example 5 is that: the surface-to-volume ratio of the positive electrode active material wound around the head and facing outward in example 5 was changed, and a double-layer active material surface-to-volume ratio=positive electrode formulation 2: positive electrode formulation 1 = 9:95 double layer coated gap coated "9:95 was replaced with 7:95, even though the surface area of the nickel active coating in the inner ring is more than 2% of the surface area of the high nickel active coating in the inner ring, the rest is unchanged.
The difference from example 5 is that: example 8 the positive electrode sheet a was preheated for 2min at 35 c before cold-pressing the pair of rolls, immediately followed by cold-pressing the pair of rolls (cold-pressing speed 20m/s at room temperature, cold-pressing pressure 6 tons), and then by baking and cutting.
Sequentially stacking a negative plate, a diaphragm and a positive plate (one positive plate in comparative example 1 and examples 1-8) to obtain a to-be-rolled body; wherein, the negative electrode plates are all coated by a graphite mass ratio of 96.7%, the other 3.3% mass materials are respectively 0.8% sp conductive carbon black (special density high manufacturer), 0.7% binder, 0.5% CMC and 1.3% PAA by using a continuous coating mode, and the CB value is set to be 1.12 (negative electrode plate/positive electrode plate); the method comprises the steps of manufacturing a winding core of a body to be wound in a winding mode, rubbing a lug of the winding core to obtain a bare cell, carrying out laser welding on a negative electrode of the bare cell and a corresponding negative electrode structural member (a spacer of the structural member is made of PP), then filling the bare cell into a shell, sealing by laser welding, carrying out laser welding on a positive electrode of the other side and the corresponding positive electrode structural member, sealing by laser welding, and then carrying out primary injection, standing, forming, secondary injection, standing, welding sealing nails, separating OCV and the like, thus manufacturing the complete 46135 cylindrical battery.
CB values were measured for the 46135 cylindrical batteries of examples 4 to 8 and comparative example 1 to obtain the data of Table 1
Wherein the CB value is calculated as follows:
Cb= (positive pole to centre radius r 1/negative pole to centre radius r 2) design CB value;
r 2 =positive electrode distance radius r 1 + (separator thickness+negative electrode coating thickness/2+positive electrode coating thickness/2);
TABLE 1
As can be seen from the data in table 1, the coating methods of examples 5 to 8 can effectively reduce the CB value of the whole nickel active coating in the inner ring, and effectively reduce the CB value of the positive electrode material CB value at the local position of the positive electrode inner ring facing to the outer side, thereby reducing the capacity fade of the positive electrode material of the inner ring high nickel active coating.
Each performance of examples 1 to 8 and comparative example 1 was tested to obtain experimental data of table 2:
Hi-pot test method: and testing the bare cell by using a Hi-port tester, wherein the positive and negative terminals of the bare cell, the positive and negative terminals of the battery and the Hi-port tester are correspondingly connected, then 220V open-circuit voltage is applied for 3s, and when the Hi-port tester detects the internal resistance of the battery to be less than 220 megaohms, the battery is judged to be bad.
K value measurement: after the capacity of the battery is divided, the voltage of the battery is adjusted to 30% SOC, the battery is placed in a 45 ℃ environment for standing for 48 hours, then the battery is placed in a normal temperature environment for standing for 12 hours, and the voltage 1 of the battery at the moment is recorded; standing for 24 hours in a normal temperature environment, and recording the battery voltage 2 at the moment; and according to the calculation method of the K value, the K value is calculated: k= (voltage 2-voltage 1)/(time difference between two voltage measurements).
The test method of the full capacitance retention rate of the 55 ℃ high temperature cycle comprises the following steps:
charging 1C CC-CV 4.2V-0.05C discharging 1C DC to 2.5V each charge-discharge was provided with a full capacitance retention rate tested under conditions of 1 minute rest time.
The method for testing the capacity attenuation and the potential of the outer ring towards the outer positive electrode and the capacity attenuation and the potential of the inner ring towards the outer positive electrode comprises the following steps:
Sampling position: the inner ring takes a pole piece at a position 2.3-3.5 mm away from the center of the circle, and the outer ring takes a pole piece at an outermost position 10-50 mm away from the center of the circle;
sample preparation method step 1: disassembling the fully-charged battery cell in an inert gas environment glove box, and then cutting out the pole piece at the required position; step 2: washing the sampling electrode plate for 1 minute by DMC, cleaning the active substance on the other side of the electrode with the required measuring potential, and manufacturing an electrode plate with one side of the electrode plate with the material; step 3: stamping the manufactured positive electrode plate into a small wafer by using stamping equipment in a glove box, and assembling the small wafer and a lithium plate into a button cell; step 4: measuring the open circuit potential of the button cell after full charge to obtain the lithium potential of different positions of the fresh cell after full charge; step 5: and measuring the capacity attenuation rate of the positive electrode with the outer ring facing outwards and the positive electrode with the inner ring facing outwards of the button cell charging 1C CC-CV 4.2V-0.05C discharging 1C DC to 2.5V.
TABLE 2
As can be seen from the comparison of example 1 and comparative example 1, the first middle nickel active coating layer and the second middle nickel active coating layer (6-series ternary material) added in example 1 can effectively isolate side reaction with electrolyte, thereby improving the full capacity retention rate of the large cylindrical battery of the high nickel ternary power battery cycle at 55 ℃ and high temperature cycle (4.89% increase compared with comparative example 1).
As can be seen from the comparison between the example 2 and the comparative example 1/example 1, the mixture of Suwei 5130 and Acomax HSV900 is adopted as the adhesive of the first middle nickel active coating and the second middle nickel active coating in the example 2, so that the defective rate of Hi-post short circuit can be effectively reduced, and the phenomenon that the wound positive plate is easy to fall off can be reduced.
As can be seen from comparison of example 3 with example 2, by reducing the content of the conductive agent enriched in the surface layers of the first middle nickel active coating layer and the second middle nickel active coating layer of example 3, the side reaction of the high nickel ternary positive electrode material can be effectively reduced, and the 55 ℃ high temperature cycle full capacity retention rate of the large cylindrical battery of the high nickel ternary power battery cycle can be improved (increased by 2.42% compared with example 2).
As can be seen from comparison between examples 5-7 and example 4, since examples 5-7 realize the "negative and positive surface" of the outside part of the positive electrode inner ring by means of gap coating, the CB value of the local position of the CB value of the positive electrode material of the positive electrode inner ring facing the outside is reduced, and the positive electrode potential of the full charge of the local position of the positive electrode inner ring can be reduced, thereby reducing side reactions with electrolyte and improving the full capacity retention rate of the 55 ℃ high-temperature cycle of the large cylindrical battery of the high-nickel ternary power battery cycle, wherein each comprehensive index of example 6 is better.
As can be seen from the comparison between examples 5 to 7 and example 8, the preheating operation is added in example 8, so that the comprehensive indexes of example 8 are optimized.
The foregoing examples represent only a few embodiments of the present disclosure, which are described in more detail and detail, but are not to be construed as limiting the scope of the disclosure. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the disclosure, which are within the scope of the disclosure. Accordingly, the scope of protection of the present disclosure should be determined by the following claims.
Claims (10)
1. The large cylindrical battery with high nickel ternary power battery circulation includes winding core and casing, the winding core is set inside the casing, the winding core is formed with negative plate, diaphragm and positive plate through lamination and winding, the positive plate includes positive current collector, first high nickel active coating and second high nickel active coating,
The positive current collector is provided with a winding inner side surface and a winding outer side surface which are oppositely arranged, the first high-nickel active coating is arranged on the winding inner side surface, and the second high-nickel active coating is arranged on the winding outer side surface; the second high-nickel active coating comprises an inner ring high-nickel active coating and a middle outer ring high-nickel active coating, the inner ring high-nickel active coating and the middle outer ring high-nickel active coating are arranged at intervals along the length direction of the positive current collector, and a preset gap is formed between the inner ring high-nickel active coating and the middle outer ring high-nickel active coating;
Wherein the surface capacity of the inner ring high-nickel active coating is 2.0% -6.0% greater than that of the middle outer ring high-nickel active coating.
2. The high nickel ternary power battery circulating large cylindrical battery of claim 1, wherein the surface capacity of the inner ring high nickel active coating is greater than 4% -6% of the surface capacity of the middle outer ring high nickel active coating.
3. The high nickel ternary power battery circulating large cylindrical battery of claim 1 wherein the length of the inner ring high nickel active coating is equal to the difference of the sum of the circumferences of all turns of the positive current collector winding start position less than or equal to 9.0mm from the center of the winding core minus the width of the preset gap.
4. The high nickel ternary power battery cycled large cylindrical battery of claim 1 wherein the inner ring high nickel active coating forms a pre-determined cut void adjacent the positive current collector winding initiation location.
5. The high nickel ternary power battery circulating large cylindrical battery of claim 1, further comprising a first middle nickel active coating and a second middle nickel active coating, wherein the first middle nickel active coating is disposed on a side of the first high nickel active coating facing away from the positive current collector, and the second middle nickel active coating is disposed on a side of the second high nickel active coating facing away from the positive current collector.
6. The high nickel ternary power battery cycled large cylindrical battery in accordance with claim 5 wherein the first high nickel active coating has a Ni content greater than or equal to 90%, and/or,
The Ni content of the second high-nickel active coating is more than or equal to 90%; and/or the number of the groups of groups,
Ni content of the first middle nickel active coating is 50% -80%; and/or the number of the groups of groups,
Ni content of the second middle nickel active coating is 50% -80%; and/or the number of the groups of groups,
The number of the first high-nickel active coatings is at least two, and the first high-nickel active coatings are sequentially stacked; and/or the number of the groups of groups,
The number of the second high-nickel active coatings is at least two, and the second high-nickel active coatings are sequentially stacked.
7. The high nickel ternary power battery cycled large cylindrical battery of claim 5 wherein the first midnickel active coating has a lower level of conductive agent than the first high nickel active coating; and/or the number of the groups of groups,
The content of the conductive agent of the second middle nickel active coating is less than the content of the conductive agent of the second high nickel active coating.
8. The preparation method of the large cylindrical battery for improving the high-nickel ternary power battery circulation is characterized by comprising the following steps of:
Acquiring a positive current collector roll;
Performing continuous coating operation on the winding inner side surface of the positive current collector roll by adopting high-nickel positive electrode slurry so as to form a first high-nickel active coating on the winding inner side surface of the positive current collector roll;
Performing gap coating operation on the winding outer side surface of the positive current collector roll by adopting high-nickel positive electrode slurry to obtain an inner ring high-nickel active coating and a middle outer ring high-nickel active coating which are arranged at intervals on the winding outer side surface of the positive current collector roll, so as to obtain a positive plate A, wherein the surface capacity of the inner ring high-nickel active coating is 2% -6% greater than that of the middle outer ring high-nickel active coating;
Rolling the positive plate A;
Baking the positive plate A after the rolling operation to obtain a positive plate B;
Cutting the positive plate B to obtain a positive plate;
Sequentially stacking a negative plate, a diaphragm and the positive plate to obtain a to-be-rolled body;
and (3) winding the to-be-wound body to obtain the large cylindrical battery with the high-nickel ternary power battery circulation according to any one of claims 1-7.
9. The method for manufacturing a large cylindrical battery for improving the cycle of a high nickel ternary power battery according to claim 8, wherein in the step of performing a gap coating operation on the wound outer side surface of the positive current collector roll using high nickel positive electrode slurry, comprising the following specific steps:
The coating machine carries out a first coating operation according to the set conditions of the middle-outer-ring high-nickel active coating;
closing a discharge port of the coating machine after the first coating operation is completed;
the coater moves the positive current collector roll according to a preset gap;
After the positive current collector roll moves to the preset gap position, opening a discharge hole of the coating machine;
and the coating machine performs a second coating operation according to the set conditions of the inner ring high-nickel active coating.
10. A battery module comprising a plurality of large cylindrical batteries with improved high-nickel ternary power battery circulation prepared by the method for preparing large cylindrical batteries with improved high-nickel ternary power battery circulation according to claim 8 or 9.
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