CN115312684A - Positive pole piece and battery - Google Patents
Positive pole piece and battery Download PDFInfo
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- CN115312684A CN115312684A CN202211018533.3A CN202211018533A CN115312684A CN 115312684 A CN115312684 A CN 115312684A CN 202211018533 A CN202211018533 A CN 202211018533A CN 115312684 A CN115312684 A CN 115312684A
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- positive electrode
- positive
- pole piece
- battery
- binder
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- 239000011230 binding agent Substances 0.000 claims abstract description 50
- 239000006258 conductive agent Substances 0.000 claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 3
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 3
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000005056 compaction Methods 0.000 abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 239000013543 active substance Substances 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 238000000605 extraction Methods 0.000 abstract 1
- 238000003780 insertion Methods 0.000 abstract 1
- 230000037431 insertion Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 39
- 239000011267 electrode slurry Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 9
- 238000003825 pressing Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
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
-
- 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
-
- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a positive pole piece and a battery, and relates to the technical field of batteries; the positive pole piece comprises a positive current collector and a positive diaphragm; the positive diaphragm is arranged on at least one side surface of the positive current collector and comprises a positive active substance, a conductive agent and a binder; the positive pole piece satisfies the formula: -0.01 < (-0.3788 XPD + 1.155). Times.p/(12 XPET) < 0.0335. On one hand, the compaction density is controlled, the performance of the lithium ion extraction and insertion process can be improved on the premise of ensuring the functional performance, the single-element conductive network in the pole piece is perfected, the internal resistance of the pole piece is reduced, and the rebound problem of the pole piece is improved; on the other hand, the density of the binding agent, the specific surface area of the active substance and the compaction density are cooperatively controlled, so that the power performance of the battery can be effectively improved while the rebound of the pole piece is ensured to be small.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a positive pole piece and a battery.
Background
In the process of charging and discharging of the battery, the pole piece is easy to rebound, the rebound refers to the phenomenon that the thickness of the pole piece is increased compared with the thickness after rolling, and the rebound of the pole piece is large, so that the service performance and the safety performance of the battery are directly influenced. In the prior art, in order to control the rebound of the pole piece, the compaction density or the rolling process of the pole piece is usually improved, but the existing scheme for improving the rebound of the pole piece influences the power performance of the battery, so that the power performance of the battery is reduced, and the service life of the battery is shortened. Therefore, the prior art lacks a pole piece which can ensure the power performance of the battery and control the rebound.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a positive pole piece and a battery with small rebound and excellent power performance.
The embodiment of the invention is realized by the following steps:
in a first aspect, the present invention provides a positive electrode plate, including:
a positive current collector;
the positive electrode diaphragm is arranged on at least one side surface of the positive electrode current collector and comprises a positive electrode active substance, a conductive agent and a binder;
the positive pole piece satisfies the formula: -0.01 < (-0.3788 × PD + 1.155) × (12 × BET) < 0.0335; wherein PD is the compaction density of the positive pole piece and the unit is g/cm 3 (ii) a Rho is the density of the binder and has the unit of g/cm 3 (ii) a BET is the specific surface area of the positive electrode active material in m 2 /g。
In an alternative embodiment, the positive electrode sheet satisfies the formula: -0.0031 < - > (-0.3788 × PD + 1.155) × ρ/(12 × BET) < 0.021;
preferably, the positive electrode plate satisfies the formula: 0 < (-0.3788 XPD + 1.155). Times.p/(12 XPBET) < 0.005.
In an alternative embodiment, the compacted density of the positive electrode sheet satisfies 2.5g/cm 3 ≤PD≤3.5g/cm 3 ；
Preferably, the compacted density of the positive pole piece meets 2.85g/cm 3 ≤PD≤3.05g/cm 3 。
In an alternative embodiment, the binder has a density of 1.70g/cm 3 ≤ρ≤1.80g/cm 3 ；
Preferably, the density of the binder satisfies 1.77g/cm 3 ≤ρ≤1.80g/cm 3 。
In an alternative embodiment, the specific surface area of the positive electrode active material satisfies 0.8m 2 /g≤BET≤5m 2 /g；
Preferably, the specific surface area of the positive electrode active material satisfies 2.2m 2 /g≤BET≤3.6m 2 /g。
In an alternative embodiment, the porosity of the positive electrode sheet ranges between 20% and 60%;
preferably, the porosity of the positive pole piece ranges from 25% to 45%.
In an alternative embodiment, the positive electrode current collector is selected from any one of an aluminum foil, a carbon-coated aluminum foil, and a nickel mesh;
and/or the presence of a gas in the gas,
the positive electrode active material is selected from any one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, and lithium phosphate having an olivine structure;
and/or the presence of a gas in the gas,
the conductive agent is selected from any one of carbon black and carbon nanotubes;
and/or the presence of a gas in the gas,
the binder is PVDF.
In an alternative embodiment, the positive membrane comprises a mass ratio of (90-97): (1-5): (1-5) the positive electrode active material, the conductive agent and the binder.
In an alternative embodiment, both side surfaces of the positive electrode current collector are provided with positive electrode diaphragms.
In a second aspect, the present invention provides a battery comprising a positive electrode sheet according to any one of the preceding embodiments.
The embodiment of the invention has at least the following advantages or beneficial effects:
the embodiment of the invention provides a pole piece, which comprises a positive pole current collector and a positive pole diaphragm; the positive diaphragm is arranged on at least one side surface of the positive current collector and comprises a positive active substance, a conductive agent and a binder; the positive pole piece satisfies the formula: -0.01 < (-0.3788 × PD + 1.155) × (12 × BET) < 0.0335; wherein PD is the compacted density of the positive pole piece, and the unit is g/cm 3 (ii) a Rho is the density of the binder and is given in g/cm 3 (ii) a BET is the specific surface area of the positive electrode active material in m 2 /g。
On one hand, the positive pole piece can improve the performance of the process of separating and embedding lithium ions by controlling the compaction density on the premise of ensuring the power performance so as to perfect a single-electron conductive network in the pole piece and reduce the internal resistance of the pole piece, thereby fully improving the rebound problem of the pole piece; on the other hand, the density of the binder, the specific surface area of the positive active material and the compaction density are cooperatively controlled, so that the power performance and the service life of the battery can be effectively improved while the rebound of the pole piece is further reduced.
The embodiment of the invention provides a battery, which comprises the positive pole piece. Therefore, the battery also has the advantages of small rebound and excellent power performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
The embodiment of the invention provides a positive pole piece, which comprises: a positive current collector; the positive electrode diaphragm is arranged on at least one side surface of the positive electrode current collector, is obtained by coating positive electrode slurry on the positive electrode current collector, drying and performing cold pressing, and the positive electrode slurry comprises a positive electrode active substance, a conductive agent and a binder; wherein, positive pole piece satisfies the formula: -0.01 < (-0.3788 × PD + 1.155) × (12 × BET) < 0.0335; wherein PD is the compacted density of the positive pole piece, and the unit is g/cm 3 (ii) a Rho is the density of the binder and has the unit of g/cm 3 (ii) a BET is the specific surface area of the positive electrode active material in m 2 /g。
When the positive electrode plate is prepared, positive electrode slurry can be prepared first, and a positive electrode active substance, a conductive agent and a binder are mixed according to a certain mass ratio, wherein the mass ratio of the positive electrode active substance, the conductive agent and the binder is (90-97): (1-5): (1-5). Then, NMP is added, and the mixture is stirred by a homogenizer to form the anode slurry which is uniformly and stably mixed. Next, the positive electrode slurry may be applied to at least one side surface of the positive electrode current collector, and dried and cold-pressed to form a positive electrode membrane on the side surface of the positive electrode current collector. And then, carrying out cold pressing treatment on the dried positive pole piece under certain pressure and roll gap, and adjusting the compaction density of the positive pole piece by adjusting cold pressing parameters. And finally, cutting the cold-pressed positive pole piece to a specified size for later use.
In the formula satisfied by the positive pole piece, PD is the compaction density of the positive pole piece, and the unit is g/cm 3 . When the lithium ion battery is charged and discharged, lithium ions are separated and embedded between the positive electrode material and the negative electrode material, and the separation and embedding processes of the lithium ions are closely related to the compacted density of the positive electrode plate. On one hand, as the compaction density of the positive pole piece is increased, the particles of the positive active material are tightly contacted with each other, the electronic conductive network in the pole piece is perfect, and the internal resistance is reduced; however, the pole piece rebounds in the circulation process due to too high compaction density, so that contact chains of the conductive agent and the adhesive with the positive active material are broken, particles among the positive active materials are mutually peeled, the charge transfer resistance is increased, and the rate capability and the circulation performance of the battery are poor. On the other hand, the compaction density of the positive pole piece is improved, the porosity in the pole piece is continuously reduced, the liquid retention amount of electrolyte in the pole piece is continuously reduced, the ionic conductivity of the pole piece is reduced, the conductive network is poor, and the internal resistance of the battery is increased. Therefore, the rebound of the positive pole piece can be reduced and the power performance of the battery can be ensured by selecting proper compaction density.
In the formula satisfied by the positive electrode sheet, the BET positive electrode represents the specific surface area of the positive electrode active material. The positive active material with small particle size has larger specific surface area and larger contact area with the electrolyte, so that the diffusion path of lithium ions is shortened, and the desorption of the lithium ions in the material under high current density is facilitated, therefore, the positive active material with small particle size is beneficial to improving the rate capability of the battery. Meanwhile, as the particle size of the positive active material particles increases, the ion transmission distance is also reduced, and thus the battery power performance can also be improved. However, when the particle diameter of the positive electrode active material is too small, the difficulty of dispersion of the slurry increases, and the manufacturing cost increases accordingly. Therefore, the selection of the appropriate specific surface area of the positive electrode active material can ensure that the lithium ion battery has excellent power performance and rate performance, prolong the service life of the lithium ion battery and control the manufacturing cost.
In the formula satisfied by the positive pole piece, rho is the density of the adhesive in the positive pole formula. On the one hand, the larger the density of the binder, the larger the volume of the binder particles, the more the conductive contact between the positive electrode active material and the conductive agent can be increased, and thus the electron conductivity can be improved. That is, increasing the binder density can collect micro-current between the active materials and between the conductive carbons to perfect the middle conductive network of the pole piece, reduce the internal resistance, and optimize the power performance. Particularly, in the rebound process of the pole piece, the larger the specific surface area is, a good conductive network can be maintained, so that the power performance of the battery is ensured. On the other hand, when the density of the binder is too low, the binder cannot maintain the close contact between the positive active material and the conductive agent, so that a perfect conductive network cannot be formed, and the problem of serious rebound of the pole piece in the later cycle period is caused, so that the capacity of the battery is seriously attenuated.
In conclusion, in the embodiment of the invention, on one hand, the rebound problem of the pole piece can be improved by controlling the compaction density on the premise of ensuring the power performance, the rate capability and the cycle performance of the battery; on the other hand, the density of the binder, the specific surface area of the positive active material and the compaction density are cooperatively controlled, so that the power performance and the service life of the battery are effectively improved while the rebound of the pole piece is further reduced.
As an optional scheme, in the embodiment of the present invention, the positive electrode plate satisfies the formula: -0.0031 < - > (-0.3788 × PD + 1.155) × ρ/(12 × BET) < 0.021; preferably, the positive electrode plate satisfies the formula: 0 < (-0.3788 XPD + 1.155). Times.p/(12 XPBET) < 0.005. When each parameter of the positive pole piece is controlled in the formula range, the pole piece rebounds less, and the power performance and the service life are better.
Exemplarily, in the embodiment of the invention, the compaction density of the positive pole piece satisfies that PD is more than or equal to 2.5 and less than or equal to 3.5; the compaction density of the positive pole piece meets the requirement that PD is more than or equal to 2.85 and less than or equal to 3.05. By selecting the compaction density within the range, the density of the binder and the specific surface area of the positive active material can be better matched, so that the formula requirements can be met. The particles of the positive active material are in closer contact with each other, so that the internal resistance of the pole piece can be reduced, the rebound of the pole piece in the circulation process is reduced, and the rate capability and the circulation performance of the battery are improved.
Illustratively, in embodiments of the present invention, the density of the binder satisfies 1.70 ≦ ρ ≦ 1.80; preferably, the density of the binder satisfies 1.77. Ltoreq. P.ltoreq.1.80. By selecting the density of the binder within the range, the compacted density of the positive pole piece and the specific surface area of the positive active material can be better matched, so that the positive active material meets the requirements of the formula. The contact area of the anode active material and the electrolyte is increased, the rate performance is better, and the ion transmission distance in the circulation process is reduced, so that the power performance of the battery is improved.
Illustratively, in the embodiments of the present invention, the specific surface area of the positive electrode active material satisfies 0.8 ≦ BET ≦ 5; preferably, the specific surface area of the positive electrode active material satisfies 2.2 BET 3.6 or less. By selecting the specific surface area of the positive electrode active material in the range, the compacted density of the positive electrode plate and the density of the binder can be better matched to meet the requirement of the formula. The micro-current between the active substance and the conductive agent particles is ensured, the power performance of the battery is improved, a good conductive network can be maintained, the rebound of a pole piece is reduced, and the power performance of the battery is improved.
Further optionally, in an embodiment of the present invention, the porosity of the positive electrode sheet ranges from 20% to 60%; preferably, the porosity of the positive electrode sheet ranges from 25% to 45%. The compaction density of the positive pole piece can influence the porosity of the positive pole piece to a certain extent. The control of the porosity can improve the ionic conductivity of the pole piece, influence a conductive network formed by the pole piece and even change the internal resistance of the battery. Therefore, the rebound of the pole piece can be further reduced by controlling the porosity on the basis of controlling the compaction density, and the power performance of the battery is ensured.
In the embodiment of the present invention, the types of the positive electrode current collector, the positive electrode active material, the conductive agent, and the binder may be selected as needed. Illustratively, the positive electrode current collector is selected from any one of aluminum foil, carbon-coated aluminum foil, and nickel mesh, and the positive electrode current collector may also be selected from composite current collectors doped with conductive substances. Illustratively, the positive active material is selected from any one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, and olivine-structured lithium-containing phosphate. The conductive agent is selected from any one of carbon black and carbon nanotubes, and the binder is PVDF.
It should be further noted that, in order to ensure the usability of the positive electrode plate, in the embodiment of the present invention, positive electrode diaphragms are disposed on both side surfaces of the positive electrode current collector. And the thickness of the anode diaphragms on the two sides is equal in size.
The embodiment of the invention also provides a battery which can be a square battery or a cylindrical or soft package battery. The battery comprises the positive pole piece, and further comprises a shell, a negative pole piece, a separation film and electrolyte. The positive pole piece, the isolating film and the negative pole piece are sequentially stacked, and the bare cell is formed in a winding or laminating mode. And after the naked electric core is arranged in the shell, electrolyte is injected into the shell to obtain the battery. The positive pole piece has the characteristics of small rebound and excellent power performance, so that the battery also has the advantages.
It should be noted that, in the embodiment of the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode membrane disposed on at least one side surface of the negative electrode current collector, and exemplarily, the negative electrode membrane is disposed on both side surfaces. The negative diaphragm is obtained by coating negative slurry on a negative current collector and drying and cold pressing the negative current collector. The negative electrode slurry comprises a negative electrode active substance, a conductive agent, a binder and a dispersing agent, wherein the negative electrode active substance can be selected from graphite, soft carbon, hard carbon, mesocarbon microbeads, silicon-based materials and the like, the conductive agent can be selected from SP, the binder can be selected from LA133, the dispersing agent can be selected from CMC, the negative electrode active substance, the conductive agent, the binder and the dispersing agent are mixed according to a certain mass ratio, then deionized water is added, and the mixture is stirred by a homogenizer to be uniformly mixed to obtain the negative electrode slurry.
It should also be noted that the isolation film can be selected according to actual requirements. For example, the isolating film can be selected from polyethylene film, polypropylene film, polyvinylidene fluoride film, non-woven fabric and the like; while the separator may have different coating layers. Such as alumina coatings, boehmite coatings, PVDF coatings, and the like. The electrolyte includes a lithium salt solute and a solvent. The types of the lithium salt and the solvent are not particularly limited and can be selected according to actual requirements. For example, the lithium salt may be LiPF 6 、LiTFSi、LiBF 4 And the like. Illustratively, an embodiment of the present invention may be selected by mixing Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) in a volume ratio of 1 6 Dissolved in the mixed organic solvent to prepare an electrolyte with the concentration of 1.2 mol/L.
The process for preparing the battery and the properties of the prepared battery will be described in detail with reference to the following specific examples:
example 1
This example provides a battery prepared by the following method:
s1: preparing a positive pole piece; mixing a positive electrode active material NCM111, a conductive agent SP and a binder PVDF according to a certain proportion, adding NMP, and stirring into uniformly-mixed stable positive electrode slurry by using a homogenizer; coating the positive electrode slurry on two side surfaces of a current collector aluminum foil, and drying and cold pressing the positive electrode slurry; continuously performing cold pressing and slitting operation to obtain a positive pole piece;
s2: preparing a negative pole piece; mixing a negative active material graphite, a conductive agent SP, a binder LA133 and a dispersant CMC according to a certain mass ratio, adding deionized water, and stirring by a homogenizer to obtain a uniformly and stably mixed negative slurry; coating the negative electrode slurry on two side surfaces of a current collector copper foil, and drying and cold pressing the current collector copper foil; continuously performing cold pressing and slitting operation to obtain a negative pole piece;
s3: preparing electrolyte; ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) were added in the same manner as described aboveMixing in a volume ratio of 1 6 Dissolving the mixture in the mixed organic solvent to prepare electrolyte with the concentration of 1.2 mol/L;
s4: a battery forming step: a polypropylene film with the thickness of 16um is used as a separation film; stacking the positive pole piece, the isolating film and the negative pole piece in sequence to enable the isolating film to be positioned between the positive pole piece and the negative pole piece, and then winding the positive pole piece, the isolating film and the negative pole piece to obtain a bare cell; and placing the bare cell in a shell, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the 8Ah lithium ion battery.
In the above preparation process, the preparation parameters of the battery are shown in table 1:
TABLE 1 parameters of example 1
Example 2
The present embodiment provides a battery, which is different from embodiment 1 in that each parameter of the battery provided in the present embodiment satisfies table 2.
TABLE 2 example 2 parameters
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite to SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 3 |
| Density of binder p (g/cm) 3 ) | 1.79 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 3.6 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | 0.00077 |
| Porosity of positive pole piece | 32％ |
Example 3
The present embodiment provides a battery, which is different from embodiment 1 in that each parameter of the battery provided in the present embodiment satisfies table 3.
TABLE 3 parameters of example 3
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite to SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 2.95 |
| Density of the binder rho (g/cm) 3 ) | 1.78 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 3.2 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | 0.0017 |
| Porosity of positive electrode sheet | 35％ |
Example 4
The present embodiment provides a battery, which is different from embodiment 1 in that each parameter of the battery provided in the present embodiment satisfies table 4.
TABLE 4 parameters of example 4
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite to SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 2.85 |
| BinderDensity of rho (g/cm) 3 ) | 1.8 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 2.2 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | 0.0051 |
| Porosity of positive pole piece | 38％ |
Example 5
The present embodiment provides a battery, which is different from embodiment 1 in that each parameter of the battery provided in the present embodiment satisfies table 5.
TABLE 5 parameters of example 5
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite to SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 2.9 |
| Density of the binder rho (g/cm) 3 ) | 1.7 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 3 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | 0.0026 |
| Porosity of positive pole piece | 37％ |
Example 6
The present embodiment provides a battery, which is different from embodiment 1 in that each parameter of the battery provided in the present embodiment satisfies table 6.
TABLE 6 parameters of example 6
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite to SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 2.5 |
| Density of the binder rho (g/cm) 3 ) | 1.7 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 5 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | 0.0058 |
| Porosity of positive pole piece | 40％ |
Comparative example 1
Comparative example 1 provides a battery, which is different from example 1 in that each parameter of the battery provided in comparative example 1 satisfies table 7.
TABLE 7 parameters of comparative example 1
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite to SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 5 |
| Density of the binder rho (g/cm) 3 ) | 1.7 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 5 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | -0.021 |
| Porosity of positive electrode sheet | 20％ |
Comparative example 2
Comparative example 2 provides a battery, which is different from example 1 in that each parameter of the battery provided in comparative example 1 satisfies table 8.
TABLE 8 parameters of comparative example 2
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite to SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 2.8 |
| Density of the binder rho (g/cm) 3 ) | 1.8 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 0.4 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | 0.0353 |
| Porosity of positive electrode sheet | 38％ |
Comparative example 3
Comparative example 3 provides a battery, which is different from example 1 in that each parameter of the battery provided in comparative example 1 satisfies table 9.
TABLE 9 parameters of comparative example 3
| Mass ratio of NCM111, SP and PVDF | 97:1.4:1.2 |
| Mass ratio of graphite, SP, LA133 and CMC | 32:0.4:0.5:0.3 |
| Compacted density PD (g/cm) of positive pole piece 3 ) | 2.5 |
| Density of the binder rho (g/cm) 3 ) | 2.4 |
| Specific surface area BET (m) of positive electrode active material 2 /g) | 1.1 |
| (-0.3788×PD+1.155)×ρ/(12×BET) | 0.0378 |
| Positive plate holeVoid fraction | 40％ |
Experimental example 1
The batteries provided in examples 1-6 and comparative examples 1-3 were subjected to the maximum charge rate test under the following conditions: at 25 ℃, the batteries prepared in examples 1 to 6 and comparative examples 1 to 3 are fully charged with x C and fully discharged with 1C for 10 times, then the batteries are fully charged with x C, then the negative pole piece is disassembled, and the lithium precipitation condition on the surface of the negative pole piece is observed. And if no lithium is separated from the surface of the negative electrode, gradually increasing the charging multiplying power xC by taking 0.1C as a gradient, and testing again until lithium is separated from the surface of the negative electrode, and stopping testing, wherein the charging multiplying power (x-0.1) C at the moment is the maximum charging multiplying power of the battery, and the test results are shown in table 10.
TABLE 10 multiplying power test results
| Item | Maximum charging rate (C) |
| Example 1 | 3.2C |
| Example 2 | 3.5C |
| Example 3 | 3.8C |
| Example 4 | 3.1C |
| Example 5 | 4.0C |
| Example 6 | 3.1C |
| Comparative example 1 | 3.0C |
| Comparative example 2 | 2.8C |
| Comparative example 3 | 1.4C |
As can be seen from the comparative data of examples 1-6 and comparative examples 1-3 in Table 10, the positive electrode sheet provided in this example satisfies the requirement that-0.01 < (-0.3788 XPD + 1.155) × ρ/(12 × BET) < 0.0335, and the rate capability of the battery prepared therefrom is more excellent. Meanwhile, as can be seen from the comparison between examples 1-6, when the positive electrode sheet satisfies the requirement of 0 < (-0.3788 × PD + 1.155) × (12 × BET) < 0.005, it has better rate capability. In addition, as can be seen from comparison of the rate data of examples 1 to 6 with that of comparative example 1, the rate performance of the battery can be effectively improved by adjusting the compaction density of the positive electrode plate in the examples of the invention. It can be seen from comparison of the rate data of examples 1 to 6 with that of comparative example 2 that the specific surface area of the positive active material of the positive electrode plate is adjusted in the examples of the present invention, so that the specific surface area meets the formula requirement of the positive electrode plate, and the rate performance of the battery can be effectively improved. Meanwhile, as can be seen from comparison of the rate data of examples 1 to 6 with the rate data of comparative example 3, the embodiment of the invention can meet the formula requirement of the positive electrode plate by adjusting the binder density of the positive electrode plate, and can also effectively improve the rate performance of the battery.
Experimental example 2
The batteries provided in examples 1 to 6 and comparative examples 1 to 3 were subjected to a power performance test under conditions of a constant current and a constant voltage at 25 ℃ for fully charging the lithium ion battery with a current of 1C, a discharge at 1C for 48min after standing for 5min, a discharge at 1045W to 2.5V after standing for 5min, and a discharge current was outputted. The test results are shown in table 11.
TABLE 11 Power test results
| Item | 1045W DC/s |
| Example 1 | 9.4 |
| Example 2 | 10.1 |
| Example 3 | 10.3 |
| Example 4 | 9.0 |
| Example 5 | 10.8 |
| Example 6 | 8.9 |
| Comparative example 1 | 8.2 |
| Comparative example 2 | 6.8 |
| Comparative example 3 | 5.5 |
As can be seen from the comparative data of examples 1-6 and comparative examples 1-3 in Table 11, the positive electrode sheet provided in this example satisfies the requirement of-0.01 < (-0.3788 XPD + 1.155) × ρ/(12 × BET) < 0.0335, and the power performance of the battery prepared therefrom is more excellent. Meanwhile, as can be seen from the comparison between examples 1-6, the positive electrode sheet has better power performance when it satisfies the requirement of 0 < (-0.3788 × PD + 1.155) × (12 × BET) < 0.005. In addition, as can be seen from the comparison of the power data of examples 1 to 6 with the power data of comparative example 1, the examples of the present invention can effectively improve the power performance of the battery by adjusting the compaction density of the positive electrode sheet. By comparing the power data of the embodiments 1 to 6 with the power data of the comparative example 2, the embodiment of the invention can adjust the specific surface area of the positive active material of the positive pole piece to meet the formula requirement of the positive pole piece, and can also effectively improve the power performance of the battery. Meanwhile, as can be seen from the comparison of the power data of the examples 1 to 6 with the power data of the comparative example 3, the embodiment of the invention can meet the formula requirement of the positive pole piece by adjusting the binder density of the positive pole piece, and can also effectively improve the power performance of the battery.
Experimental example 2
The batteries provided in examples 1 to 6 and comparative examples 1 to 3 were tested for the rebound rate of the positive electrode sheet under the following test conditions: and (3) measuring the thickness of the rolled cathode pole piece immediately by using a ten-thousandth micrometer, standing for two hours, and then measuring the thickness of the pole piece, wherein the calculation formula of the rebound rate is the thickness difference of the anode pole piece before and after two hours after rolling and the thickness of the anode pole piece after rolling. The test results are shown in table 12.
TABLE 12 thickness rebound Rate test results
| Item | Thickness rebound Rate (%) |
| Example 1 | 5.21％ |
| Example 2 | 5.10％ |
| Example 3 | 3.37％ |
| Example 4 | 5.30％ |
| Example 5 | 2.25％ |
| Example 6 | 5.23％ |
| Comparative example 1 | 6.55％ |
| Comparative example 2 | 8.00％ |
| Comparative example 3 | 7.02％ |
According to the comparative data of examples 1-6 and comparative examples 1-3 in table 12, it can be seen that when the positive electrode sheet provided by this example satisfies the requirement of-0.01 < (-0.3788 × PD + 1.155) × ρ/(12 × BET) < 0.0335, the cell prepared from the positive electrode sheet has a lower rebound rate and a smaller rebound rate. Meanwhile, as can be seen from the comparison between examples 1 to 6, when the positive electrode sheet satisfies the requirement of 0 < (-0.3788 XPD + 1.155) × (12 XPET) < 0.005, it has a lower rebound rate. In addition, as can be seen from comparison of the data of examples 1 to 6 with the data of comparative example 1, the rebound rate of the positive electrode sheet can be effectively reduced by adjusting the compaction density of the positive electrode sheet in the examples of the present invention. It can be seen from the comparison of the data of examples 1 to 6 with comparative examples 2 and 3 that the examples of the present invention can satisfy the formula requirement of the positive electrode sheet by adjusting the specific surface area of the positive active material of the positive electrode sheet and the binder density of the positive electrode sheet, and can also effectively reduce the rebound rate of the sheet.
In summary, the positive electrode plate and the battery provided by the embodiment of the invention can improve the rebound problem of the electrode plate by controlling the compaction density on the premise of ensuring the power performance, the rate capability and the cycle performance of the battery; meanwhile, the density of the binder, the specific surface area of the positive active material and the compaction density are cooperatively controlled, so that the rebound of the pole piece is further reduced, and the power performance and the service life of the battery are effectively improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A positive electrode sheet, comprising:
a positive current collector;
a positive electrode diaphragm disposed on at least one side surface of the positive electrode current collector, the positive electrode diaphragm including a positive electrode active material, a conductive agent, and a binder;
the positive pole piece meets the formula: -0.01 < (-0.3788 × PD + 1.155) × ρ/(12 × BET) < 0.0335; wherein PD is the compacted density of the positive pole piece, and the unit is g/cm 3 (ii) a Rho is the density of the binder and has the unit of g/cm 3 (ii) a BET is the specific surface area of the positive electrode active material in m 2 /g。
2. The positive electrode sheet according to claim 1, wherein:
the positive pole piece meets the formula: -0.0031 < - > (-0.3788 × PD + 1.155) × ρ/(12 × BET) < 0.021;
preferably, the positive electrode plate satisfies the formula: 0 < (-0.3788 XPD + 1.155). Times.p/(12 XPBET) < 0.005.
3. The positive electrode sheet according to claim 1, characterized in that:
the compacted density of the positive pole piece meets 2.5g/cm 3 ≤PD≤3.5g/cm 3 ；
Preferably, the compacted density of the positive pole piece meets 2.85g/cm 3 ≤PD≤3.05g/cm 3 。
4. The positive electrode sheet according to claim 1, wherein:
the density of the binder meets 1.70g/cm 3 ≤ρ≤1.80g/cm 3 ；
Preferably, the density of the binder satisfies 1.77g/cm 3 ≤ρ≤1.80g/cm 3 。
5. The positive electrode sheet according to claim 1, wherein:
the specific surface area of the positive electrode active material is 0.8m 2 /g≤BET≤5m 2 /g；
Preferably, the specific surface area of the positive electrode active material satisfies 2.2m 2 /g≤BET≤3.6m 2 /g。
6. The positive electrode sheet according to claim 1, wherein:
the porosity of the positive pole piece ranges from 20% to 60%;
preferably, the porosity of the positive pole piece ranges from 25% to 45%.
7. The positive electrode sheet according to claim 1, wherein:
the positive current collector is selected from any one of aluminum foil, carbon-coated aluminum foil and nickel mesh;
and/or the presence of a gas in the atmosphere,
the positive active material is selected from any one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, and lithium-containing phosphate of olivine structure;
and/or the presence of a gas in the gas,
the conductive agent is selected from any one of carbon black and carbon nanotubes;
and/or the presence of a gas in the gas,
the binder is PVDF.
8. The positive electrode sheet according to claim 1, wherein:
the positive membrane comprises the following components in percentage by mass (90-97): (1-5): the positive electrode active material, the conductive agent, and the binder of (1-5).
9. The positive electrode sheet according to claim 1, characterized in that:
and the two side surfaces of the positive current collector are provided with the positive diaphragm.
10. A battery comprising the positive electrode sheet according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1830104A (en) * | 2003-07-28 | 2006-09-06 | 昭和电工株式会社 | High density electrode and battery using the electrode |
| CN109494349A (en) * | 2018-10-17 | 2019-03-19 | 宁德时代新能源科技股份有限公司 | Negative pole piece and secondary battery |
| CN113086978A (en) * | 2021-03-30 | 2021-07-09 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830104A (en) * | 2003-07-28 | 2006-09-06 | 昭和电工株式会社 | High density electrode and battery using the electrode |
| CN109494349A (en) * | 2018-10-17 | 2019-03-19 | 宁德时代新能源科技股份有限公司 | Negative pole piece and secondary battery |
| CN113086978A (en) * | 2021-03-30 | 2021-07-09 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
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