CN116525761A - Negative pole piece, energy storage device and electric equipment - Google Patents
Negative pole piece, energy storage device and electric equipment Download PDFInfo
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- CN116525761A CN116525761A CN202310747554.7A CN202310747554A CN116525761A CN 116525761 A CN116525761 A CN 116525761A CN 202310747554 A CN202310747554 A CN 202310747554A CN 116525761 A CN116525761 A CN 116525761A
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- 238000004146 energy storage Methods 0.000 title claims abstract description 16
- 238000005524 ceramic coating Methods 0.000 claims abstract description 122
- 239000002105 nanoparticle Substances 0.000 claims abstract description 97
- 239000000919 ceramic Substances 0.000 claims abstract description 76
- 239000007773 negative electrode material Substances 0.000 claims abstract description 43
- 239000002002 slurry Substances 0.000 claims description 72
- 239000002131 composite material Substances 0.000 claims description 50
- 239000003792 electrolyte Substances 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000006183 anode active material Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 21
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 239000010410 layer Substances 0.000 description 210
- 239000002033 PVDF binder Substances 0.000 description 22
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 18
- 239000011267 electrode slurry Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 11
- 229910021383 artificial graphite Inorganic materials 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000008595 infiltration Effects 0.000 description 7
- 238000001764 infiltration Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- -1 lithium salt lithium hexafluorophosphate Chemical compound 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-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
-
- 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
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present disclosure provides a negative pole piece, energy storage device and consumer, this negative pole piece includes: the current collector, negative electrode active layer and ceramic coating, negative electrode active layer set up on the current collector, and ceramic coating stacks up and sets up in negative electrode active layer one side of keeping away from the current collector, and negative electrode active layer includes negative electrode active material, and ceramic coating includes ceramic nanoparticle. Compared with the traditional pole piece without the ceramic coating, the negative pole piece has obviously higher liquid absorption capacity, and the liquid absorption capacity of the battery can be further improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a negative pole piece, an energy storage device and electric equipment.
Background
The secondary battery is an energy storage device, and can be used as an energy source of various electric devices, and is applied to the current production and living in a large scale. Among them, lithium ion batteries, which have relatively high specific energy and mature production processes, have become the largest secondary batteries of current commercial regulations.
In general, lithium ion batteries contain electrolyte, and the content of the electrolyte in the lithium ion batteries has a great influence on the cycle performance and the rate performance of the lithium ion batteries. In current production processes, the electrolyte is typically adsorbed by the cell structure itself, and the non-adsorbed electrolyte is removed in the production process. The current liquid absorption capacity of the battery is still to be further improved.
Disclosure of Invention
In view of this, in order to increase the liquid absorption amount of the battery, it is necessary to provide a negative electrode tab. Further, an energy storage device and electric equipment are provided.
According to some embodiments of the present disclosure, there is provided a negative electrode tab, a current collector, a negative electrode active layer and a ceramic coating layer, wherein the negative electrode active layer is stacked on the current collector, the ceramic coating layer is stacked on one side of the negative electrode active layer away from the current collector, the negative electrode active layer comprises a negative electrode active material, the ceramic coating layer comprises ceramic nanoparticles, the porosity of the ceramic layer is greater than that of the negative electrode active layer, and the ratio of the thickness of the ceramic coating layer to that of the negative electrode active layer is 1 (10-30).
In some embodiments of the present disclosure, the negative electrode active layer includes a substrate sub-layer and a composite sub-layer sequentially disposed from bottom to top, the composite sub-layer is disposed between the ceramic coating and the substrate sub-layer, and the composite sub-layer is in contact with the substrate sub-layer and the ceramic coating, the substrate sub-layer includes the negative electrode active material, and the composite sub-layer includes the ceramic nanoparticle and the negative electrode active material.
In some embodiments of the present disclosure, the mass ratio of the ceramic nanoparticles in the composite sub-layer gradually increases in a direction away from the current collector.
In some embodiments of the present disclosure, the composite sublayer is 0.6 μm to 0.9 μm.
In some embodiments of the present disclosure, the ceramic nanoparticles have an average particle size of 20 μm to 60 μm.
In some embodiments of the present disclosure, the ceramic coating has a thickness of 6 μm or less.
In some embodiments of the present disclosure, the thickness of the anode active layer is 30 μm to 90 μm.
In some embodiments of the present disclosure, the negative electrode active material includes a carbon material.
In some embodiments of the present disclosure, the ceramic nanoparticles comprise alumina nanoparticles.
In some embodiments of the present disclosure, the porosity of the anode active layer is 20% -40%.
In some embodiments of the present disclosure, the ceramic coating has a porosity of 30% -50%.
Further, the present disclosure also provides a method for preparing the negative electrode sheet according to the above embodiment, which includes the following steps:
coating a first slurry containing the anode active material on the current collector to form a first slurry layer;
coating a second slurry containing the ceramic nano particles on the current collector to form a ceramic coating;
the anode active layer is formed based on the first slurry layer.
In some embodiments of the present disclosure, the step of forming the anode active layer based on the first slurry layer includes: penetrating the ceramic nanoparticles in the second slurry into the first slurry layer, forming a substrate sub-layer and a composite sub-layer in the first slurry layer, the negative electrode active layer including the substrate sub-layer and the composite sub-layer; the substrate sub-layer includes the negative electrode active material, and the composite sub-layer includes the ceramic nanoparticle and the negative electrode active material mixed.
In some embodiments of the present disclosure, in the step of coating the second slurry containing the ceramic nanoparticles on the current collector, a portion of the solvent remaining in the first slurry layer is controlled so that the ceramic nanoparticles can infiltrate into the first slurry layer.
Further, the present disclosure also provides an energy storage device, comprising:
the positive pole piece, negative pole piece and electrolyte, the positive pole piece with the negative pole piece sets up relatively, the electrolyte set up in the positive pole piece with between the negative pole piece, the negative pole piece is the negative pole piece of any embodiment above.
Further, the present disclosure also provides a powered device, which includes a functional component and an energy storage device according to any one of the above embodiments, where the energy storage device is configured to supply power to the functional component.
The negative electrode plate comprises a negative electrode active layer and a ceramic coating which are arranged in a laminated mode, wherein the ceramic coating comprises ceramic nano particles, and the negative electrode active layer comprises a negative electrode active material. Nanometer micropores are formed among ceramic nano particles in the ceramic coating, so that the ceramic coating has higher porosity and is favorable for infiltration and absorption of electrolyte. And the porosity in the ceramic coating is higher than the porosity of the anode active layer, and the ratio of the thickness of the ceramic coating to the thickness of the anode active layer is designed to be 1 (10-30), so that electrolyte solvent molecules stored between ceramic nano particles can fully infiltrate the anode active layer and provide a sufficient path for conducting lithium ions, and normal charge and discharge of the anode active material are ensured. Therefore, compared with the traditional pole piece without the ceramic coating, the negative pole piece can ensure that the negative pole piece has obviously higher liquid absorption capacity under the condition of normal charge and discharge, and the liquid absorption capacity of the battery can be further improved.
In addition, the ceramic coating also has a certain blocking effect, is laminated on the negative electrode active layer, can prevent the negative electrode active material in the negative electrode plate from being directly contacted with the positive electrode active material when accidents occur, reduces the probability of short circuit in the battery, and can further improve the safety performance of the battery.
Drawings
FIG. 1 is a schematic view of a negative electrode sheet;
FIG. 2 is a schematic diagram of method steps for preparing a negative electrode sheet;
fig. 3 is a schematic view of a structure in which a first slurry layer is formed on a current collector;
fig. 4 is a schematic structural view of forming a second slurry layer on a current collector;
wherein, each reference sign and meaning are as follows:
100. a current collector; 101. a first slurry layer; 102. a second slurry layer; 110. a negative electrode active layer; 111. a substrate sub-layer; 112. a composite sub-layer; 120. and (3) a ceramic coating.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, and "multiple" as used herein includes two or more of the items.
In the present invention, the sum of the parts of the components in the composition may be 100 parts by weight, if not stated to the contrary. Unless otherwise indicated, the percentages (including weight percent) of the present invention are based on the total weight of the composition, and, in addition, "wt%" herein means mass percent and "at%" means atomic percent.
In this context, unless otherwise indicated, the individual reaction steps may or may not be performed in the order herein. For example, other steps may be included between the respective reaction steps, and the order of the reaction steps may be appropriately changed. This can be determined by the skilled person based on routine knowledge and experience. Preferably, the reaction processes herein are performed sequentially.
Typically, the battery includes a separator and an electrode, each of which can adsorb a small amount of electrolyte. In order to improve the liquid retention of the battery, a glue layer is coated on the surface of the separator to improve the liquid retention of the separator. However, the additional coating of the gel layer on the surface of the separator may significantly affect the conduction of lithium ions, which may instead result in degradation of the cycle performance and rate performance of the battery.
Fig. 1 is a schematic structural view of a negative electrode tab of the present disclosure. Referring to fig. 1, the present disclosure provides a negative electrode tab, comprising: the current collector 100, the negative electrode active layer 110 and the ceramic coating 120, wherein the negative electrode active layer 110 is arranged on the current collector 100 in a lamination mode, the ceramic coating 120 is arranged on one side, far away from the current collector 100, of the negative electrode active layer 110, the negative electrode active layer 110 comprises a negative electrode active material, and the ceramic coating 120 comprises ceramic nano particles.
The negative electrode plate comprises a negative electrode active layer 110 and a ceramic coating 120 which are stacked, wherein the ceramic coating 120 comprises ceramic nano particles, and the negative electrode active layer 110 comprises a negative electrode active material. Nano-scale micropores are formed among ceramic nano-particles in the ceramic coating 120, so that the ceramic coating 120 has higher porosity, and is favorable for infiltration and absorption of electrolyte. And, the porosity in the ceramic coating 120 is set to be higher than that of the anode active layer, and the ratio of the thickness of the ceramic coating 120 to the thickness of the anode active layer 110 is designed to be 1 (10-30), so that electrolyte solvent molecules stored between ceramic nano particles can fully infiltrate the anode active layer and provide a sufficient path for conducting lithium ions, and normal charge and discharge of the anode active material are ensured. Therefore, compared with the conventional electrode sheet without the ceramic coating 120, the negative electrode sheet can ensure that the negative electrode sheet has a significantly higher liquid absorption capacity under the condition of normal charge and discharge, which can further improve the liquid absorption capacity of the battery.
In addition, the ceramic coating 120 has a certain blocking effect, and is laminated on the negative electrode active layer 110, so that the negative electrode active material in the negative electrode plate can be prevented from being directly contacted with the positive electrode active material when an accident occurs, the probability of short circuit inside the battery is reduced, and the safety performance of the battery can be improved.
It is understood that in the negative electrode tab of the present disclosure, ceramic nanoparticles are included in the ceramic coating 120, and gaps exist between the ceramic nanoparticles, which enable the electrolyte to infiltrate the ceramic coating 120. The ceramic nanoparticles may be in contact or bonded together and multiple ceramic nanoparticles may be combined in ceramic coating 120 to form a larger aggregate, which is still believed to include ceramic nanoparticles.
In the negative electrode tab of the present disclosure, the porosity in the ceramic coating 120 should be greater than the porosity of the negative electrode active layer 110, and the ratio of the thickness of the ceramic coating 120 to the thickness of the negative electrode active layer 110 is 1 (10-30). This enables the electrolyte to more sufficiently infiltrate the ceramic coating 120 and facilitates the electrolyte to infiltrate through the ceramic coating 120 to the underlying anode active layer 110. It will be appreciated that when the thickness of the ceramic coating 120 is too high, the micropore paths therein are too long and even blocked, which makes it difficult for ions to conduct effectively, and when the thickness of the ceramic coating 120 is too low, the ceramic coating 120 is difficult to contain enough electrolyte, which affects the overall liquid retention of the electrode and thus the electrical performance. Further, the ceramic coating 120 is provided with higher porosity on the basis of thickness, so that the ceramic coating 120 can effectively infiltrate the anode active layer 110 after absorbing electrolyte, the electrolyte absorbed by the ceramic coating 120 can fully act on the anode active layer 110, and the ion conductivity of the whole anode piece is effectively improved.
In some examples of this embodiment, the ratio of the thickness of the ceramic coating 120 to the anode active layer 110 may be 1:10, 1:15, 1:20, 1:25, or 1:30, and the ratio of the thickness of the ceramic coating 120 to the anode active layer 110 may also be in a range between any two of the ratios described above.
In some examples of this embodiment, the porosity of the ceramic coating 120 is 30% -50%. The porosity of the ceramic coating 120 is 30% -50%, so that effective infiltration of the ceramic coating 120 and the anode active layer 110 can be ensured, normal conduction of ions is further ensured, and the ceramic coating 120 additionally arranged on the anode active layer 110 hardly has negative influence on the internal resistance of the battery. When the porosity of the ceramic coating 120 is high, the structural stability of the ceramic coating 120 is affected. When the porosity of the ceramic coating 120 is low, this in turn causes the internal resistance of the battery to begin to increase significantly. Further, the porosity of the ceramic coating 120 may be 30%, 35%, 40%, 45%, or 50%, or the porosity of the ceramic coating 120 may be in a range between any two of the above.
It will be appreciated that the overall liquid absorption of the negative electrode sheet is related to the thickness of the ceramic coating 120 and the porosity of the ceramic coating 120. In general, the greater the thickness and porosity of the ceramic coating 120, the greater the liquid uptake of the negative electrode sheet. For example, when the porosity is within a certain range, the liquid absorption amount of the ceramic coating 120 has a linear relationship with the thickness thereof.
It is understood that the porosity of the ceramic coating 120 may be controlled by the method of preparation and/or the particle size of the ceramic nanoparticles therein. In some examples of this embodiment, the average particle diameter of the ceramic nanoparticles may be controlled to be 20 μm to 60 μm. For ceramic nano-particles with average particle diameters of 20-60 μm, the ceramic coating 120 with higher porosity and stable structure can be spontaneously formed during coating, so that the performance of the ceramic coating 120 can be improved, and the preparation mode of the ceramic coating is simplified. Further, the average particle diameter of the ceramic nanoparticles may be 20 μm, 30 μm, 40 μm, 50 μm or 60 μm, or the average particle diameter of the ceramic nanoparticles may be in a range between any of the above particle diameters.
In some examples of this embodiment, the porosity of the anode active layer 110 is 20% -40%, and by controlling the porosity of the anode active layer 110 to be 20% -40%, the anode active layer 110 can be fully soaked by the electrolyte, so that the overall anode active layer 110 has better charge-discharge performance. Further, the porosity of the anode active layer 110 may be 20%, 25%, 30%, 35%, or 40%, or the porosity of the anode active layer 110 may be in a range between any two of the above-described porosities. It is understood that the color of the ceramic coating 120 may be different from that of the ceramic coating 120 due to the difference between the ceramic barrier material and the negative active material. This makes it possible to observe the negative electrode sheet with an apparatus such as an optical microscope or an electron microscope, generally in regions of different colors, which correspond to the region where the ceramic coating 120 is located and the region where the negative electrode active layer 110 is located, respectively.
In some examples of this embodiment, the ceramic coating 120 may be prepared on the anode active layer 110 by coating, for example, using a slurry containing ceramic nanoparticles and coating it on the anode active layer 110 to form the ceramic coating 120. The ceramic coating 120 may directly contact the negative electrode active layer 110, so that the electrolyte absorbed in the ceramic coating 120 may also directly infiltrate the negative electrode active layer 110, thereby ensuring normal conduction of lithium ions.
In some examples of this embodiment, referring to fig. 1, the anode active layer 110 includes a base material sub-layer 111 and a composite sub-layer 112 sequentially disposed from bottom to top, the composite sub-layer 112 is disposed between the ceramic coating layer 120 and the base material sub-layer 111, and the composite sub-layer 112 is in contact with the base material sub-layer 111 and the ceramic coating layer 120, the base material sub-layer 111 includes an anode active material, and the composite sub-layer 112 includes ceramic nanoparticles and an anode active material mixed.
It will be appreciated that the substrate sub-layer 111 may contain a negative electrode active material without ceramic nano-particles, and the composite sub-layer 112 may contain certain ceramic nano-particles. Further, the ceramic coating 120 may not contain a negative electrode active material. The composite sub-layer 112 may serve as a transition region between the substrate sub-layer 111 and the ceramic coating 120, with the mass ratio of ceramic nanoparticles in the composite sub-layer 112 being between the ceramic coating 120 and the substrate sub-layer 111. The composite sublayer 112 containing the ceramic nanoparticles and the anode active material may serve as a guiding layer for the electrolyte so that the electrolyte can diffuse into the anode active material along the ceramic nanoparticles, which can further increase the wettability of the electrolyte to the anode active layer 110 as a whole and further improve the ionic conductivity of the anode sheet.
In some examples of this embodiment, the ceramic nanoparticles in the composite sublayer 112 account for 10% -50% of the mass of the composite sublayer 112. The mass ratio of the ceramic nano particles is set to be 10% -50%, the diffusion of the electrolyte from the ceramic coating 120 to the substrate sub-layer 111 is better guided, and the infiltration uniformity is improved. The higher or lower mass ratio of the ceramic nanoparticles affects the uniform diffusion and wetting of the electrolyte from the ceramic coating 120 into the substrate sub-layer 111. Further, the mass ratio of the ceramic nanoparticles in the composite sublayer 112 may be 10%, 20%, 30%, 40% or 50%, or the mass ratio of the ceramic nanoparticles may be between any two of the mass ratios.
In some examples of this embodiment, the mass fraction of ceramic nanoparticles in the composite sublayer 112 gradually increases in a direction away from the current collector 100. By arranging the ceramic nanoparticles in the composite sub-layer 112 with gradually increasing mass ratio, the transition from the ceramic resistance layer to the substrate sub-layer 111 in the negative electrode active layer 110 can be smoother, which is favorable for uniform infiltration of the negative electrode active layer 110 and ensures stable combination between the ceramic coating 120 and the negative electrode active layer 110.
It is understood that the base material sub-layer 111 in the anode active layer 110 in this embodiment corresponds to a single anode active layer 110 in the conventional art. Other materials are not generally provided on the surface of the anode active layer 110 in the conventional art because this hinders the infiltration of the anode active layer 110 into the electrolyte and reduces the ion conductive performance of the battery. The present disclosure further provides a ceramic coating 120 on the anode active layer 110, and ceramic nanoparticles in the ceramic coating 120 can create a microporous environment, which maintains ion conductivity while effectively adsorbing an electrolyte. Further, the composite sub-layer 112 is disposed in the anode active layer 110, so that the electrolyte is soaked more uniformly, and stable combination between the ceramic coating 120 and the anode active layer 110 is ensured.
It will be appreciated that the composite sublayer 112 serves as a transition region between the substrate sublayer 111 and the ceramic coating 120, and that the composite sublayer 112 includes ceramic nanoparticles and a negative electrode active material therein, so that when the negative electrode sheet is viewed using an apparatus such as an optical microscope or an electron microscope, the color of the composite sublayer 112 is different from that between the substrate sublayer 111 and the ceramic coating 120, and that the color of the composite sublayer 112 may be intermediate between the substrate and the ceramic coating 120.
In some examples of this embodiment, the ceramic coating 120 has a thickness of 6 μm or less. By controlling the thickness of the ceramic coating 120 to be less than 6 μm, the influence of the ceramic coating 120 on ion conduction can be reduced as much as possible, and the problem that ions are blocked or cannot be conducted due to the too thick ceramic coating 120 is avoided. Further, the thickness of the ceramic coating 120 may be 1 μm to 6 μm. For example, the thickness of the ceramic coating 120 may be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, or the thickness of the ceramic coating 120 may be in a range between any two of the above.
In some examples of this embodiment, the thickness of the anode active layer 110 is 30 μm to 90 μm. For example, the thickness of the anode active layer 110 may be 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 90 μm, or the thickness of the anode active layer 110 may be in a range between any two of the above. The thickness of the anode active layer 110 is set to be 30-90 μm, so that the anode active layer 110 can be soaked by electrolyte more fully while having higher energy density, and effective conduction of ions is facilitated.
In some examples of this embodiment, the negative electrode active material includes a carbon material. The carbon material may include, among other things, one or more of graphite, hard carbon, and mesophase carbon microbeads.
In some examples of this embodiment, the ceramic nanoparticles include oxide nanoparticles. The compatibility between the oxide and the electrolyte and between the carbon materials is good, and the oxide can be stably attached to the anode active layer 110 while ensuring the infiltration and absorption of the electrolyte. In addition, more abundant micropores can be formed among the oxide nanoparticles.
In some examples of this embodiment, the ceramic nanoparticles comprise alumina nanoparticles.
In some examples of this embodiment, a binder may also be included in the ceramic coating 120, and the ceramic nanoparticles may be bonded to each other by the binder to form a stable structure. Wherein the binder may include, but is not limited to, polyvinylidene fluoride.
In some examples of this embodiment, the mass ratio of ceramic nanoparticles in the ceramic coating 120 may be above 70%. For example, the mass fraction of ceramic nanoparticles may be 70% -95%. Further, the mass ratio of the ceramic nanoparticles may be 70%, 75%, 80%, 85%, 90% or 95%, or the mass ratio of the ceramic nanoparticles may be in a range between any two percentages mentioned above. The ceramic nano particles are arranged to have higher mass ratio, so that the adsorption quantity of the ceramic nano particles to the electrolyte is improved, and the integral structural stability of the ceramic coating 120 is ensured.
In some examples of this embodiment, the specific surface area of the anode active material is 1.32cm 2 /g~1.8cm 2 And/g, so that the negative electrode active material has proper liquid absorption amount, and the electrical property of the negative electrode material is ensured. For example, the specific surface area of the anode active material may be 1.32cm 2 /g、1.4cm 2 /g、1.5cm 2 /g、1.6cm 2 /g、1.7cm 2 /g or 1.8cm 2 The specific surface area of the negative electrode active material may be in the range between any two of the above specific surface areas.
In some examples of this embodiment, the negative electrode active material has a compacted density of 1.2g/cm 3 ~1.9g/cm 3 . For example, the compacted density of the anode active material may be 1.2g/cm 3 、1.4g/cm 3 、1.5g/cm 3 、1.6g/cm 3 、1.8g/cm 3 Or 1.9g/cm 3 The compacted density of the anode active material may also be in a range between any two of the compacted densities described above. This is advantageous in reducing the internal resistance of the anode active layer 110.
It is understood that the current collector 100 serves to conduct electrons in the negative active layer 110 to an external circuit. In some examples of this embodiment, current collector 100 may include a metallic material. For example, the current collector 100 may be copper foil.
In some examples of this embodiment, a conductive agent and a binder may also be included in the anode active layer 110. Wherein the conductive agent may be conductive carbon black. The binder may be polyvinylidene fluoride.
In some examples of this embodiment, the mass ratio of the conductive agent in the anode active layer 110 may be 1% -5%. For example, the mass ratio of the conductive agent in the anode active layer 110 may be 1%, 2%, 3%, 4% or 5%, and the mass ratio of the conductive agent in the anode active layer 110 may be in a range between any two of the above-described mass ratios.
In some examples of this embodiment, the mass ratio of the binder in the anode active layer 110 may be 1% -8%. For example, the mass ratio of the binder in the anode active layer 110 may be 1%, 2%, 4%, 6% or 8%, and the mass ratio of the binder in the anode active layer 110 may be in a range between any two of the above-described mass ratios.
Fig. 2 is a schematic diagram of the method steps for preparing a negative electrode sheet. Referring to fig. 2, the disclosure further provides a preparation method of the negative electrode plate, which includes steps S1 to S2, specifically as follows.
In step S1, a first slurry including a negative electrode active material is coated on a current collector 100.
Wherein, after the first paste is coated, the first paste layer 101 can be formed on the current collector 100.
Fig. 3 is a schematic view of a structure in which a first slurry layer 101 is formed on a current collector 100. Referring to fig. 3, a first slurry layer 101 is stacked on a current collector 100.
In some examples of this embodiment, copper foil may be employed as the current collector 100.
In some examples of this embodiment, a conductive agent and a binder may also be included in the first paste.
In some examples of this embodiment, azomethylpyrrolidone may be employed as the dispersant for the first slurry.
In some examples of this embodiment, mesophase carbon microbeads may be employed as the negative electrode active material, super P as the conductive agent, and polyvinylidene fluoride as the binder. The mass ratio among the anode active material, the conductive agent and the binder is 94:2:4.
In some examples of this embodiment, the solid phase components in the first slurry may be added to the dispersant after being mixed uniformly to form the first slurry.
In some examples of this embodiment, the first slurry may be applied to current collector 100 by knife coating.
It will be appreciated that after the first slurry is applied, the first slurry may be subjected to a drying process to remove the dispersant from the first slurry. However, in some examples of this embodiment, the degree of drying may be controlled or the drying process may not be performed so that the dispersant may remain in the formed first slurry layer 101. This can allow the anode active material to have a certain fluidity in the first slurry layer 101, so that ceramic nanoparticles can be properly embedded in the first slurry layer 101.
Step S2, a second paste containing ceramic nanoparticles is coated on the first paste layer 101.
Wherein, after the second paste is applied, a second paste layer 102 can be formed on the current collector 100.
Fig. 4 is a schematic diagram of a structure in which a second slurry layer 102 is formed on a current collector 100. Referring to fig. 4, the second slurry layer 102 is stacked on the first slurry layer 101.
In some examples of this embodiment, a binder may also be included in the second slurry.
In some examples of this embodiment, azomethylpyrrolidone may be employed as the dispersant for the second slurry.
In some examples of this embodiment, alumina nanoparticles may be used as the ceramic nanoparticles and polyvinylidene fluoride may be used as the binder. Further, the mass ratio of the ceramic nano particles to the polyvinylidene fluoride can be controlled to be (8-9): 1-2.
In some examples of this embodiment, the ceramic nanoparticles may be added to the dispersant after the binder is uniformly dispersed in the dispersant.
In some examples of this embodiment, the second slurry may be applied to the already prepared first slurry layer 101 by blade coating.
In some examples of this embodiment, the anode active layer 110 may be formed based on the first slurry layer 101. For example, the step of forming the anode active layer 110 based on the first slurry layer 101 includes: penetrating ceramic nanoparticles in the second slurry into the first slurry layer 101, forming a base material sub-layer 111 and a composite sub-layer 112 in the first slurry layer 101, the anode active layer 110 including the base material sub-layer 111 and the composite sub-layer 112; the substrate sub-layer 111 includes a negative electrode active material, and the composite sub-layer 112 includes ceramic nano-particles and a negative electrode active material mixed. It will be appreciated that if the dispersant in the pre-prepared first slurry layer 101 is not completely removed, the ceramic nanoparticles may penetrate into the first slurry layer 101 and form the composite sub-layer 112 during the step of coating the second slurry. The region of the first slurry layer 101 near the bottom is not infiltrated with ceramic nanoparticles, and thus may serve as a substrate sub-layer 111.
In some examples of this embodiment, after the second slurry containing ceramic nanoparticles is coated on the first slurry layer 101, the second slurry may also be subjected to a drying process to remove the dispersant in the second slurry and cause the second slurry layer 102 to form the ceramic coating 120. It will be appreciated that if a portion of the dispersant remains in the first slurry layer 101, the dispersant in the first slurry layer 101 can also be completely removed in this step. Thereby forming the anode active layer 110 and the ceramic coating layer 120 which are structurally stable.
It can be appreciated that the negative electrode tab shown in fig. 1 can be prepared by the above steps S1 to S2.
The disclosure also provides an energy storage device, which comprises a positive pole piece, a negative pole piece and an electrolyte, wherein the positive pole piece and the negative pole piece are oppositely arranged, the electrolyte is arranged between the positive pole piece and the negative pole piece, and the negative pole piece is the negative pole piece according to the embodiment. It is understood that the energy storage device may be a battery, further that the energy storage device may be, but is not limited to, a lithium ion battery.
The disclosure further provides an electrical device comprising a functional component and an energy storage device as in the above embodiments, the energy storage device being configured to supply power to the functional component. The powered device may be, but is not limited to, a portable electronic device or an electric vehicle.
In order that the invention may be more readily understood and put into practical effect, the following more particular examples and comparative examples are provided as reference. The various embodiments of the present invention and their advantages will also be apparent from the following description of specific examples and comparative examples and performance results. In the following test examples and comparative examples, the raw materials used in the following examples and comparative examples are commercially available as usual unless otherwise specified.
Example 1
Adopting artificial graphite as a negative electrode active material, mixing the negative electrode active material, super P and polyvinylidene fluoride as binders according to the mass ratio of 94:2:4, adding the mixture into azomethyl pyrrolidone to prepare negative electrode slurry, and coating the negative electrode slurry on copper foil to form a first slurry layer;
respectively adding polyvinylidene fluoride and alumina nano particles with average particle size of 40 mu m into nitrogen methyl pyrrolidone according to the mass ratio of 2:8, adding the alumina nano particles after the polyvinylidene fluoride is fully dissolved, uniformly stirring, coating the mixture on a first slurry layer, and drying to remove the nitrogen methyl pyrrolidone to respectively form a negative electrode active layer and a ceramic coating, wherein the negative electrode active layer at least comprises a substrate sub-layer and a composite sub-layer, the substrate sub-layer does not contain the alumina nano particles, and the composite sub-layer contains the alumina nano particles and artificial graphite;
wherein the thickness of the ceramic coating layer was 3 μm and the total thickness of the anode active layer was 60 μm.
Example 2
Adopting artificial graphite as a negative electrode active material, mixing the negative electrode active material, super P and polyvinylidene fluoride binder in a mass ratio of 94:2:4, adding the mixture into nitrogen methyl pyrrolidone to prepare negative electrode slurry, coating the negative electrode slurry on copper foil, and drying the nitrogen methyl pyrrolidone to form a negative electrode active layer;
respectively adding polyvinylidene fluoride and alumina nano particles with average particle size of 40 mu m into azomethyl pyrrolidone according to the mass ratio of 2:8, adding the alumina nano particles after the polyvinylidene fluoride is fully dissolved, uniformly stirring, coating the mixture on a first slurry layer, and drying to remove the azomethyl pyrrolidone to form a ceramic coating;
wherein the thickness of the ceramic coating layer was 3 μm and the thickness of the anode active layer was 60 μm.
Example 3
Adopting artificial graphite as a negative electrode active material, mixing the negative electrode active material, super P and polyvinylidene fluoride as binders according to the mass ratio of 94:2:4, adding the mixture into azomethyl pyrrolidone to prepare negative electrode slurry, and coating the negative electrode slurry on copper foil to form a first slurry layer;
respectively adding polyvinylidene fluoride and alumina nano particles with average particle size of 40 mu m into nitrogen methyl pyrrolidone according to the mass ratio of 2:8, adding the alumina nano particles after the polyvinylidene fluoride is fully dissolved, uniformly stirring, coating the mixture on a first slurry layer, and drying to remove the nitrogen methyl pyrrolidone to respectively form a negative electrode active layer and a ceramic coating, wherein the negative electrode active layer at least comprises a substrate sub-layer and a composite sub-layer from bottom, the substrate sub-layer does not contain the alumina nano particles, and the composite sub-layer contains the alumina nano particles and artificial graphite;
wherein the thickness of the ceramic coating layer was 2 μm and the total thickness of the anode active layer was 60 μm. Comparative example 1
Adopting artificial graphite as a negative electrode active material, mixing the negative electrode active material, super P and polyvinylidene fluoride binder in a mass ratio of 94:2:4, adding the mixture into nitrogen methyl pyrrolidone to prepare negative electrode slurry, coating the negative electrode slurry on copper foil, and drying to remove the nitrogen methyl pyrrolidone to form a negative electrode active layer; wherein the thickness of the anode active layer was 64 μm.
Comparative example 2
Adopting artificial graphite as a negative electrode active material, mixing the negative electrode active material, super P and polyvinylidene fluoride as binders according to the mass ratio of 94:2:4, adding the mixture into azomethyl pyrrolidone to prepare negative electrode slurry, and coating the negative electrode slurry on copper foil to form a first slurry layer;
respectively adding polyvinylidene fluoride and alumina nano particles with average particle size of 1 mu m into nitrogen methyl pyrrolidone according to the mass ratio of 2:8, adding the alumina nano particles after the polyvinylidene fluoride is fully dissolved, uniformly stirring, coating the mixture on a first slurry layer, and drying to remove the nitrogen methyl pyrrolidone to respectively form a negative electrode active layer and a ceramic coating, wherein the negative electrode active layer at least comprises a substrate sub-layer and a composite sub-layer, the substrate sub-layer does not contain the alumina nano particles, and the composite sub-layer contains the alumina nano particles and artificial graphite;
wherein the thickness of the ceramic coating layer was 3 μm and the total thickness of the anode active layer was 60 μm.
Comparative example 3
Adopting artificial graphite as a negative electrode active material, mixing the negative electrode active material, super P and polyvinylidene fluoride as binders according to the mass ratio of 94:2:4, adding the mixture into azomethyl pyrrolidone to prepare negative electrode slurry, and coating the negative electrode slurry on copper foil to form a first slurry layer;
respectively adding polyvinylidene fluoride and alumina nano particles with average particle size of 40 mu m into nitrogen methyl pyrrolidone according to the mass ratio of 2:8, adding the alumina nano particles after the polyvinylidene fluoride is fully dissolved, uniformly stirring, coating the mixture on a first slurry layer, and drying to remove the nitrogen methyl pyrrolidone to respectively form a negative electrode active layer and a ceramic coating, wherein the negative electrode active layer at least comprises a substrate sub-layer and a composite sub-layer, the substrate sub-layer does not contain the alumina nano particles, and the composite sub-layer contains the alumina nano particles and artificial graphite;
wherein the thickness of the ceramic coating layer is 10 μm and the total thickness of the anode active layer is 60 μm.
Among them, the negative electrode sheets prepared in comparative examples 2 and 3 had significantly high internal resistance, and were not suitable for preparing batteries.
Test 1: the negative electrode sheets prepared in each example and comparative example 1 were taken out after being placed in an electrolyte, and after the electrolyte was sufficiently absorbed, the liquid absorption amount was measured, and the results can be seen in table 1.
Test 2: the negative electrode sheets prepared in each example and comparative example 1 were assembled with a positive electrode sheet, a separator and an electrolyte to form a button cell, and the capacity retention after 100 cycles was measured, and the results are shown in table 1.
Test 3: the negative electrode sheets prepared in each example and comparative example 1 were assembled with a positive electrode sheet, a separator and an electrolyte to form a button cell, and thermal runaway test was performed, and the results are shown in table 1.
Wherein, the positive electrode plate used in each test exampleThe preparation method of (2) is as follows: lithium nickel cobalt manganate (LiNi) 1/3 Co 1/ 3 Mn 1/3 O 2 ) And (3) mixing the positive electrode active material, super P and polyvinylidene fluoride serving as an adhesive in a mass ratio of 93:3:4, adding the mixture into azomethyl pyrrolidone to prepare positive electrode slurry, coating the positive electrode slurry on an aluminum foil, and then drying and rolling the aluminum foil to form the positive electrode plate.
The electrolyte used in each test example was prepared as follows: ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) were mixed as an organic solvent in a volume ratio of 1:1:1, followed by a sufficiently dry lithium salt lithium hexafluorophosphate (LiPF 6 ) Dissolving in organic solvent according to the proportion of 1mol/L to prepare electrolyte.
TABLE 1
Referring to table 1, each of examples 1 to 3 was provided with a ceramic coating, and comparative example 1 was not provided with a ceramic coating. Compared with comparative example 1, the liquid absorption of the negative electrode sheet of examples 1-3 is obviously improved, which means that the ceramic coating can effectively improve the liquid absorption of the negative electrode sheet, and the electrolyte is used for wetting the negative electrode active layer, so that the diaphragm resistance is reduced, and the circulation capacity retention rate is improved. Further, example 1 has a higher liquid absorption and a lower sheet resistance than example 2, indicating that the introduced composite sub-layer can further enhance the wetting of the anode active layer by the electrolyte. Example 1 also has a higher liquid absorption and a lower sheet resistance than example 3, mainly because the ceramic coating thickness in example 3 is lower than the anode active layer thickness, affecting the liquid absorption and wettability of the anode active layer.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (13)
1. A negative electrode tab, comprising: the current collector comprises a current collector body, a negative electrode active layer and a ceramic coating, wherein the negative electrode active layer is arranged on the current collector body in a layer-by-layer mode, the ceramic coating is arranged on one side, far away from the current collector body, of the negative electrode active layer, the negative electrode active layer comprises a negative electrode active material, the ceramic coating comprises ceramic nano particles, the porosity of the ceramic coating is larger than that of the negative electrode active layer, and the thickness ratio of the ceramic coating to the negative electrode active layer is 1 (10-30).
2. The negative electrode tab of claim 1, wherein the negative electrode active layer comprises a substrate sub-layer and a composite sub-layer sequentially disposed from bottom to top, the composite sub-layer is disposed between the ceramic coating and the substrate sub-layer, and the composite sub-layer is in contact with the substrate sub-layer and the ceramic coating, the substrate sub-layer comprises the negative electrode active material, and the composite sub-layer comprises the ceramic nanoparticles and the negative electrode active material.
3. The negative electrode tab of claim 2, wherein the mass ratio of the ceramic nanoparticles in the composite sub-layer gradually increases in a direction away from the current collector.
4. The negative electrode tab of claim 2, wherein the composite sublayer is 0.6-0.9 μm.
5. The negative electrode sheet according to any one of claims 1 to 4, wherein the average particle diameter of the ceramic nanoparticles is 20 μm to 60 μm.
6. The negative electrode sheet according to any one of claims 1 to 4, wherein the thickness of the ceramic coating is 6 μm or less; and/or the number of the groups of groups,
the thickness of the negative electrode active layer is 30-90 mu m.
7. The negative electrode tab according to any one of claims 1 to 4, wherein the negative electrode active material comprises a carbon material; and/or the number of the groups of groups,
the ceramic nanoparticles include alumina nanoparticles.
8. The negative electrode sheet according to any one of claims 1 to 4, wherein the porosity of the negative electrode active layer is 20% to 40%; and/or the number of the groups of groups,
the porosity of the ceramic coating is 30% -50%.
9. A method for preparing the negative electrode sheet according to any one of claims 1 to 8, comprising the steps of:
coating a first slurry containing the anode active material on the current collector to form a first slurry layer;
coating a second slurry containing the ceramic nano particles on the current collector to form a ceramic coating;
the anode active layer is formed based on the first slurry layer.
10. The method of producing a negative electrode sheet according to claim 9, wherein the step of forming the negative electrode active layer based on the first slurry layer comprises: penetrating the ceramic nanoparticles in the second slurry into the first slurry layer, forming a substrate sub-layer and a composite sub-layer in the first slurry layer, the negative electrode active layer including the substrate sub-layer and the composite sub-layer; the substrate sub-layer includes the negative electrode active material, and the composite sub-layer includes the ceramic nanoparticle and the negative electrode active material mixed.
11. The method according to claim 10, wherein in the step of coating the second slurry containing the ceramic nanoparticles on the current collector, a portion of the solvent remains in the first slurry layer is controlled so that the ceramic nanoparticles can infiltrate into the first slurry layer.
12. An energy storage device, comprising:
the positive pole piece, negative pole piece and electrolyte, the positive pole piece with the negative pole piece sets up relatively, the electrolyte set up in between positive pole piece with the negative pole piece, the negative pole piece is the negative pole piece according to any one of claims 1~ 8.
13. A powered device comprising a functional component and an energy storage device according to claim 12 for powering the functional component.
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