CN116470004A - Porous negative electrode, preparation method thereof and battery - Google Patents
Porous negative electrode, preparation method thereof and battery Download PDFInfo
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- CN116470004A CN116470004A CN202310450272.0A CN202310450272A CN116470004A CN 116470004 A CN116470004 A CN 116470004A CN 202310450272 A CN202310450272 A CN 202310450272A CN 116470004 A CN116470004 A CN 116470004A
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- 239000011148 porous material Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims description 27
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- 238000001035 drying Methods 0.000 claims description 16
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- 238000002156 mixing Methods 0.000 claims description 9
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 5
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- 239000010703 silicon Substances 0.000 abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 21
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 239000010410 layer Substances 0.000 description 103
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 43
- 239000000463 material Substances 0.000 description 26
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- 230000008569 process Effects 0.000 description 10
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- 238000005056 compaction Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 239000002210 silicon-based material Substances 0.000 description 7
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 102000004310 Ion Channels Human genes 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
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- 230000008093 supporting effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- 230000002349 favourable effect Effects 0.000 description 4
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- 238000004080 punching Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
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- 229920002312 polyamide-imide Polymers 0.000 description 3
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- 239000000661 sodium alginate Substances 0.000 description 3
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- 229940005550 sodium alginate Drugs 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Polymers [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
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- 238000004537 pulping Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
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- 239000004925 Acrylic resin Substances 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- -1 nickel cobalt aluminum Chemical compound 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
-
- 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
- H01M4/64—Carriers or 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
- 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
Landscapes
- 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 invention provides a porous negative electrode, a preparation method thereof and a battery, and belongs to the technical field of batteries. Wherein the porous anode comprises a current collector; the porous layer is arranged on the surface of the current collector, and a plurality of pore channels are formed in one end face, away from the current collector, of the porous layer; and a dense layer disposed on a side of the porous layer facing away from the current collector. The porous anode provided by the embodiment of the invention has a pore structure which is uniformly arranged, an expansion space is provided for the expansion of silicon, and the pore structure can improve the wettability of electrolyte, the shuttle speed of lithium ions and the utilization rate of silicon.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a porous negative electrode, a preparation method thereof and a battery.
Background
Silicon materials have been widely studied as a recent research and application of lithium battery anode materials. The focus of the current research is to construct a three-dimensional structure from different dimensions, use a novel binder, compound silicon with other anode materials, and the like, aiming at the problem of large expansion of the silicon material in the charge-discharge process.
Three-dimensional structures are constructed from material dimensions, such as the preparation of porous silicon materials. The preparation difficulty of the porous silicon material is high, and the porous material is unfavorable for the release of electrolyte, so that the volume energy density of the battery core is reduced. The novel binder, such as acrylic resin (Acrylic acid Polymers, PAA) and the like, can improve the adhesion between the negative electrode materials and between the negative electrode host and the current collector due to its network structure, and can improve the expansion of the silicon negative electrode to some extent. However, in the case of a high silicon negative electrode system, PAA has a high glass transition temperature, which causes the electrode sheet to become brittle, and the addition of PAA reduces the improvement of expansion, so that this method, although the expansion is improved, reduces other properties of the negative electrode, and the overall improvement of the performance of the negative electrode is not desirable.
Disclosure of Invention
In view of the above, the present invention provides a porous anode, a method of manufacturing the same, and a battery, in which a porous layer of the porous anode is provided with pores that provide advantageous space for expansion of silicon during a later cycle.
Some embodiments of the present application provide a porous anode. The present application is described in terms of various aspects, embodiments and advantages of which are referred to below.
In a first aspect, the present invention provides a porous anode comprising:
a current collector;
the porous layer is arranged on the surface of the current collector, and a plurality of pore channels are formed in one end face, away from the current collector, of the porous layer; and
the compact layer is arranged on one side of the porous layer, which is away from the current collector.
As an example of the first aspect, the diameter of the pore canal ranges between 1 and 1000 micrometers.
As an embodiment of the first aspect, the hole spacing between the plurality of said holes is between 10 and 1000 microns.
As an embodiment of the first aspect, the pore depth of the pore canal is 30-95% of the thickness of the porous layer, wherein the thickness direction of the porous layer is an extending direction from an end adjacent to the dense layer to an end adjacent to the current collector.
As an example of the first aspect, the compacted density of the porous layer, the compacted density of the dense layer is 1.5 to 1.75g/cc.
As an embodiment of the first aspect, the ratio of the thickness of the porous layer to the thickness of the dense layer is 2:8.
as an embodiment of the first aspect, the thickness of the porous layer is 51 to 99% of the total thickness of the porous anode.
The invention also discloses a preparation method of the porous anode in the second aspect, which comprises the following steps:
s1, providing a current collector;
s2, covering the surface of the current collector with the first slurry, and drying and compacting to obtain a layer structure;
s3, arranging a plurality of pore channels at one end of the layer structure, which is far away from the current collector, so as to obtain a porous layer on the surface of the current collector;
and S4, covering the surface of the porous layer, which is far away from the current collector, with second slurry, drying and compacting to form a compact layer on the surface of the porous layer, and finally obtaining the porous anode.
As an embodiment of the second aspect, in S2, the first slurry is obtained by mixing a first negative electrode material with a first binder and a first conductive agent in proportion.
As an embodiment of the second aspect, in S4, the second paste is obtained by mixing a second negative electrode paste with a second binder and a second conductive agent in proportion.
As an embodiment of the second aspect, the first negative electrode slurry is one or more of nano silicon, micro silicon, silicon oxygen material, silicon carbon material, silicon oxygen/graphite mixed material.
As an example of the second aspect, the first binder and the second binder may be one or more of styrene-butadiene rubber, polyacrylic acid, polyvinylidene fluoride, polyimide, polyamideimide, sodium alginate, polyacrylate, and the like.
As an embodiment of the second aspect, the first conductive agent and the second conductive agent are one or more of conductive carbon black, multi-wall carbon tube, single-wall carbon tube, conductive graphite, graphene, and the like.
As an embodiment of the second aspect, the ratio of the first negative electrode material to the first binder to the first conductive agent is (60 to 98): (1-20): (1-20); the proportion of the second anode material to the second binder to the second conductive agent is (60-98): (1-20): (1-20).
As an embodiment of the second aspect, the second negative electrode slurry is one or more of artificial graphite, natural graphite, mesocarbon microbeads, soft carbon, hard carbon, and graphene.
As an example of the second aspect, the diameter of the pore canal ranges between 1 and 1000 micrometers.
As an example of the second aspect, the hole pitch between the plurality of the holes is between 10 and 1000 micrometers.
As an embodiment of the second aspect, the pore depth of the pore canal is 30 to 95% of the thickness of the porous layer, wherein the thickness direction of the porous layer is an extending direction from one end adjacent to the dense layer to one end adjacent to the current collector.
As an example of the second aspect, the dense layer and the porous layer have a compacted density of 1.5 to 1.75g/cc.
As an embodiment of the second aspect, the ratio of the thickness of the porous layer to the thickness of the dense layer is 2:8.
as an embodiment of the second aspect, the thickness of the porous layer is 51 to 99% of the total thickness of the porous anode.
In a third aspect, the invention also discloses a battery, which comprises a stacked porous anode, a solid electrolyte membrane and a positive electrode, wherein the porous anode is the porous anode according to the embodiment of the first aspect.
The technical scheme of the invention has at least one of the following beneficial effects:
according to the porous anode provided by the embodiment of the invention, the porous layer and the compact layer have a double-layer structure, the porous layer is positioned at one side close to the current collector, and the compact layer is positioned at one layer contacted with the electrolyte. The porous layer has a uniform arrangement of cell structures that provides space for expansion of the silicon to expand. The pore canal structure can improve the wettability of electrolyte, the shuttle speed of lithium ions and the utilization rate of silicon. In addition, the preparation method of the porous negative electrode is simple in preparation process and easy to popularize.
Drawings
FIG. 1 is a schematic side sectional view of a porous anode according to an embodiment of the present invention;
FIG. 2 is a top view of a porous layer according to one embodiment of the present invention;
fig. 3 is a flowchart of a method for preparing a porous anode according to an embodiment of the present invention.
Reference numerals
A porous anode 100; a current collector 10; a porous layer 20; a duct 21; dense layer 30.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The porous anode according to the embodiment of the present invention is described below with reference to the drawings.
Referring to fig. 1, fig. 1 shows a schematic side sectional structure of a porous anode according to an embodiment of the present invention. As shown in fig. 1, the porous anode includes a current collector, a porous layer, and a dense layer. The porous layer is arranged on the surface of the current collector, and a plurality of pore channels are formed in one end face, away from the current collector, of the porous layer. The compact layer is arranged on one side of the porous layer, which is away from the current collector.
According to the porous cathode provided by the embodiment of the invention, the porous layer is provided with the plurality of holes, so that a space can be reserved for the expansion of silicon in the charge and discharge process of the battery, and meanwhile, the wettability of electrolyte is improved, and the multiplying power performance of a battery core is improved. In addition, as the silicon material in the conventional pole piece, which is close to the current collector, has large distance for lithium ions to reach and poor electrolyte wettability, a large part of the silicon material does not participate in charge-discharge reaction, so that the capacity is wasted, and the utilization rate of silicon can be improved by the pore channel structure. In addition, the porous layer is arranged on the surface of the porous layer, so that structural change of the porous layer can be restrained, and unstable pole pieces caused by collapse of pore channels in the cell circulation process are prevented.
As shown in fig. 1, the perforation (pore canal) starts at the side of the porous layer facing the dense layer, wherein the pores may be blind pores (non-through pores), i.e. the side facing the current collector is not perforated. The invention adopts the blind hole, on one hand, the problem that the open hole is easy to increase the probability of the current collector to cause short circuit can be solved. On the other hand, when the upper and lower ends of the hole are both openings (through holes), the supporting force of the upper and lower ends of the porous layer is weakened, and corner collapse is easily generated in the charge and discharge process. The non-through hole structure (blind hole) can maintain the integrity of the pore structure, avoid corner collapse and improve the stability of the cathode.
In an embodiment of the invention, the pore spacing between the plurality of pores is between 10 and 1000 microns. Preferably, the hole spacing is between 100 and 1000 microns. The excessive hole spacing reduces the proportion of effective silicon in the porous layer (silicon in the middle part of the pore canal does not participate in charge-discharge reaction). Meanwhile, in an effective space, the expansion control of silicon is reduced, and the circulation performance is reduced; the lithium ion channels are reduced, and the rate performance is also reduced. The too small hole spacing is easy to cause collapse of the pore canal, so that the negative electrode is unstable, and more time and manpower and material resources are consumed during punching. Therefore, the adoption of the pore spacing in the range is beneficial to maintaining the cycle performance of the battery, can maintain the multiplying power performance of the battery, can avoid the collapse of pore channels and the like, and can maintain the stability of the electrode plate.
In embodiments of the invention, the diameter of the pore canal ranges from 1 to 1000 microns. In preferred embodiments of the present application, the diameter of the holes ranges between 30 and 80 microns, for example, 40 microns, 50 microns, 60 microns, or 70 microns, etc. The pore diameter in the range can ensure the expansion space of silicon, and is beneficial to improving the cycle performance and the multiplying power performance of the battery.
Referring to fig. 2, fig. 2 shows a top view of a porous layer of one embodiment of the present invention. As shown in fig. 2, the porous layer structure obtained by the preparation method has a plurality of pores arranged in order. Wherein, the spacing between the pore channels is 144.7 μm, 142.5 μm and 140.6 μm, and the pore diameter of the pore channels is 47.1 μm and 48.9 μm. The existence of the porous layer can ensure the expansion space of silicon in the charge and discharge of the battery, thereby being beneficial to improving the cycle performance and the multiplying power performance of the battery.
In one embodiment of the present invention, the pore depth of the pore canal accounts for 30-95% of the thickness of the porous layer, and further may be 70-80%. The thickness direction of the porous layer is the extending direction from one end adjacent to the dense layer to one end adjacent to the current collector (the distance from the top to the bottom of the porous layer as shown in fig. 1 is the thickness of the porous layer). When the depth of the pore canal is too small, the proportion of effective silicon in the porous layer is reduced (namely, the proportion of silicon which is close to the current collector and does not participate in charge and discharge is increased). And when the expansion space of silicon is reduced, the cycle performance of the battery is reduced, the lithium ion channel is reduced, and the multiplying power performance is also reduced.
In one embodiment of the invention, the compacted density of the porous layer, the compacted density of the dense layer may be in the range of 1.5 to 1.75g/cc. Preferably, the porous layer has a compacted density of between 1.6 and 1.7g/cc, which provides effective support for the cells. And the compacted density is favorable for lithium ion shuttling, and can improve the rate capability.
In embodiments of the present invention, the densified layer can have a compacted density of 1.5 to 1.75g/cc. Preferably, the compacted density may be between 1.55 and 1.6 g/cc. The compaction density has good supporting force, and can effectively avoid the unstable pole piece condition caused by the collapse of the pore canal in the cell circulation process.
The ratio of the thickness of the porous layer to the thickness of the dense layer was 2:8. and the thickness of the porous layer accounts for 51-99% of the total thickness of the porous cathode. The proportion can better avoid the collapse of the pore canal on one hand, and on the other hand, the thickness of the proportion is proper, thereby being beneficial to the shuttling of lithium ions and improving the multiplying power performance of the battery.
Therefore, according to the porous anode provided by the embodiment of the invention, the space is reserved for the expansion of silicon, the wettability of electrolyte is improved, and the multiplying power performance of the battery cell is improved. And the channel structure can improve the utilization rate of silicon. Has the characteristics of high capacity, high cycle stability and excellent quick-charging performance.
The method for preparing the porous anode according to the embodiment of the invention is described below with reference to the accompanying drawings.
It should be noted that the source of the raw materials not mentioned in the present invention may be commercially available or prepared by a conventional method, and the present invention is not limited thereto.
Referring to fig. 3, fig. 3 shows a flowchart of a method of manufacturing a porous anode according to an embodiment of the present invention. As shown in FIG. 1, the method includes S1-S4, each of which is described below.
In S1, a current collector is provided.
In the embodiment of the invention, the current collector can be one or more of common smooth copper foil, carbon coated copper foil and rough copper foil.
In S2, covering the surface of the current collector with the first slurry, drying and compacting to obtain a layer structure.
Wherein the first slurry is a mixture of a plurality of materials. The mixture can comprise a first anode material, a first binder and a first conductive agent, and the raw materials are mixed according to a proportion to obtain first slurry.
In some embodiments, the ratio of the first anode material to the first binder, the first conductive agent is (60-98): (1-20): (1-20), for example, 60:1:1, 98:20:20, 80:15:13, etc. After the materials with the proportion are mixed, the bonding between the layers is facilitated, meanwhile, the compaction density of the compact layer is ensured, and a strong supporting effect is ensured.
In some embodiments, the first negative electrode paste may employ one or more of high-capacity nano-silicon, micro-silicon, silicon oxygen materials, silicon carbon materials, silicon oxygen/graphite mixed materials. In the present invention, a silicon oxide material may be preferable, and silicon near the current collector for the entire electrode sheet does not take part in the charge-discharge reaction due to poor wettability of the electrolyte, and thus does not exert capacity. And the silicon oxide materials with the same proportion are arranged on the inner side of the pole piece and a three-dimensional pore canal structure is constructed, the pore canal provides a favorable space for the expansion of silicon, and the wettability of electrolyte, the shuttle speed of lithium ions and the utilization rate of silicon can be improved.
In embodiments of the present invention, the first slurry may be coated on the surface of the current collector. It may also be sprayed, deposited, or the like, such that the first slurry covers the surface of the current collector.
In some embodiments, the first binder may employ one or more of styrene-butadiene rubber SBR, polyacrylic acid PAA, polyvinylidene fluoride PVDF, polyimide PI, imide PAI, sodium alginate, polyacrylate, and the like.
The first conductive agent may be one or more of conductive carbon black, multi-wall carbon tube, single-wall carbon tube, conductive graphite, graphene, and the like.
In the embodiment of the invention, in the drying process, one-time drying or multiple-time drying can be adopted, and the drying temperature is 90-180 ℃.
In some embodiments, the porous layer has a compacted density of 1.5-1.75 g/cc, has good support, and the compacted density facilitates lithium ion shuttling, and can improve rate capability.
In S3, a plurality of cells are provided at an end of the layer structure facing away from the current collector to obtain a porous layer on the surface of the current collector.
Wherein, after the layer structure is dried and compacted, a laser etching device may be used to punch holes on a side of the layer structure facing away from the current collector, so as to form a porous layer as shown in fig. 1 and 2. The holes can also be punched by adopting a mechanical punching device and the like.
In the invention, the diameter of the pore canal is between 1 and 1000 micrometers. The hole spacing between the plurality of holes is between 10 and 1000 microns. The pore depth of the pore canal accounts for 30-95% of the thickness of the porous layer. The ratio of the thickness of the porous layer to the thickness of the dense layer was 2: and 8, the thickness of the porous layer accounts for 51-99% of the total thickness of the porous anode. The size of the hole and the like are described in the above embodiments, and the operation and effect thereof are not described here.
And S4, covering the surface of the porous layer, which is far away from the current collector, with the second slurry, drying and compacting to form a compact layer on the surface of the porous layer, and finally obtaining the porous anode.
The second slurry is obtained by mixing the second negative electrode slurry with a second binder and a second conductive agent according to a proportion.
The proportion of the second anode material to the second binder to the second conductive agent is (60-98): (1-20): (1-20). After the materials with the proportion are mixed, the bonding between the layers is facilitated, meanwhile, the compaction density of the compact layer is ensured, and a strong supporting effect is ensured.
In some embodiments, the second negative electrode slurry may employ one or more of artificial graphite, natural graphite, mesophase carbon microbeads (Mesocarbon Microbeads, MCMB), soft carbon, hard carbon, graphene.
In some embodiments, the second binder may employ one or more of Styrene-butadiene rubber (Styrene, 1,3-butadiene polymer, SBR), polyacrylic acid (Acrylic acid Polymers, PAA), polyvinylidene fluoride (Polyvinylidene Fluoride, PVDF), polyimide (PI), polyamideimide (PAI), sodium alginate, polyacrylate, and the like.
In some embodiments, the second conductive agent may employ one or more of conductive carbon black, multi-walled carbon tubes, single-walled carbon tubes, conductive graphite, graphene, and the like.
In the invention, in the drying process, one-time drying can be adopted, and the drying can be carried out for many times, wherein the drying temperature is 90-180 ℃.
In embodiments of the present invention, the densified layer has a compacted density of 1.5 to 1.75g/cc. The compaction density has good supporting force, and can effectively avoid the unstable pole piece condition caused by the collapse of the pore canal in the cell circulation process.
According to the preparation method of the porous anode, the preparation process is simple, the porous anode prepared by the preparation method has a double-layer structure of the porous layer and the compact layer, the porous layer is positioned on one side close to the current collector, and the compact layer is positioned on one layer contacted with the electrolyte. The porous layer has a uniform arrangement of cell structures that provides space for expansion of the silicon to expand. The pore canal structure can improve the wettability of electrolyte, the shuttle speed of lithium ions and the utilization rate of silicon. .
The porous anode of the embodiment of the invention can be applied to a battery. The battery type includes, but is not limited to, lithium ion batteries, lithium metal batteries, fuel cells, air batteries, sodium sulfur batteries, cadmium nickel batteries, hydrogen nickel batteries, and the like, preferably lithium ion batteries. Including but not limited to button cells, cylindrical cells, square aluminum shell cells, and pouch cells, preferably pouch cells. The positive electrode active material of the lithium ion battery comprises, but is not limited to, lithium cobaltate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material, lithium iron phosphate, lithium manganate, lithium-rich manganese, lithium nickel manganate and the like, and preferably nickel cobalt manganese 811 ternary material.
In addition, the positive electrode material of the battery may be aluminum foil or other materials, and the source of all raw materials is not particularly limited in the invention, and the positive electrode material is a commercially available material meeting the process requirements.
The invention also discloses a preparation method of the battery. Wherein the negative electrode in the battery is a porous negative electrode as described in the above embodiments. The prepared porous negative electrode is made into a sheet shape, and is assembled into a soft package battery together with a ternary lithium battery (NCM 811) positive electrode sheet, a 12+4 ceramic diaphragm and an electrolyte solvent, such as a high nickel electrolyte. The specific preparation process may refer to the preparation process of the battery in the prior art, and will not be described in detail herein.
The battery prepared by the invention has the battery capacity of 9Ah and the battery size of 80mm multiplied by 60mm multiplied by 8.55mm. The high-capacity high-cycle-stability high-pressure water pump has the characteristics of high capacity, high cycle stability and excellent quick-charge performance.
The method for preparing the porous anode according to the embodiment of the present invention is further described below with reference to specific examples.
Comparative example
(1) Taking silicon oxygen material and graphite powder according to the following proportion of 8:2 as the main active material.
(2) Mixing the active material with carbon black powder, sodium carboxymethyl cellulose and styrene-butadiene rubber, and stirring to prepare graphite cathode slurry. Wherein the content of the active material is 85%, the content of the carbon black is 5%, and the content of the binder sodium carboxymethyl cellulose and the styrene-butadiene rubber is 10%.
(3) And then coating the negative electrode slurry on a copper foil to obtain a negative electrode plate.
Example 1
Selecting silicon oxygen material, polyacrylic acid (adhesive), carbon black, single-wall carbon nano tube (conductive agent) and the like according to 90:5:5, mixing and pulping;
coating, drying and rolling the slurry obtained in the step (1) on a common smooth copper foil, wherein the coating thickness is 120mm, and the compaction density is 1.7g/cc, so as to obtain an initial pole piece with a layer structure;
and (3) punching the layer structure obtained in the step (2) by using a laser punching device, wherein the aperture is 100 micrometers, the depth of the holes is 100mm, and the distance between the holes is 100 micrometers.
Artificial graphite, styrene-butadiene rubber (binder), carbon black (conductive agent) and the like are selected according to 90:5:5, mixing and pulping in proportion;
and (3) coating, drying at 100 ℃ and rolling on the primary pole piece obtained in the step (3) by using the slurry obtained in the step (4). Wherein the coating thickness is 30mm, the compaction density is 1.6g/cc, and the porous pole piece is obtained.
Example 2
The preparation process was the same as in example 1 except that the negative electrode material was a nano-silicon material.
Example 3
The procedure was the same as in example 1 except that the compacted density in step (2) was reduced to 1.65 g/cc.
Example 4
The procedure was the same as in example 1 except that the pore size in step (3) was changed to 50. Mu.m.
Example 5
The procedure was the same as in example 1 except that the hole depth in step (3) was changed to 60. Mu.m.
Example 6
The procedure was the same as in example 1 except that the hole spacing in step (3) was changed to 200. Mu.m.
Example 7
The procedure was the same as in example 1 except that the thickness of the rolled coating layer in step (5) was changed to 15 mm.
Example 8
The procedure was the same as in example 1 except that the thickness of the rolled coating layer in step (5) was changed to 60 mm.
The negative electrode plate prepared in the comparative example and the porous electrode plate prepared in the example are respectively prepared into a button cell and a full cell, and the preparation methods are the same. The gram capacity of the negative electrode sheet, the energy density of the secondary full cell, the cycle life and the rate performance were each tested, and the test results are shown in table 1.
Table 1 test results
From the above test results, it was found that the secondary batteries fabricated with the porous negative plates prepared in examples 1 to 8 of the present invention exhibited higher energy density and excellent cycle stability than the secondary batteries fabricated with the composite negative plates prepared by directly mixing the silicon oxygen material with the graphite material.
The above test data are analyzed as follows.
As shown in table 1, it is found from the analysis of the test results of comparative example and example 1 that in the uniformly mixed anode material, the volume expansion of silicon occurs during charge and discharge, resulting in repeated cracking and generation of the solid electrolyte interface SEI film, resulting in poor cycle stability. In addition, silicon near the current collector has poor wettability to the entire electrode sheet, and does not participate in the charge-discharge reaction, and thus does not exhibit capacity. And the silicon oxide material with the same proportion is arranged on the inner side of the pole piece, and a three-dimensional pore canal structure is constructed, and the pore canal provides a favorable space for the expansion of silicon. In addition, the wettability of the electrolyte, the shuttle speed of lithium ions and the utilization rate of silicon can be improved.
Analysis of the test results of examples 1 and 2 shows that the nano-silicon material has a higher gram capacity of 1800mAh/g relative to the silicon oxygen material. In which, since the silicon oxide material is a matrix of SiOx formed by replacing a part of silicon atoms with oxygen atoms, lithium ions are not intercalated into SiOx during charging, that is, siOx is generated by passivating a part of silicon, thereby not providing capacity. In addition, siOx does not expand because lithium intercalation does not occur during charging, and thus SiOx is considered to function as a base to confine (exert capacity of) silicon. Therefore, the same ratio of silicon to silicon oxygen materials, the capacity of pure silicon materials is large. For the pure silicon raw material of nano silicon, the expansion is larger due to the lack of oxygen, so the cycle stability is poor. However, since lithium ions can directly contact and react with silicon, the rate performance of the battery corresponding to the example 2 using nano silicon as a raw material is improved.
As can be seen from the analysis of the test results of examples 1 and 3, the reduction of the compaction density is more favorable for lithium ion shuttling in the negative electrode plate main material part, and the rate performance is improved. It follows that reasonable values of compaction density are critical to the improvement of rate capability.
From the analysis of the test results of examples 1 and 4, it was found that the pore diameter was reduced, the silicon content was increased, and the negative electrode capacity was increased, but the expansion space for silicon was reduced, and the cycle performance was reduced from 600 cycles to 550 cycles in the examples. The lithium ion channels decreased and the rate performance also decreased as shown in table 1 from 3C rate to 2.5 rate. It follows that reasonable values of compaction density are critical to the improvement of rate capability.
As is clear from the analysis of the test results of example 1 and example 5, the pore depth was reduced, and the proportion of effective silicon in the porous layer was reduced (i.e., the proportion of silicon near the current collector that did not participate in charge and discharge was increased). For a decrease in the expansion space of silicon, the cycle performance decreases from 600 cycles to 550 cycles as in table 1. The lithium ion channels decreased and the rate performance also decreased as shown in table 1 from 3C rate to 2.5 rate. It follows that a reasonable pore depth is critical to the improvement of cycle performance and rate performance of the battery.
As is clear from the analysis of the test results of example 1 and example 6, the proportion of effective silicon in the porous layer decreases (silicon in the middle portion of the cell channels does not participate in the charge-discharge reaction) by increasing the cell pitch. For the reduction in expansion space of silicon, the cycle performance reduction was reduced from 600 cycles to 550 cycles as in table 1. The lithium ion channels decreased and the rate performance also decreased as shown in table 1 from 3C rate to 2.5 rate. It follows that a reasonable pore spacing is critical to the improvement of cycle performance and rate performance of the battery.
From the analysis of the test results of examples 1, 7 and 8, the effect of the thickness of the dense layer on the cell was found. The thicker the dense layer, the lower the proportion of silicon that can effectively exert capacity, and the lower the negative electrode capacity, for example, from 1000mAh/g to 750mAh/g and 650mAh/g, respectively, in Table 1, and the lower the cell energy density, for example, from 350Wh/kg to 330Wh/kg and 320Wh/kg, respectively, in Table 1. The expansion constraint of the thick dense layer on the porous layer was also large, so the cycle performance was improved, as shown in table 1 from 600 cycles to 800 cycles. In addition, the thicker dense layer affects the shuttling of lithium ions to some extent, resulting in a reduction in rate performance. Therefore, the reasonable selection of the thickness of the compact layer influences the indexes of the cathode capacity, the energy density, the cycle performance, the multiplying power performance and the like.
It should be noted that in the examples and descriptions of this patent, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
While the present application has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present application.
Claims (10)
1. A porous anode, characterized in that the porous anode comprises:
a current collector;
the porous layer is arranged on the surface of the current collector, and a plurality of pore channels are formed in one end face, away from the current collector, of the porous layer; and
the compact layer is arranged on one side of the porous layer, which is away from the current collector.
2. The porous anode according to claim 1, wherein the pore channels have a diameter in the range of 1 to 1000 microns; the hole spacing between the plurality of the pore channels is between 10 and 1000 microns.
3. The porous anode according to claim 1 or 2, wherein the cells are blind holes.
4. The porous anode according to claim 3, wherein the blind holes have a hole depth of 30 to 95% of the thickness of the porous layer, and wherein the direction of the thickness of the porous layer is an extending direction from one end adjacent to the dense layer to one end adjacent to the current collector.
5. The porous anode according to claim 1, wherein the compacted density of the porous layer and the compacted density of the dense layer are 1.5 to 1.75g/cc.
6. The porous anode according to claim 1, wherein the ratio of the thickness of the porous layer to the thickness of the dense layer is 2:8, 8; the thickness of the porous layer accounts for 51-99% of the total thickness of the porous anode.
7. A method for preparing a porous anode, comprising the steps of:
s1, providing a current collector;
s2, covering the surface of the current collector with the first slurry, and drying and compacting to obtain a layer structure;
s3, arranging a plurality of pore channels at one end of the layer structure, which is far away from the current collector, so as to obtain a porous layer on the surface of the current collector;
and S4, covering the surface of the porous layer, which is far away from the current collector, with second slurry, drying and compacting to form a compact layer on the surface of the porous layer, and finally obtaining the porous anode.
8. The method according to claim 7, wherein in S2, the first slurry is obtained by mixing a first anode material with a first binder and a first conductive agent in proportion;
the second slurry is obtained by mixing the second negative electrode slurry with a second binder and a second conductive agent according to a proportion.
9. The method according to claim 8, wherein the ratio of the first negative electrode material to the first binder to the first conductive agent is (60 to 98): (1-20): (1-20); the proportion of the second anode material to the second binder to the second conductive agent is (60-98): (1-20): (1-20).
10. A battery comprising a stacked porous anode, a solid electrolyte membrane, and a cathode, wherein the porous anode is the porous anode of any one of claims 1 to 6.
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