CN114899410B - Current collector and manufacturing method thereof - Google Patents
Current collector and manufacturing method thereof Download PDFInfo
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- CN114899410B CN114899410B CN202210620779.1A CN202210620779A CN114899410B CN 114899410 B CN114899410 B CN 114899410B CN 202210620779 A CN202210620779 A CN 202210620779A CN 114899410 B CN114899410 B CN 114899410B
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- sodium
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- buffer layer
- conductive
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 262
- 239000011734 sodium Substances 0.000 claims abstract description 175
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 173
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 172
- 230000001502 supplementing effect Effects 0.000 claims abstract description 92
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 77
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000011247 coating layer Substances 0.000 claims abstract description 26
- 230000009471 action Effects 0.000 claims abstract description 10
- 239000011241 protective layer Substances 0.000 claims description 37
- -1 polydimethylsiloxane Polymers 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims 3
- 239000008187 granular material Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-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
- H01M4/64—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a current collector, which comprises a sodium supplementing buffer layer, two substrate layers and two conductive layers, wherein the sodium supplementing buffer layer, the two substrate layers and the two conductive layers are arranged in a stacked mode, the two substrate layers are respectively positioned at two sides of the sodium supplementing buffer layer, the two conductive layers are respectively positioned at one side, away from the sodium supplementing buffer layer, of the two substrate layers, a conductive structure is arranged in the substrate layers, the conductive structure is used for electrically connecting the sodium supplementing buffer layer with the conductive layers, the sodium supplementing buffer layer comprises a plurality of sodium supplementing particles, the sodium supplementing particles comprise sodium supplementing material bodies and coating layers coated on the surfaces of the sodium supplementing material bodies, the sodium supplementing material bodies can release sodium ions through the coating layers, and the sodium ions released by the sodium supplementing material bodies can pass through the substrate layers to reach the conductive layers under the action of voltage. The sodium supplementing buffer layer is arranged between the two base material layers of the current collector, and microsphere particles are arranged in the sodium supplementing buffer layer, so that sodium ions can be released after the current collector is discharged for the first time and lost, the quantity of the sodium ions in the current collector is improved, and the energy density of the battery is ensured. The invention also provides a manufacturing method of the current collector.
Description
Technical Field
The present invention relates to the field of batteries, and in particular to a current collector and a manufacturing method for manufacturing the current collector.
Background
Sodium ion batteries have the advantages of high energy density (i.e. the amount of electric energy emitted by electrode materials of unit mass participating in electrode reactions), good safety performance, low price and the like, and are expected to become substitutes for lithium ion batteries in the energy storage field, but sodium ion batteries have not been popularized all the time because sodium ion batteries still have a plurality of disadvantages compared with mainstream lithium batteries, for example, the theoretical energy density of sodium ion batteries is less than one half of that of lithium ion batteries due to the higher relative atomic mass of sodium element; in the first charge process, sodium ions react with the negative electrode to cause large irreversible capacity loss, particularly in a hard carbon negative electrode, because the radius of the sodium ions is large, the intercalation/deintercalation between carbon layers is difficult, and an irreversible SEI passivation layer is easy to form in the first charge and discharge process, a large amount of sodium ions are consumed, and the first irreversible capacity loss can reach 20%.
Therefore, how to provide a current collector structure capable of compensating sodium ions in a battery to ensure the energy density of the battery is a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a current collector and a manufacturing method for manufacturing the current collector, wherein the current collector can automatically compensate the concentration of sodium ions and ensure the energy density of a battery.
To achieve the above object, as one aspect of the present invention, there is provided a current collector including a sodium compensating buffer layer, two base material layers and two conductive layers stacked together, wherein the two base material layers are respectively located at two sides of the sodium compensating buffer layer, the two conductive layers are respectively located at two sides of the base material layers facing away from the sodium compensating buffer layer, a conductive structure is disposed in the base material layers, the conductive structure is used for electrically connecting the sodium compensating buffer layer with the conductive layers, the sodium compensating buffer layer includes a plurality of sodium compensating particles, the sodium compensating particles include a sodium compensating material body and a coating layer coated on the surface of the sodium compensating material body, the sodium compensating material body can release sodium ions through the coating layer, and the sodium ions released by the sodium compensating material body can pass through the base material layer to reach the conductive layer under the voltage action between the conductive layer and the sodium compensating buffer layer.
Optionally, the coating layer comprises a flexible protection layer and a rigid protection layer which are laminated and coated on the surface of the sodium supplementing material body, and the elasticity of the flexible protection layer is higher than that of the rigid protection layer.
Optionally, the flexible protection layer is coated on the surface of the sodium supplementing material body, the rigid protection layer is coated on the outer side of the flexible protection layer, the flexible protection layer is made of an organic polymer material, and the rigid protection layer is made of an inorganic substance.
Optionally, the material of the flexible protective layer includes at least one of polyvinylidene fluoride, polydimethylsiloxane and polyacrylic acid.
Optionally, the material of the rigid protection layer includes at least one of titanium dioxide, tin oxide, and metallic tin.
Optionally, the sodium compensating buffer layer further comprises a binder for binding a plurality of the sodium compensating particles.
Optionally, the conductive structure includes a plurality of conductive strips, a plurality of accommodating through holes penetrating through the substrate layer along a thickness direction are formed in the substrate layer, at least part of the accommodating through holes are provided with the conductive strips, one ends of the conductive strips are in electrical contact with the sodium compensating buffer layer, and the other ends of the conductive strips are in electrical contact with the corresponding conductive layers.
Optionally, the material of the conductive strip includes at least one of conductive carbon black, carbon nanotubes, and graphene.
As a second aspect of the present invention, there is provided a method of manufacturing a current collector, the method comprising:
manufacturing a sodium supplementing buffer layer on the first substrate layer and manufacturing a second substrate layer on the sodium supplementing buffer layer, wherein the sodium supplementing buffer layer comprises a plurality of sodium supplementing particles, the sodium supplementing particles comprise sodium supplementing material bodies and coating layers coated on the surfaces of the sodium supplementing material bodies, the sodium supplementing material bodies can release sodium ions through the coating layers, and the sodium ions can pass through the substrate layers under the action of voltage;
and manufacturing a conductive structure in the first substrate layer and the second substrate layer, and manufacturing conductive layers on one sides of the first substrate layer and the second substrate layer, which are away from the sodium supplementing buffer layer, respectively, so that the sodium supplementing buffer layer is electrically connected with each conductive layer through the conductive structure.
Optionally, the conductive structure includes a plurality of conductive strips, and the fabricating the conductive structure in the first substrate layer and the second substrate layer includes:
and manufacturing a plurality of accommodating through holes penetrating in the thickness direction in the first substrate layer and the second substrate layer, and placing a plurality of conducting strips in at least part of the accommodating through holes in a one-to-one correspondence manner, so that one end of each conducting strip is in electrical contact with the sodium supplementing buffer layer, and the other end of each conducting strip is flush with the surface of one side, facing away from the sodium supplementing buffer layer, of the corresponding substrate layer.
In the manufacturing method of the current collector and the current collector, the sodium supplementing buffer layer is arranged between the two base material layers, a plurality of microsphere particles are arranged in the sodium supplementing buffer layer, sodium supplementing material bodies (namely, the particle bodies of substances containing sodium elements) are contained in the microsphere particles, sodium ions released by the sodium supplementing material bodies can pass through the coating layers to escape from the microsphere particles, so that after the current collector is firstly discharged to form the passivation layer and a large amount of sodium ions are lost, the sodium supplementing material bodies can release the sodium ions outwards through the coating layers, and the released sodium ions can move to the conductive layer through electrolyte under the action of voltage applied to the sodium supplementing buffer layer by the conductive layer through the conductive structure, so that the quantity of the sodium ions participating in battery reaction in the current collector is improved, the sodium ions in the battery are compensated, and the energy density of the battery is further ensured.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
fig. 1 is a schematic structural view of a current collector according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of sodium compensating particles in a current collector according to an embodiment of the present invention.
Reference numerals illustrate:
100: sodium compensating buffer layer 200: substrate layer
300: conductive layer 310: sodium supplementing material body
320: coating 321: flexible protective layer
322: rigid protective layer 500: conductive strip
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In order to solve the above-mentioned technical problem, as an aspect of the present invention, a current collector is provided, which includes a sodium compensating buffer layer 100, two substrate layers 200 and two conductive layers 300 stacked together, wherein the two substrate layers 200 are respectively located at two sides of the sodium compensating buffer layer 100, the two conductive layers 300 are respectively located at one side of the two substrate layers 200 away from the sodium compensating buffer layer 100, a conductive structure is disposed in the substrate layers 200, the conductive structure is used for electrically connecting the sodium compensating buffer layer 100 with the conductive layers 300, and the sodium compensating buffer layer 100 includes a plurality of sodium compensating particles. As shown in fig. 2, the sodium compensating particle includes a sodium compensating material body 310 and a coating layer 320 coated on the surface of the sodium compensating material body 310, wherein the sodium compensating material body 310 can release sodium ions through the coating layer 320, and the sodium ions released by the sodium compensating material body can pass through the substrate layer 200 to reach the conductive layer 300 under the voltage between the conductive layer 300 and the sodium compensating buffer layer 100.
It should be noted that, the current collector is immersed in the electrolyte of the battery in the use state, that is, the sodium compensating buffer layer 100, the substrate layer 200 and other structures between the two conductive layers 300 may draw in the electrolyte, so that sodium ions may pass through the substrate layer 200 to reach the conductive layers 300 through the electrolyte in actual use.
In the current collector provided by the invention, a sandwich structure of the sodium supplementing buffer layer 100 is arranged between two substrate layers 200, a plurality of microsphere particles are arranged in the sodium supplementing buffer layer 100, sodium supplementing material bodies 310 (namely, the particle bodies of substances containing sodium elements) are contained in the microsphere particles, sodium ions released by the sodium supplementing material bodies 310 can escape from the microsphere particles through the coating layers 320, so that after the current collector is firstly discharged to form an SEI passivation layer and a large amount of sodium ions are lost, the sodium supplementing material bodies 310 can release the sodium ions outwards through the coating layers 320, and the released sodium ions can move to the conductive layer 300 through electrolyte under the action of voltage applied to the sodium supplementing buffer layer 100 by the conductive layer 300 through the conductive structure, so that the quantity of sodium ions participating in battery reaction in the current collector is increased, the sodium ions in a battery are compensated, and the energy density of the battery is further ensured.
In a preferred embodiment of the present invention, the conductive layer 300 may be made of a metal material having good conductivity, and for example, the conductive layer 300 may be made of aluminum, an aluminum alloy, pure copper, nickel-plated copper, or the like.
As an alternative embodiment of the present invention, the thickness of the conductive layer 300 is 0.5 μm to 10 μm. For example, 1 μm can be selected.
To ensure the structural integrity of the sodium compensating particles and to improve the flexibility of the overall structure of the current collector, as a preferred embodiment of the present invention, as shown in fig. 2, the coating layer 320 includes a flexible protective layer 321 and a rigid protective layer 322 laminated and coated on the surface of the sodium compensating material body 310, and the flexible protective layer 321 has higher elasticity than the rigid protective layer 322.
In the embodiment of the invention, the coating layer 320 includes a flexible protection layer 321 and a rigid protection layer 322 that are laminated and coated on the surface of the sodium supplementing material body 310, wherein the rigid protection layer 322 can prevent sodium ions in the sodium supplementing material body 310 inside sodium supplementing particles from being released once caused by breakage of the sodium supplementing particles in extrusion and collision, and the flexible protection layer 321 can enable the sodium supplementing particles to have certain elasticity, so that the flexibility of the sodium supplementing buffer layer 100 is improved, the breakage of the sodium supplementing buffer layer 100 caused by overhigh hardness in bending is avoided, the flexibility of the overall structure of the current collector is further improved, and the safety of the current collector in the use process is ensured.
As shown in fig. 2, in a preferred embodiment of the present invention, a flexible protective layer 321 is coated on the surface of a sodium supplementing material body 310, a rigid protective layer 322 is coated on the outer side of the flexible protective layer 321, the flexible protective layer 321 is made of an organic polymer material, and the rigid protective layer 322 is made of an inorganic material.
That is, in the embodiment of the present invention, the flexible protective layer 321 made of an organic polymer material is wrapped on the outer side of the sodium supplementing material body 310, and the rigid protective layer 322 made of an inorganic material is wrapped on the outer side of the flexible protective layer 321, so that the softer flexible protective layer 321 can be prevented from deforming under the soaking action of the electrolyte, and the rigid protective layer 322 made of an inorganic material is not easy to deform at a high temperature, so that the whole volume of the sodium supplementing particles can be maintained, the internal stress generated by the expansion of the positive electrode and the negative electrode in the use process of the battery is reduced, and the cycle performance of the sodium battery is further improved.
As an alternative embodiment of the present invention, the material of the sodium supplementing material body 310 may be a sodium compound, for example, the material of the sodium supplementing material body 310 may include sodium nitride (Na 3 N), sodium oxide (Na 2 O), sodium phosphide (Na 3 P), sodium fluoride (NaF).
As an alternative embodiment of the present invention, the material of the flexible protective layer 321 may include at least one of polyvinylidene fluoride (Polyvinylidene Difluoride, PVDF), polydimethylsiloxane (Polydimethylsiloxane) and Polyacrylic acid (Polyacrylic acid).
As an alternative embodiment of the present invention, the material of the rigid protection layer 322 may be a metal oxide or a partial alloy, for example, the material of the rigid protection layer 322 may include at least one of titanium dioxide, tin oxide, and metallic tin.
As an alternative embodiment of the present invention, the flexible protective layer 321 and the rigid protective layer 322 coated on the sodium compensating material body 310 may be manufactured by using at least one of a chemical vapor deposition method, a physical vapor deposition method, and a liquid phase coating method.
As an alternative embodiment of the invention, the mass percentage of the rigid protective layer 322 in the sodium compensating particles is 1-20%wt, the mass percentage of the flexible protective layer 321 is 1-20%wt, and the mass percentage of the sodium compensating material body 310 is 60% -90%wt.
As an alternative embodiment of the invention, the particle size of the sodium compensating particles is 0.2 μm-3 μm.
As an alternative embodiment of the present invention, the sodium compensating buffer layer 100 further includes a binder for binding the plurality of sodium compensating particles.
As an alternative embodiment of the present invention, the binder includes at least one of polyvinylidene fluoride, polyacrylate (Polyacrylate), sodium Polyacrylate (Sodium Polyacrylate), polyimides, carboxymethyl cellulose (Carboxymethyl Cellulose), and styrene butadiene rubber (Polymerized Styrene Butadiene Rubber, SBR).
In order to improve the escape efficiency of sodium ions, the sodium compensating buffer layer 100 further includes a conductive agent as a preferred embodiment of the present invention.
As an alternative embodiment of the present invention, the conductive agent includes at least one of conductive carbon black, carbon nanotubes, graphene.
To ensure the humidity of the sodium compensating buffer layer 100, as an alternative embodiment of the present invention, the sodium compensating buffer layer 100 further includes a wetting agent and a preset solvent, and the wetting agent is used to increase the amount of the preset solvent absorbed by the sodium compensating buffer layer 100.
For example, the preset solvent may be water (H2O), and the wetting agent includes at least one of fluoroalkyl methoxy ether alcohol, sodium polyacrylate, acetylenic glycol vinyl ether, fatty Acid polyoxyethylene ether, and ammonium polyacrylate (Acrylic Acid).
As an alternative embodiment of the invention, the mass percentage of the binder in the sodium supplementing buffer layer 100 is 1-10 percent by weight, the mass percentage of the conductive agent is 1-5 percent by weight, the mass percentage of the sodium supplementing microsphere is 90-98 percent by weight, and the mass percentage of the wetting agent is 0.1-2 percent by weight.
As an alternative embodiment of the present invention, the sodium compensating buffer layer 100 may have a thickness of 0.5 μm to 5 μm. For example, 2 μm can be selected.
The shape and material of the conductive structure in the embodiment of the present invention are not particularly limited, as long as the conductive structure can electrically connect the sodium compensating buffer layer 100 and the conductive layer 300, for example, the conductive structure may be in a wire shape, a block shape, a sheet shape, or the like, and the conductive structure may be a non-metal conductor or a metal conductor resistant to corrosion of an electrolyte.
To improve the flow efficiency of carriers in the current collector, as an alternative embodiment of the present invention, as shown in fig. 1, the conductive structure includes a plurality of conductive strips 500, a plurality of receiving through holes penetrating the substrate layer 200 in the thickness direction are formed in the substrate layer 200, and the conductive strips 500 are disposed at least in part in the receiving through holes, one ends of the conductive strips 500 are in electrical contact with the sodium compensating buffer layer 100, and the other ends are in electrical contact with the corresponding conductive layers 300.
In the embodiment of the invention, the conductive structure comprises a plurality of conductive strips 500 arranged in a plurality of accommodating through holes, so that the number of connection points between the conductive layer 300 and the sodium compensating buffer layer 100 and the uniformity of distribution of the connection points are improved, the efficiency of loading voltage to the sodium compensating buffer layer 100 by the conductive layer 300 is ensured, the efficiency of releasing sodium ions by sodium compensating particles is further improved, and the quantity of sodium ions in the battery is ensured.
Optionally, a conductive strip 500 is disposed in each receiving through hole.
As an alternative embodiment of the present invention, the receiving through-holes in the substrate layer 200 are formed by an etching method.
As an alternative embodiment of the present invention, the material of the conductive strip 500 includes at least one of conductive carbon black, carbon nanotubes, and graphene.
As an alternative embodiment of the present invention, the material of the substrate layer 200 may include at least one of Polyethylene (PE), polypropylene (PP), polyethylene terephthalate (Polyethylene Glycol Terephthalate, PET), polyethylene naphthalate, polyimide (PI) and Polycarbonate (PC).
As an alternative embodiment of the present invention, the thickness of the base material layer 200 may be 2 μm to 20 μm. For example, the thickness of the substrate layer 200 may be selected to be 4 μm.
As a second aspect of the present invention, there is provided a method of manufacturing a current collector, the method comprising:
step S1, a sodium-compensating buffer layer 100 is fabricated on the first substrate layer (i.e. one substrate layer 200 in the current collector provided by the present invention), and a second substrate layer (i.e. the other substrate layer 200 in the current collector provided by the present invention) is fabricated on the sodium-compensating buffer layer 100. The sodium-compensating buffer layer 100 includes a plurality of sodium-compensating particles, the sodium-compensating particles include a sodium-compensating material body 310 and a coating layer 320 coated on the surface of the sodium-compensating material body 310, the sodium-compensating material body 310 can release sodium ions through the coating layer 320, and the sodium ions can pass through the substrate layer (i.e. the first substrate layer or the second substrate layer) under the action of voltage;
step S2, a conductive structure is fabricated in the first substrate layer and the second substrate layer, and conductive layers 300 are fabricated on the sides of the first substrate layer and the second substrate layer facing away from the sodium compensating buffer layer 100, respectively, so that the sodium compensating buffer layer 100 is electrically connected with each conductive layer 300 through the conductive structure.
In the current collector manufactured by the manufacturing method of the current collector provided by the invention, a sandwich structure of the sodium supplementing buffer layer 100 is arranged between two substrate layers 200 (namely, the first substrate layer and the second substrate layer), a plurality of microsphere particles are arranged in the sodium supplementing buffer layer 100, sodium supplementing material bodies 310 are contained in the microsphere particles, sodium ions released by the sodium supplementing material bodies 310 can escape from the microsphere particles through the coating layers 320, so that after the current collector is initially discharged to form an SEI passivation layer and a large amount of sodium ions are lost, the sodium supplementing material bodies 310 can release sodium ions outwards through the coating layers 320, and the released sodium ions can move to the conductive layer 300 through electrolyte under the action of voltage applied to the sodium supplementing buffer layer 100 by the conductive layer 300 through the conductive structure, so that the amount of sodium ions participating in battery reaction in the current collector is improved, sodium ions in a battery are compensated, and the energy density of the battery is further ensured.
In order to improve the flow efficiency of carriers in the current collector, as an alternative embodiment of the present invention, the conductive structure includes a plurality of conductive strips 500, and the step of fabricating the conductive structure in the first substrate layer and the second substrate layer in step S2 specifically includes:
and a plurality of accommodating through holes penetrating through (corresponding to the film layer) in the thickness direction are formed in the first substrate layer and the second substrate layer, and a plurality of conducting strips 500 are placed in at least part of the accommodating through holes in a one-to-one correspondence manner, so that one end of each conducting strip 500 is in electrical contact with the sodium supplementing buffer layer, the other end of each conducting strip 500 is flush with the surface of the side, away from the sodium supplementing buffer layer 100, of the corresponding substrate layer (namely the corresponding first substrate layer or the second substrate layer), and therefore the subsequently manufactured conductive layers 300 can be ensured to be in electrical contact with the conducting strips 500.
As an alternative embodiment of the present invention, the method for manufacturing a current collector further includes the step of manufacturing a flexible protective layer 321 and a rigid protective layer 322 on the sodium compensating material body 310 to obtain sodium compensating particles.
As an alternative embodiment of the present invention, the flexible protective layer 321 and the rigid protective layer 322 coated on the sodium compensating material body 310 may be manufactured by using at least one of a chemical vapor deposition method, a physical vapor deposition method, and a liquid phase coating method.
As an alternative embodiment of the present invention, the method for manufacturing the current collector further includes a step of mixing the sodium compensating particles with other materials (e.g., binder, conductive agent, wetting agent, preset solvent) of the sodium compensating buffer layer 100 to obtain the sodium compensating buffer layer 100.
For the convenience of understanding of the skilled person, two specific examples of manufacturing the current collector by using the manufacturing method of the current collector provided by the invention are given below:
embodiment one:
the polyvinylidene fluoride glue solution is uniformly coated on the surface of the sodium phosphide powder (namely the sodium supplementing material body 310) by a liquid phase coating method (namely the flexible protective layer 321 is manufactured).
Depositing a uniform alumina (Al) on the surface of the structure coated with polyvinylidene fluoride glue solution by chemical vapor deposition 2 O 3 ) The protective layer (i.e., the rigid protective layer 322 is formed) to obtain sodium compensating particles.
10% wt of polyacrylate (binder) and 2% wt of conductive agent and 87.5% wt of sodium supplementing particles are mixed with water, and uniformly stirred, so as to prepare a slurry, wherein the slurry is coated on a PET (polyethylene terephthalate) film (namely a layer of substrate layer 200) with the thickness of 4 mu m, and the coating thickness is 2 mu m (namely the sodium supplementing buffer layer 100 is manufactured on the first substrate layer).
Manufacturing a PET film with the thickness of 4 mu m on the coating layer (namely manufacturing a second substrate layer on the sodium supplementing buffer layer 100) through a thermal compounding process;
punching a plurality of holes (namely, manufacturing a plurality of containing through holes) in the substrate layers on two sides of the manufactured rechecking film layer, and placing conductive carbon black (namely, a conductive strip 500) in each hole;
the surfaces of the PET films on both sides are respectively plated with an aluminum conductive layer with a thickness of 1 μm by a vacuum evaporation process, namely, a conductive layer 300 is respectively manufactured on one side of the first substrate layer and one side of the second substrate layer, which are away from the sodium supplementing buffer layer 100.
Embodiment two:
the polyvinylidene fluoride glue solution is uniformly coated on the surface of the sodium phosphide powder (namely the sodium supplementing material body 310) by a liquid phase coating method (namely the flexible protective layer 321 is manufactured).
Depositing on the surface of the structure coated with polyvinylidene fluoride glue solution by chemical vapor depositionA layer of uniform titanium oxide (TiO) 2 ) The protective layer (i.e., the rigid protective layer 322 is formed) to obtain sodium compensating particles.
10% wt of polyacrylate (binder) and 2% wt of conductive agent and 87.5% wt of sodium supplementing particles are mixed with water, and uniformly stirred, so as to prepare a slurry, wherein the slurry is coated on a PET film (namely a base material layer 200) with the thickness of 4 mu m, and the coating thickness is 2 mu m (namely a sodium supplementing buffer layer 100 is manufactured on a first base material layer).
A PI film having a thickness of 4 μm was formed on the coating layer by a thermal compounding process (i.e., a second base material layer was formed on the sodium compensating buffer layer 100).
Punching a plurality of holes (namely, manufacturing a plurality of containing through holes) in the substrate layers on two sides of the manufactured rechecking film layer, and placing conductive carbon black (namely, a conductive strip 500) in each hole;
the surfaces of the PET film and the PI film are respectively plated with an aluminum conductive layer with the thickness of 1 mu m through a vacuum evaporation process, namely, one conductive layer 300 is respectively manufactured on one side of the first substrate layer and one side of the second substrate layer, which are away from the sodium supplementing buffer layer 100.
As a third aspect of the present invention, there is provided a battery including the current collector provided by the embodiment of the present invention.
In the battery provided by the invention, a sandwich structure of the sodium supplementing buffer layer 100 is arranged between two substrate layers 200 of the current collector, a plurality of microsphere particles are arranged in the sodium supplementing buffer layer 100, sodium ions released by the sodium supplementing material 310 can pass through the coating layer 320 to escape from the microsphere particles, so that after the current collector is firstly discharged to form an SEI passivation layer and a large amount of sodium ions are lost, the sodium supplementing material 310 can release sodium ions outwards through the coating layer 320, and the released sodium ions can move to the conductive layer 300 through electrolyte under the action of the voltage applied to the sodium supplementing buffer layer 100 by the conductive layer 300 through the conductive structure, so that the quantity of sodium ions participating in the battery reaction in the current collector is improved, the sodium ions in the battery are compensated, and the energy density of the battery is further ensured.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (4)
1. The utility model provides a current collector, its characterized in that includes the sodium compensation buffer layer, two substrate layers and two conducting layers of range upon range of setting, two the substrate layer is located respectively the both sides of sodium compensation buffer layer, two the conducting layer is located respectively two the substrate layer deviates from one side of sodium compensation buffer layer, be provided with electrically conductive structure in the substrate layer, electrically conductive structure is used for with sodium compensation buffer layer with electrically conductive layer connects, sodium compensation buffer layer includes a plurality of sodium compensation granule, sodium compensation granule includes the sodium compensation material body and cladding in the cladding on sodium compensation material body surface, the sodium compensation material body can see through the cladding release sodium ion, and the sodium ion that the sodium compensation material body released can pass through the substrate layer under the effect of voltage between conducting layer and the sodium compensation buffer layer reaches the conducting layer.
The coating layer comprises a flexible protection layer and a rigid protection layer which are laminated and coated on the surface of the sodium supplementing material body, and the elasticity of the flexible protection layer is higher than that of the rigid protection layer; the flexible protective layer is coated on the surface of the sodium supplementing material body, and the rigid protective layer is coated on the outer side of the flexible protective layer; the flexible protective layer is made of at least one of polyvinylidene fluoride, polydimethylsiloxane and polyacrylic acid; the rigid protective layer is made of at least one of titanium dioxide, tin oxide and metallic tin;
the conductive structure comprises a plurality of conductive strips, a plurality of containing through holes penetrating through the substrate layer in the thickness direction are formed in the substrate layer, at least part of the containing through holes are provided with the conductive strips, one ends of the conductive strips are in electrical contact with the sodium supplementing buffer layers, and the other ends of the conductive strips are in electrical contact with the corresponding conductive layers; the conductive strips are made of at least one of conductive carbon black, carbon nanotubes and graphene.
2. The current collector of claim 1, wherein the sodium compensating buffer layer further comprises a binder for binding a plurality of the sodium compensating particles.
3. A method of manufacturing a current collector according to claim 1 or 2, comprising:
manufacturing a sodium supplementing buffer layer on the first substrate layer and manufacturing a second substrate layer on the sodium supplementing buffer layer, wherein the sodium supplementing buffer layer comprises a plurality of sodium supplementing particles, the sodium supplementing particles comprise sodium supplementing material bodies and coating layers coated on the surfaces of the sodium supplementing material bodies, the sodium supplementing material bodies can release sodium ions through the coating layers, and the sodium ions can pass through the substrate layers under the action of voltage;
and manufacturing a conductive structure in the first substrate layer and the second substrate layer, and manufacturing conductive layers on one sides of the first substrate layer and the second substrate layer, which are away from the sodium supplementing buffer layer, respectively, so that the sodium supplementing buffer layer is electrically connected with each conductive layer through the conductive structure.
4. A method of making a current collector according to claim 3 wherein the conductive structure comprises a plurality of conductive strips, the making conductive structures in the first and second substrate layers comprising:
and manufacturing a plurality of accommodating through holes penetrating in the thickness direction in the first substrate layer and the second substrate layer, and placing a plurality of conducting strips in at least part of the accommodating through holes in a one-to-one correspondence manner, so that one end of each conducting strip is in electrical contact with the sodium supplementing buffer layer, and the other end of each conducting strip is flush with the surface of one side, facing away from the sodium supplementing buffer layer, of the corresponding substrate layer.
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