CN114899410A - Current collector and manufacturing method thereof - Google Patents
Current collector and manufacturing method thereof Download PDFInfo
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- CN114899410A CN114899410A CN202210620779.1A CN202210620779A CN114899410A CN 114899410 A CN114899410 A CN 114899410A CN 202210620779 A CN202210620779 A CN 202210620779A CN 114899410 A CN114899410 A CN 114899410A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000010410 layer Substances 0.000 claims abstract description 273
- 229940091252 sodium supplement Drugs 0.000 claims abstract description 141
- 239000000463 material Substances 0.000 claims abstract description 83
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000011734 sodium Substances 0.000 claims abstract description 41
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 38
- 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 37
- 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 26
- 238000000034 method Methods 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 11
- -1 polydimethylsiloxane 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 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
- 239000000126 substance Substances 0.000 claims description 5
- 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
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 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 1
- 230000000694 effects Effects 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 230000001502 supplementing effect Effects 0.000 abstract description 15
- 239000004005 microsphere Substances 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 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
- 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
- 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
- 238000002156 mixing Methods 0.000 description 3
- 230000000149 penetrating effect Effects 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
- 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
- 238000005229 chemical vapour deposition 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
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000004080 punching Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000007740 vapor deposition 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
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 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
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- 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
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 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
- 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
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—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 base material layers and two conducting layers, wherein the two base material layers are arranged in a stacked mode and are respectively positioned on two sides of the sodium supplementing buffer layer, the two conducting layers are respectively positioned on one sides, away from the sodium supplementing buffer layer, of the two base material layers, a conducting structure is arranged in the base material layers and is used for electrically connecting the sodium supplementing buffer layer with the conducting 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 penetrate through the coating layers to release sodium ions, and the sodium ions released by the sodium supplementing material bodies can penetrate through the base material layers to reach the conducting layers under the action of voltage. According to the current collector, the sodium supplement buffer layer is arranged between the two substrate layers, and the sodium supplement buffer layer is provided with the microsphere particles, so that sodium ions can be released after the sodium ions in the current collector are lost through initial discharge, the amount of the sodium ions in the current collector is increased, and the energy density of a battery is ensured. The invention also provides a manufacturing method of the current collector.
Description
Technical Field
The invention relates to the field of batteries, in particular to a current collector and a manufacturing method for manufacturing the current collector.
Background
The sodium ion battery has the advantages of high energy density (namely the amount of electric energy discharged by electrode materials participating in electrode reaction in unit mass), good safety performance, low price and the like, is expected to become a substitute of the lithium ion battery in the field of energy storage, and the sodium ion battery is not popularized all the time because the sodium ion battery still has a plurality of defects compared with a mainstream lithium battery, for example, the theoretical energy density of the sodium ion battery is less than one half of that of the lithium ion battery due to the higher relative atomic mass of sodium element; in the first charging 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 insertion/removal between carbon layers is difficult, an irreversible SEI passivation layer is easily formed during the first charging and discharging, a large amount of sodium ions are consumed, and further 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 becomes a technical problem to be solved in the field.
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.
In order to achieve the above object, as an aspect of the present invention, there is provided a current collector, including a sodium supplement buffer layer, two substrate layers and two conductive layers, the two substrate layers are respectively located at two sides of the sodium supplement buffer layer, the two conductive layers are respectively located at one side of the two substrate layers away from the sodium supplement buffer layer, the substrate layer is provided with a conductive structure which is used for electrically connecting the sodium supplementing buffer layer with the conductive layer, the sodium supplement buffer layer comprises a plurality of sodium supplement particles, the sodium supplement particles comprise a sodium supplement material body and a coating layer coated on the surface of the sodium supplement material body, the sodium supplement material body can release sodium ions through the coating layer, and sodium ions released by the sodium supplement material body can penetrate through the base material layer to reach the conductive layer under the action of voltage between the conductive layer and the sodium supplement buffer layer.
Optionally, the coating layer includes a flexible protection layer and a rigid protection layer laminated and coated on the surface of the sodium supplement material, and elasticity of the flexible protection layer is higher than that of the rigid protection layer.
Optionally, the flexible protective layer is coated on the surface of the sodium supplement material body, the rigid protective layer is coated on the outer side of the flexible protective layer, the flexible protective layer is made of an organic polymer material, and the rigid protective layer is made of an inorganic substance.
Optionally, the material of the flexible protection 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 supplement buffer layer further comprises a binder for binding a plurality of the sodium supplement particles.
Optionally, the conductive structure includes a plurality of conductive strips, a plurality of accommodating through holes penetrating through the substrate layer in the thickness direction are formed in the substrate layer, and at least part of the accommodating through holes are provided with the conductive strips, one end of each conductive strip is in electrical contact with the sodium supplement buffer layer, and the other end of each conductive strip is in electrical contact with the corresponding conductive layer.
Optionally, the conductive strip is made of at least one of conductive carbon black, carbon nanotube, 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 supplement buffer layer on a first substrate layer, and manufacturing a second substrate layer on the sodium supplement buffer layer, wherein the sodium supplement buffer layer comprises a plurality of sodium supplement particles, the sodium supplement particles comprise sodium supplement material bodies and coating layers coated on the surfaces of the sodium supplement material bodies, the sodium supplement material bodies can penetrate through the coating layers to release sodium ions, and the sodium ions can penetrate through the substrate layer 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 the sides of the first substrate layer and the second substrate layer, which deviate from the sodium supplement buffer layer, so that the sodium supplement 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:
first substrate layer with make a plurality of holding through-holes that link up along the thickness direction in the second substrate layer, and at least part place a plurality ofly in holding the through-hole one-to-one the conducting strip makes the one end of conducting strip with mend the electrical contact of sodium buffer layer, the other end of conducting strip deviates from with the substrate layer that corresponds the surperficial parallel and level of mending sodium buffer layer one side.
In the current collector and the manufacturing method of the current collector, a sodium supplement buffer layer is arranged between two substrate layers, a plurality of micro-sphere particles are arranged in the sodium supplement buffer layer, sodium supplement material bodies (namely particle bodies of substances containing sodium elements) are contained in the micro-sphere particles, sodium ions released by the sodium supplement material bodies can penetrate through a coating layer to escape from the micro-sphere particles, so that after a passivation layer is formed by initial discharge of the current collector and a large amount of sodium ions are lost, the sodium supplement material bodies can release the sodium ions outwards through the coating layer, and the released sodium ions can move to a conductive layer through electrolyte under the action of voltage applied to the sodium supplement buffer layer by the conductive layer through a conductive structure, so that the amount of the sodium ions participating in battery reaction in the current collector is increased, the sodium ions in a compensation battery are realized, and the energy density of the battery is further ensured.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural diagram of a current collector provided in an embodiment of the present invention;
fig. 2 is a schematic structural diagram of sodium supplement particles in the current collector provided in the embodiment of the present invention.
Description of reference numerals:
100: sodium supplement buffer layer 200: substrate layer
300: conductive layer 310: sodium supplementing material
320: coating 321: flexible protective layer
322: rigid protective layer 500: conductive strip
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In order to solve the above technical problems, an aspect of the present invention provides a current collector, which includes a sodium supplement buffer layer 100, two substrate layers 200, and two conductive layers 300, which are stacked, where the two substrate layers 200 are located at two sides of the sodium supplement buffer layer 100, the two conductive layers 300 are located at one side of the two substrate layers 200 away from the sodium supplement buffer layer 100, a conductive structure is disposed in the substrate layers 200, the conductive structure is used to electrically connect the sodium supplement buffer layer 100 with the conductive layers 300, and the sodium supplement buffer layer 100 includes a plurality of sodium supplement particles. As shown in fig. 2, the sodium supplement particle includes a sodium supplement material body 310 and a coating layer 320 coated on the surface of the sodium supplement material body 310, the sodium supplement material body 310 can release sodium ions through the coating layer 320, and the sodium ions released by the sodium supplement material body can pass through the substrate layer 200 to reach the conductive layer 300 under the action of a voltage between the conductive layer 300 and the sodium supplement buffer layer 100.
Note that, since the current collector is immersed in the electrolyte of the battery in a use state, that is, the structures of the sodium supplement buffer layer 100, the base material layer 200, and the like between the two conductive layers 300 absorb the electrolyte, sodium ions can pass through the base material layer 200 to reach the conductive layer 300 via the electrolyte in actual use.
In the current collector provided by the invention, a sandwich structure of a sodium supplement buffer layer 100 is arranged between two substrate layers 200, the sodium supplement buffer layer 100 is provided with a plurality of microspherical particles, the inside of each microspherical particle contains a sodium supplement material body 310 (namely a particle body of a substance containing sodium element), sodium ions released by the sodium supplement material body 310 can pass through a coating layer 320 to escape from the microspherical particle, so that after the current collector is discharged for the first time to form an SEI passivation layer and lose a large amount of sodium ions, the sodium supplement material body 310 can release the sodium ions outwards through the coating layer 320, and the released sodium ions can move to a conductive layer 300 through an electrolyte under the action of voltage applied to the sodium supplement buffer layer 100 by the conductive layer 300 through a conductive structure, so that the amount of the sodium ions participating in battery reaction in the current collector is increased, the sodium ions in a compensation battery are realized, 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 the conductive layer 300 may be made of aluminum, an aluminum alloy, pure copper, nickel-plated copper, or the like.
In 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 may be selected.
In order to ensure the structural integrity of the sodium supplement particles and improve the flexibility of the overall structure of the current collector, as shown in fig. 2, as a preferred embodiment of the present invention, the coating layer 320 includes a flexible protection layer 321 and a rigid protection layer 322 laminated and coated on the surface of the sodium supplement material body 310, and the elasticity of the flexible protection layer 321 is higher than that of the rigid protection layer 322.
In the embodiment of the present invention, the coating layer 320 includes a flexible protection layer 321 and a rigid protection layer 322 laminated and coated on the surface of the sodium supplement material body 310, wherein the rigid protection layer 322 can prevent sodium supplement particles from being damaged in extrusion and collision to cause one-time release of sodium ions in the sodium supplement material body 310 inside the sodium supplement particles, and the flexible protection layer 321 can enable the sodium supplement particles to have certain elasticity, improve flexibility of the sodium supplement buffer layer 100, and prevent the sodium supplement buffer layer 100 from being broken when being bent due to excessively high hardness, so as to improve flexibility of the overall structure of the current collector, and ensure safety of the current collector in a use process.
As shown in fig. 2, in a preferred embodiment of the present invention, the flexible protection layer 321 is coated on the surface of the sodium supplement material body 310, the rigid protection layer 322 is coated outside the flexible protection layer 321, the flexible protection layer 321 is made of an organic polymer material, and the rigid protection layer 322 is made of an inorganic material.
That is, in the embodiment of the present invention, the flexible protection layer 321 made of an organic polymer material is wrapped outside the sodium supplement material body 310, and the rigid protection layer 322 made of an inorganic material is wrapped outside the flexible protection layer 321, so that the softer flexible protection layer 321 can be prevented from deforming under the soaking action of the electrolyte, and the rigid protection layer 322 made of an inorganic material is not easily deformed at a high temperature, so that the overall volume of the sodium supplement particles can be maintained, the internal stress generated by the expansion of the positive electrode and the negative electrode of the battery in the use process is reduced, and the cycle performance of the sodium battery is further improved.
In an alternative embodiment of the present invention, the material of the sodium supplement material body 310 may be a sodium compound, for example, the material of the sodium supplement material body 310 may include sodium nitride (Na) 3 N), sodium oxide (Na) 2 O), sodium phosphide (Na) 3 P) and sodium fluoride (NaF).
As an alternative embodiment of the present invention, the material of the flexible protection layer 321 may include at least one of Polyvinylidene fluoride (PVDF), Polydimethylsiloxane (polydimethysiloxane), 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 protection layer 321 and the rigid protection layer 322 coated on the sodium supplement 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 optional embodiment of the invention, the mass percent of the rigid protective layer 322 in the sodium supplement particles is 1-20% wt, the mass percent of the flexible protective layer 321 is 1-20% wt, and the mass percent of the sodium supplement material body 310 is 60-90% wt.
In an alternative embodiment of the invention, the sodium supplement particles have a particle size of from 0.2 μm to 3 μm.
As an alternative embodiment of the present invention, the sodium supplement buffer layer 100 further includes a binder for binding the plurality of sodium supplement particles.
As an alternative embodiment of the present invention, the binder includes at least one of polyvinylidene fluoride, Polyacrylate (Polyacrylate), Sodium Polyacrylate (Sodium Polyacrylate), polyimide, Carboxymethyl Cellulose (Carboxymethyl Cellulose), and Styrene Butadiene Rubber (SBR).
In order to improve the escape efficiency of sodium ions, as a preferred embodiment of the present invention, the sodium supplement buffer layer 100 further includes a conductive agent.
As an alternative embodiment of the present invention, the conductive agent includes at least one of conductive carbon black, carbon nanotubes, and graphene.
In order to ensure the humidity of the sodium supplement buffer layer 100, as an alternative embodiment of the present invention, the sodium supplement buffer layer 100 further includes a wetting agent and a predetermined solvent, and the wetting agent is used to increase the amount of the predetermined solvent absorbed by the sodium supplement buffer layer 100.
For example, the predetermined solvent may alternatively be water (H2O), and the wetting agent includes at least one of fluoroalkyl methoxy ether alcohol, sodium polyacrylate, acetylenic diol vinyl ether, fatty Acid polyoxyethylene ether, and ammonium polyacrylate (Acrylic Acid).
As an optional implementation mode of the invention, the mass percent of the binder in the sodium supplement buffer layer 100 is 1-10 wt%, the mass percent of the conductive agent is 1-5 wt%, the mass percent of the sodium supplement microspheres is 90-98 wt%, and the mass percent of the wetting agent is 0.1-2 wt%.
In an alternative embodiment of the present invention, the thickness of the sodium supplement buffer layer 100 may be 0.5 μm to 5 μm. For example, 2 μm may 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 supplement buffer layer 100 and the conductive layer 300, for example, the conductive structure may be in the shape of a wire, a block, a sheet, or the like, and the material of the conductive structure may be a non-metal conductor or a metal conductor resistant to corrosion of the electrolyte.
In order 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 through the substrate layer 200 in the thickness direction are formed in the substrate layer 200, and at least some of the receiving through holes are provided with the conductive strips 500, one end of each conductive strip 500 is in electrical contact with the sodium supplement buffer layer 100, and the other end is in electrical contact with the corresponding conductive layer 300.
In the embodiment of the present invention, the conductive structure includes a plurality of conductive strips 500 disposed in the plurality of receiving through holes, so as to improve the number of connection points between the conductive layer 300 and the sodium supplement buffer layer 100 and the distribution uniformity of the connection points, ensure the efficiency of the conductive layer 300 for applying voltage to the sodium supplement buffer layer 100, further improve the efficiency of releasing sodium ions from the sodium supplement particles, and ensure the amount of sodium ions in the battery.
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 optional embodiment of the present invention, the material of the conductive strip 500 includes at least one of conductive carbon black, carbon nanotube, 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 (PET), Polyethylene naphthalate, Polyimide (PI), and Polycarbonate (PC).
As an alternative embodiment of the present invention, the thickness of the substrate layer 200 may be 2 μm to 20 μm. For example, the thickness of the base material 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 including:
step S1 is to fabricate a sodium supplement buffer layer 100 on the first substrate layer (i.e., one substrate layer 200 in the current collector provided by the present invention), and fabricate a second substrate layer (i.e., another substrate layer 200 in the current collector provided by the present invention) on the sodium supplement buffer layer 100. The sodium supplement buffer layer 100 comprises a plurality of sodium supplement particles, each sodium supplement particle comprises a sodium supplement material body 310 and a coating layer 320 coated on the surface of the sodium supplement material body 310, the sodium supplement material body 310 can penetrate through the coating layer 320 to release sodium ions, and the sodium ions can penetrate through a substrate layer (namely a first substrate layer or a second substrate layer) under the action of voltage;
step S2, conductive structures are 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 away from the sodium supplement buffer layer 100, so that the sodium supplement buffer layer 100 is electrically connected to each conductive layer 300 through the conductive structures.
In the current collector manufactured by the manufacturing method of the current collector provided by the invention, a sandwich structure of the sodium supplement buffer layer 100 is arranged between two substrate layers 200 (namely a first substrate layer and a second substrate layer), the sodium supplement buffer layer 100 is provided with a plurality of microsphere particles, the interior of the microsphere particles contains a sodium supplement material body 310, sodium ions released by the sodium supplement material body 310 can pass through the coating layer 320 to escape from the microsphere particles, so that after the current collector is discharged for the first time to form an SEI passivation layer and lose a large amount of sodium ions, the sodium supplement material body 310 can release sodium ions outwards through the coating layer 320, and the released sodium ions can be applied by the voltage applied to the sodium supplement buffer layer 100 by the conductive layer 300 through the conductive structure, the electrolyte moves to the conductive layer 300 to increase the amount of sodium ions participating in the reaction of the battery in the current collector, so that the sodium ions in the battery are compensated, and the energy density of the battery is ensured.
In order to improve the flow efficiency of carriers in the current collector, as an optional 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:
a plurality of accommodating through holes penetrating (corresponding to the film layers) in the thickness direction are manufactured in the first substrate layer and the second substrate layer, and a plurality of conductive strips 500 are placed in at least part of the accommodating through holes in a one-to-one correspondence manner, so that one ends of the conductive strips 500 are in electric contact with the sodium supplementing buffer layer, and the other ends of the conductive strips 500 are parallel and level to the surface of one side of the corresponding substrate layer (namely the corresponding first substrate layer or second substrate layer) deviating from the sodium supplementing buffer layer 100, thereby ensuring that the manufactured conductive layer 300 manufactured subsequently can be in electric contact with the conductive strips 500.
As an alternative embodiment of the present invention, the method for manufacturing the current collector further includes a step of manufacturing a flexible protection layer 321 and a rigid protection layer 322 on the sodium supplement material body 310 to obtain sodium supplement particles.
As an alternative embodiment of the present invention, the flexible protection layer 321 and the rigid protection layer 322 coated on the sodium supplement 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 optional embodiment of the present invention, the method for manufacturing the current collector further includes a step of mixing the sodium supplement particles with other materials (e.g., a binder, a conductive agent, a wetting agent, and a predetermined solvent) of the sodium supplement buffer layer 100 to obtain the sodium supplement buffer layer 100.
To facilitate 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 present invention are given below:
the first embodiment is as follows:
the surface of the sodium phosphide powder (i.e. the sodium supplement material body 310) is uniformly coated with the polyvinylidene fluoride glue solution (i.e. the flexible protective layer 321 is manufactured) by a liquid phase coating method.
Depositing a layer of uniform aluminum oxide (Al) on the surface of the structure coated with the polyvinylidene fluoride glue solution by a vapor deposition method 2 O 3 ) And (4) preparing a protective layer (namely manufacturing a rigid protective layer 322) to obtain the sodium supplement particles.
Mixing 10 wt% of polyacrylate (binder), 2 wt% of conductive agent, 87.5 wt% of sodium supplement particles and 0.5 wt% of sodium polyacrylate (wetting agent) with water, uniformly stirring, preparing slurry, coating the slurry on a PET (polyethylene terephthalate) film (namely a substrate layer 200) with the thickness of 4 mu m, and coating the slurry with the thickness of 2 mu m (namely a sodium supplement buffer layer 100 is manufactured on a first substrate layer).
A PET film with the thickness of 4 mu m is manufactured on the coating layer through a thermal compounding process (namely, a second base material layer is manufactured on the sodium supplement buffer layer 100);
punching a plurality of holes (namely, manufacturing a plurality of accommodating through holes) in the substrate layer on two sides of the manufactured review film layer, and placing conductive carbon black (namely, a conductive strip 500) in each hole;
the surfaces of the two side PET films are respectively plated with an aluminum conducting layer with the thickness of 1 μm by a vacuum evaporation process, that is, a conducting layer 300 is respectively manufactured on one side of the first base material layer and one side of the second base material layer which are far away from the sodium supplement buffer layer 100.
Example two:
the surface of the sodium phosphide powder (i.e. the sodium supplement material body 310) is uniformly coated with the polyvinylidene fluoride glue solution (i.e. the flexible protective layer 321 is manufactured) by a liquid phase coating method.
Depositing a layer of uniform titanium oxide (TiO) on the surface of the structure coated with the polyvinylidene fluoride glue solution by a vapor deposition method 2 ) And (4) preparing a protective layer (namely manufacturing a rigid protective layer 322) to obtain the sodium supplement particles.
Mixing 10 wt% of polyacrylate (binder), 2 wt% of conductive agent, 87.5 wt% of sodium supplement particles and 0.5 wt% of sodium polyacrylate (wetting agent) with water, uniformly stirring, preparing slurry, coating the slurry on a PET film (namely a substrate layer 200) with the thickness of 4 mu m, and coating the slurry with the thickness of 2 mu m (namely manufacturing a sodium supplement buffer layer 100 on a first substrate layer).
A PI film with a thickness of 4 μm is formed on the coating layer by a thermal lamination process (i.e., a second substrate layer is formed on the sodium supplement buffer layer 100).
Punching a plurality of holes (namely, manufacturing a plurality of accommodating through holes) in the substrate layer on two sides of the manufactured review film layer, and placing conductive carbon black (namely, a conductive strip 500) in each hole;
and respectively plating an aluminum conducting layer with the thickness of 1 mu m on the surfaces of the PET film and the PI film through a vacuum evaporation process, namely respectively manufacturing a conducting layer 300 on one side of the first base material layer and one side of the second base material layer, which are far away from the sodium supplement buffer layer 100.
As a third aspect of the present invention, there is provided a battery including the current collector provided in the embodiments of the present invention.
In the battery provided by the invention, a sandwich structure of a sodium supplement buffer layer 100 is arranged between two substrate layers 200 of a current collector, the sodium supplement buffer layer 100 is provided with a plurality of microsphere particles, the interior of each microsphere particle contains a sodium supplement material body 310, and sodium ions released by the sodium supplement material bodies 310 can escape from the microsphere particles through a coating layer 320, so that after the current collector is discharged for the first time to form an SEI passivation layer and lose a large amount of sodium ions, the sodium supplement material bodies 310 can release the sodium ions outwards through the coating layer 320, and the released sodium ions can move to a conductive layer 300 through electrolyte under the action of voltage applied to the sodium supplement buffer layer 100 by the conductive layer 300 through a conductive structure, so that the amount of the sodium ions participating in battery reaction in the current collector is increased, the sodium ions in the battery are compensated, and the energy density of the battery is further ensured.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. The utility model provides a mass flow body, its characterized in that, including the benefit sodium 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 benefit sodium buffer layer, two the conducting layer is located two respectively the substrate layer deviates from one side of benefit sodium buffer layer, be provided with conductive structure in the substrate layer, conductive structure be used for with benefit sodium buffer layer with the conducting layer electricity is connected, benefit sodium buffer layer includes a plurality of benefit sodium particles, it includes benefit sodium material body and cladding at to benefit sodium material body surface's coating, it can see through to benefit sodium material body coating release sodium ion, just the sodium ion of benefit sodium material body release can the conducting layer with pass under the voltage effect between the benefit sodium buffer layer the substrate layer reachs the conducting layer.
2. The current collector of claim 1, wherein the coating layer comprises a flexible protective layer and a rigid protective layer laminated and coated on the surface of the sodium supplement material, and the elasticity of the flexible protective layer is higher than that of the rigid protective layer.
3. The current collector of claim 2, wherein the flexible protective layer covers the surface of the sodium supplement material body, the rigid protective layer covers the outer side of the flexible protective layer, the flexible protective layer is made of an organic polymer material, and the rigid protective layer is made of an inorganic substance.
4. The current collector of claim 3, wherein the material of the flexible protective layer comprises at least one of polyvinylidene fluoride, polydimethylsiloxane, and polyacrylic acid.
5. The current collector of claim 3, wherein the material of the rigid protective layer comprises at least one of titanium dioxide, tin oxide, and metallic tin.
6. The current collector of any one of claims 1 to 5, wherein the sodium supplement buffer layer further comprises a binder for binding the plurality of sodium supplement particles.
7. The current collector of any one of claims 1 to 5, wherein the conductive structure comprises a plurality of conductive strips, the substrate layer has a plurality of receiving through holes formed therein and extending through the substrate layer in a thickness direction, and at least some of the receiving through holes have the conductive strips disposed therein, one end of each conductive strip is in electrical contact with the sodium-supplementing buffer layer, and the other end of each conductive strip is in electrical contact with the corresponding conductive layer.
8. The current collector of claim 7, wherein the conductive strip comprises at least one of conductive carbon black, carbon nanotubes, and graphene.
9. A method of making a current collector, the method comprising:
the method comprises the following steps of manufacturing a sodium supplement buffer layer on a first substrate layer, and manufacturing a second substrate layer on the sodium supplement buffer layer, wherein the sodium supplement buffer layer comprises a plurality of sodium supplement particles, the sodium supplement particles comprise sodium supplement material bodies and coating layers coated on the surfaces of the sodium supplement material bodies, the sodium supplement material bodies can penetrate through the coating layers to release sodium ions, and the sodium ions can penetrate through the substrate layer 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 the sides of the first substrate layer and the second substrate layer, which deviate from the sodium supplement buffer layer, so that the sodium supplement buffer layer is electrically connected with each conductive layer through the conductive structure.
10. The method for manufacturing the current collector as claimed in claim 9, wherein the conductive structure comprises a plurality of conductive strips, and the manufacturing the conductive structure in the first substrate layer and the second substrate layer comprises:
first substrate layer with make a plurality of holding through-holes that link up along the thickness direction in the second substrate layer, and at least part place a plurality ofly in holding the through-hole one-to-one the conducting strip makes the one end of conducting strip with mend the electrical contact of sodium buffer layer, the other end of conducting strip deviates from with the substrate layer that corresponds the surperficial parallel and level of mending sodium buffer layer one side.
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