WO2023217191A1 - Collecteur de courant et batterie au sodium-métal - Google Patents

Collecteur de courant et batterie au sodium-métal Download PDF

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Publication number
WO2023217191A1
WO2023217191A1 PCT/CN2023/093317 CN2023093317W WO2023217191A1 WO 2023217191 A1 WO2023217191 A1 WO 2023217191A1 CN 2023093317 W CN2023093317 W CN 2023093317W WO 2023217191 A1 WO2023217191 A1 WO 2023217191A1
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WO
WIPO (PCT)
Prior art keywords
current collector
sodium
particles
coating
carbon
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PCT/CN2023/093317
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English (en)
Chinese (zh)
Inventor
黄华文
赵伟
李素丽
Original Assignee
珠海冠宇电池股份有限公司
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Priority claimed from CN202210509236.2A external-priority patent/CN117080451A/zh
Priority claimed from CN202210692647.XA external-priority patent/CN114843524A/zh
Application filed by 珠海冠宇电池股份有限公司 filed Critical 珠海冠宇电池股份有限公司
Publication of WO2023217191A1 publication Critical patent/WO2023217191A1/fr

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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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • H01M4/66—Selection of materials

Definitions

  • the present disclosure belongs to the technical field of secondary ion batteries, and specifically relates to a current collector and a sodium metal battery including the current collector.
  • the sodium metal anode has a high theoretical capacity (1166mAh g -1 ) and a low reaction site (-2.73V vs. SHE), and has been proposed to build high-energy-density batteries.
  • Negative-electrode-free sodium metal batteries use a current collector as the negative electrode during the assembly process. During the charging process, the sodium ions released from the positive electrode are deposited on the current collector to form a sodium metal negative electrode. Since there is no negative active material layer, the mass and volume of the battery can be greatly reduced and the energy density of the battery can be increased. However, due to the high chemical/electrochemical activity and deposition nucleation potential of metallic sodium, it is easy to react with the electrolyte and deposit unevenly, causing instability of the SEI film and growth of sodium dendrites, resulting in low Coulombic efficiency and short battery cycle life. ; In addition, since metallic sodium is directly deposited on the current collector, it will cause a great change in the cell volume, which brings great challenges to the cell structure design and hinders the practical application of negative electrode-free batteries.
  • the present disclosure provides a current collector and a sodium metal battery including the current collector.
  • the current collector has the characteristics of low nucleation potential of metallic sodium by coating the current collector substrate with a carbon material embedded with sodium-philic particles, and/or is obtained by designing a corrugated or zigzag step coating.
  • the reserved space can improve the huge volume changes caused by the deposition/dissolution process of metallic sodium to the battery core, stabilize the battery core structure, and improve the cycle stability, Coulombic efficiency and cycle life of the battery.
  • a first aspect of the present disclosure provides a current collector.
  • the current collector includes a current collector substrate and a coating disposed on at least one side surface of the current collector substrate.
  • the coating includes carbon embedded with sodium-philic particles. material, and/or the coating includes a corrugated or jagged step coating.
  • the coating includes a carbon material embedded with sodium-philic particles, and the carbon material embedded with sodium-philic particles includes carbon particles and sodium-philic particles embedded in the carbon particles.
  • the coating includes a corrugated or jagged step coating
  • the coating path of the corrugated step coating is a water corrugated curve, a sine curve or a cosine curve, and the zigzag step coating
  • the coating path of the coating is a polyline.
  • the coating includes a carbon material embedded with sodium-philic particles, the carbon material embedded with sodium-philic particles includes carbon particles and sodium-philic particles embedded in the carbon particles, and the coating
  • the layer includes a corrugated or zigzag step coating, the coating path of the corrugated step coating is a water ripple curve, a sine curve or a cosine curve, and the coating path of the zigzag step coating is a zigzag line .
  • a second aspect of the disclosure provides a sodium metal battery, which includes the current collector described in the first aspect of the disclosure.
  • the present disclosure provides a current collector used in sodium metal batteries.
  • the current collector of the present disclosure can slow down the repeated deposition/dissolution process of metallic sodium to bring large volume changes to the battery core, stabilize the battery core structure, and improve the cycle stability of the battery. , Coulombic efficiency and cycle life.
  • Figure 1 is a schematic structural diagram of the current collector of the present disclosure.
  • Figure 2 is a top view of a current collector with a corrugated step coating of the present disclosure.
  • Figure 3 is a top view of a current collector with a zigzag step coating of the present disclosure.
  • FIG. 4 is an oblique side view of a current collector with a corrugated or zigzag step coating of the present disclosure.
  • Figure 5 is a front view of a current collector with a corrugated or zigzag step coating of the present disclosure.
  • a first aspect of the present disclosure provides a current collector.
  • the current collector includes a current collector substrate and a coating disposed on at least one side surface of the current collector substrate.
  • the coating includes carbon embedded with sodium-philic particles. material, and/or the coating includes a corrugated or jagged step coating.
  • the coating includes a carbon material embedded with sodium-philic particles, and the carbon material embedded with sodium-philic particles includes carbon particles and sodium-philic particles embedded in the carbon particles.
  • the coating includes a corrugated or jagged step coating
  • the coating path of the corrugated step coating is a water corrugated curve, a sine curve or a cosine curve, and the zigzag step coating
  • the coating path of the coating is a polyline.
  • the coating includes a carbon material embedded with sodium-philic particles, the carbon material embedded with sodium-philic particles includes carbon particles and sodium-philic particles embedded in the carbon particles, and the coating
  • the layer includes a corrugated or jagged step coating, and the coating path of the corrugated step coating is a water corrugated curve, a normal Chordal curve or cosine curve, the coating path of the zigzag step coating is a polyline.
  • the coating includes a carbon material embedded with sodium-philic particles.
  • a current collector is obtained by coating a carbon material with embedded sodium-philic particles on a current collector substrate.
  • the embedded particles in the carbon material with embedded sodium-philic particles can be used to reduce the deposition overpotential of metallic sodium and improve the deposition of metallic sodium/
  • the dissolution performance process brings huge volume changes to the battery core, stabilizes the battery core structure, and improves the cycle stability of the battery.
  • the positive electrode sodium ions will deposit metallic sodium in situ on the current collector, thereby achieving uniform and reversible deposition/dissolution of metallic sodium and improving the Coulombic efficiency of the battery.
  • the carbon material embedded with sodium-philic particles includes carbon particles and sodium-philic particles embedded in the carbon particles.
  • the carbon particles are carbon particles with a hollow structure and/or a porous structure.
  • the hollow structure and/or porous structure can also provide space for the deposition of metallic sodium, slowing down the repeated deposition/dissolution process of metallic sodium that brings a large volume to the battery core. changes, stabilizes the cell structure, and improves the cycle stability of the battery.
  • the hollow structure refers to a geometric structure constructed on the basis of a conventional structure, so that one or more internal cavities are generated inside the particles, and the special morphology of the shell is formed around these cavities.
  • the hollow structure is a single-cavity hollow structure or a multi-cavity hollow structure.
  • the porous structure refers to a structure with regular pores or irregular pores inside.
  • the porous structure is a regular porous structure or an irregular porous structure.
  • the embedding may be, for example, embedded in a hollow structure and/or porous structure, or may be embedded inside carbon particles.
  • the carbon particles have a porosity of 20% to 80% (eg, 20%, 30%, 40%, 50%, 60%, 70%, 80%).
  • porosity of the carbon particles is limited to the above-mentioned specific range, it can be beneficial to the storage of sodium clusters and reduce the generation of sodium dendrites.
  • the median particle diameter D v 50 of the carbon particles is 0.5 ⁇ m to 10 ⁇ m (eg, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m or 10 ⁇ m).
  • the median particle size can be measured using a laser particle size analyzer.
  • the carbon particles are amorphous carbon particles.
  • the amorphous carbon is selected from metal-organic framework material pyrolytic carbon, resin pyrolytic carbon, organic polymer pyrolytic carbon, pyrolytic carbon black, biomass pyrolytic carbon, petroleum coke, needle coke at least one of them.
  • the sodium-philic particles may include metal elements and/or metal compounds.
  • the sodium-philic particles are selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), zinc (Zn), Zinc oxide (ZnO), copper (Cu), copper oxide (CuO), tin (Sn), tin oxide (SnO), antimony (Sb), antimony oxide (Sb 2 O 3 , Sb 2 O 5 ), bismuth (Bi ), bismuth oxide (Bi 2 O 3 ), aluminum oxide (Al 2 O 3 ), and the like.
  • the sodium-philic particles selected from the above range can effectively reduce the deposition potential of sodium, which is beneficial to the uniform deposition and reversible circulation of metallic sodium.
  • the median particle diameter D v 50 of the sodium-philic particles is 2 nm to 100 nm (for example, 2 nm, 3 nm, 5 nm, 8 nm, 10 nm, 12 nm, 15 nm, 18 nm, 20 nm, 30 nm, 35 nm, 40 nm, 45 nm , 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm).
  • the median particle size can be measured using a laser particle size analyzer.
  • the median particle diameter of the sodium-loving particles is limited to the above-mentioned specific range, it is beneficial to obtain better processing performance and at the same time, the sodium-loving particles have a larger active surface to participate in the induction of sodium deposition, which is beneficial to Improve battery cycle performance.
  • the weight content of the sodium-philic particles is 0.5wt%-30wt% (for example, 0.5wt%, 1wt%, 2wt%, 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 24wt%, 25wt%, 26wt%, 28wt%, 30wt%).
  • Naphilic particles are inactive components in the battery and will affect the energy density of the battery. By limiting the weight content of the sodium-philic particles in the carbon material embedded with the sodium-philic particles, it is possible to achieve better induction of metallic sodium deposition. It also reduces the energy density loss of the battery.
  • the weight content of the carbon particles is 70wt%-99.5wt% (for example, 70wt%, 72wt%, 75wt%, 78wt% , 80wt%, 82wt%, 85wt%, 88wt%, 90wt%, 92wt%, 95wt%, 96wt%, 98wt%, 99wt%, 99.5wt%).
  • the median particle diameter D v 50 of the carbon material embedded with the sodium-philic particles is 0.5 ⁇ m-10 ⁇ m (for example, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m).
  • the median particle size can be measured using a laser particle size analyzer.
  • the coating further includes a first binder, a first conductive agent and a thickener.
  • the weight content of the carbon material embedded with the sodium-philic particles is 75wt% to 98wt% (for example, 75wt%, 78wt%, 80wt%, 82wt%, 85wt%, 88wt%, 90wt%, 92wt%, 95wt%, 96wt%, 98wt%).
  • the weight content of the carbon material embedded with sodium-philic particles is 85 wt% to 96 wt%.
  • the weight content of the first binder is 0wt% to 10wt% (for example, 0wt%, 0.5wt%, 1wt%, 2wt%, 3wt% , 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%)
  • the weight content of the first conductive agent is 0wt% ⁇ 15wt% (for example, 0wt%, 0.5wt%, 1wt% ,2wt%,3wt%,4wt%,5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%)
  • the weight content of the thickener is 0wt% to 15wt% (for example, 0wt% , 0.5wt%, 1wt%, 2wt%, 3wt% , 4
  • the coating does not contain the first binder.
  • the weight content of the first conductive agent is 0 wt%, it means that the coating does not contain the conductive agent.
  • the weight content of the thickener is 0 wt%, it means that the coating does not contain the thickener.
  • the weight content of the first binder is 2wt% ⁇ 8wt%, and the weight content of the first conductive agent is 2wt% ⁇ 10wt%, so The weight content of the thickener is 2wt% to 10wt%.
  • the first binder includes, but is not limited to: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), nitrile rubber (NBR), water-based acrylic One or more of resin, polyvinyl alcohol, polyvinyl butyral, polyurethane, fluorinated rubber, carboxymethyl cellulose (CMC) and polyacrylic acid (PAA).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • water-based acrylic water-based acrylic
  • resin polyvinyl alcohol
  • polyvinyl butyral polyurethane
  • fluorinated rubber fluorinated rubber
  • CMC carboxymethyl cellulose
  • PAA polyacrylic acid
  • the first conductive agent includes, but is not limited to, one or more of carbon-based materials, metal-based materials, and conductive polymers.
  • the carbon-based material is selected from one or more of natural graphite, artificial graphite, graphene, carbon black, acetylene black, Ketjen black and carbon fiber.
  • the thickening agent includes, but is not limited to: sodium carboxymethylcellulose and/or lithium carboxymethylcellulose.
  • the thickness of the coating does not exceed 20 ⁇ m.
  • the thickness of the coating is 1 to 20 ⁇ m (eg, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 13 ⁇ m, 15 ⁇ m, 20 ⁇ m).
  • the thickness of the coating is 5-10 ⁇ m.
  • the thickness of the coating is limited to the above-mentioned specific range, the overall performance of the battery can be further improved; when the thickness of the coating is higher than 10 ⁇ m, the thickness of the coating is too thick and will affect the volumetric energy density of the battery; When the thickness of the coating is less than 5 ⁇ m, the thickness of the coating is too thin, and the coating cannot effectively induce sodium metal deposition.
  • the coating covers the surface of the current collector substrate by coating.
  • the current collector substrate includes, but is not limited to: one of copper foil, perforated copper foil, nickel foil, aluminum foil, perforated aluminum foil, stainless steel foil, titanium foil, nickel foam and copper foam, or Various.
  • the thickness of the current collector substrate may be 5 ⁇ m-20 ⁇ m (eg, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 13 ⁇ m, 15 ⁇ m, 20 ⁇ m).
  • the thickener is dispersed in a solvent (such as water) to form a uniform slurry.
  • the slurry is coated on the current collector base material, and after drying and other processes, the current collector is obtained.
  • the carbon material embedded with sodium-philic particles includes carbon particles and sodium-philic particles embedded in the carbon particles.
  • the carbon particles are carbon particles with a hollow structure and/or a porous structure.
  • the carbon material embedded with sodium-philic particles can be prepared by selecting methods known in the art.
  • the carbon material embedded with sodium-philic particles can be prepared by the following method: first prepare carbon particles with a hollow structure and/or a porous structure, and then deposit the sodium-philic particles inside them.
  • the carbon particles with hollow structure and/or porous structure can be prepared by hard template method, soft template method and template-free method.
  • the hard template method uses a hard template with a fixed structure to combine with a carbon precursor and perform high-temperature carbonization in an inert gas.
  • the hard template is then removed by chemical etching or dissolution to obtain a hollow structure.
  • And/or porous structure such as silicon-based template, metal oxide template, organic template, salt template method, ice template, etc.
  • the soft template in the soft template method refers to a type of surfactant or block copolymer that can be assembled to form a specific form in a solvent.
  • soft templates typically self-assemble with each other to form micelles, which are charged with the hydrophilic ends facing outward. These charged ends attract nearby carbon precursor molecules through electrostatic interactions, and then link these molecules to the soft template surface through covalent bonds, forming rigid organic micelles wrapped by the carbon precursor.
  • the soft template decomposes or evaporates to generate pores in situ, obtaining a hollow structure and/or porous structure.
  • the template-free method is to pyrolyze a selected carbon precursor to obtain a carbon structure dominated by macropores. Secondly, a large number of mesopores and micropores are introduced through chemical activation or physical activation, without adding additional template agents during the process.
  • metal elements and/or metal compounds can be embedded into the pores of porous carbon particles through physical adsorption or chemical/electrochemical methods.
  • the method for preparing a carbon material with a porous structure embedded with sodium-philic particles includes the following steps: using an activation method or a template method to prepare a carbon material with a porous structure, and then combining the carbon material with a porous structure with the sodium-philic particles. After ultrasonic mixing in the solution, through the effect of physical adsorption, the sodium-philic particles are adsorbed in the pore structure of the carbon material with a porous structure, and a carbon material with a porous structure embedded with the sodium-philic particles is obtained.
  • the carbon material embedded with sodium-philic particles can also be prepared by the following method: doping metal ions that form the sodium-philic particles into carbon particles that form a hollow structure and/or a porous structure.
  • metal ions are reduced to metal elements and embedded Inside the carbon particles with hollow structure and/or porous structure.
  • the preparation method of carbon particles with hollow structure and/or porous structure includes activation method and template method; the method of depositing sodium-philic particles inside carbon particles with hollow structure and/or porous structure includes Physical adsorption, chemical deposition, electrochemical reduction, etc.
  • the method for preparing a carbon material with a hollow structure embedded with sodium-philic particles includes the following steps: doping the metal ions that form the sodium-philic particles into a precursor for forming carbon particles with a hollow structure, and during the carbonization process , metal ions are reduced to metal elements and embedded inside carbon particles with a hollow structure.
  • the preparation method of the carbon material with a hollow structure embedded with sodium philic particles includes the following steps: compounding the metal salt and the organic material to form a physical or chemical mixed composite, and during the carbonization process, the carbon is heated under the influence of heat.
  • the reduction property under the conditions reduces the metal ions to metal elements, forming a carbon material with a hollow structure embedded with sodium-philic particles.
  • the preparation method of the carbon material with a hollow structure embedded with sodium philic particles includes the following steps: preparing a metal-organic framework material, heating in an inert atmosphere, the organic ligands will be converted into carbon, and the metal ions will be reduced into metal elements, i.e., sodium-philic particles, to obtain a carbon material with a hollow structure embedded with sodium-philic particles.
  • the coating is a corrugated or zigzag step coating.
  • a corrugated or jagged step coating By setting up a corrugated or jagged step coating, a reserved space is obtained on the surface of the current collector, which slows down the huge volume changes brought to the battery core by the repeated deposition/dissolution process of metallic sodium, stabilizes the battery core structure, and improves the battery performance. Cycling stability.
  • the corrugated or zigzag step coating is a coating with a certain thickness formed by back-and-forth coating at a certain angle with the width direction of the current collector substrate.
  • the top view of the current collector shown in Figures 2 and 3.
  • the coating path of the corrugated step coating is a water corrugated curve, a sine curve or a cosine curve
  • the coating path of the zigzag step coating is a polyline.
  • the coating path of the corrugated or zigzag step coating has periodic distribution characteristics.
  • the current collector satisfies: 0.2W ⁇ L ⁇ 1W.
  • the current collector satisfies: W1 ⁇ W; where W1 is the width of the corrugated or zigzag step coating, and W is the width of the current collector substrate.
  • W1 is the width of the corrugated or zigzag step coating
  • W is the width of the current collector substrate.
  • the width W1 of the corrugated or zigzag step coating refers to the distance between the outermost edges of both transverse sides of the step coating.
  • the width W1 of the corrugated or zigzag step coating ⁇ the width of the matched cathode paste; wherein the width of the matched cathode paste is the active material layer of the matched cathode sheet width.
  • the width W2 of the corrugated or zigzag step coating satisfies: 1mm ⁇ W2 ⁇ 20mm (for example, W2 is 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm , 12mm, 13mm, 15mm, 18mm, 20mm).
  • W2 is 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm , 12mm, 13mm, 15mm, 18mm, 20mm.
  • the width W2 of the corrugated or zigzag step coating refers to the width of the coating path of the corrugated or zigzag step coating.
  • the thickness H2 of the corrugated or zigzag step coating can be adjusted with the change of the surface capacity of the positive electrode sheet of the designed battery core.
  • the thickness H2 of the corrugated or zigzag step coating satisfies: 5 ⁇ m ⁇ H2 ⁇ 50 ⁇ m (for example, H2 is 5 ⁇ m, 6 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 25 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 35 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 45 ⁇ m, 48 ⁇ m, 50 ⁇ m).
  • the thickness of the step is to reserve a certain space for the deposition of metallic sodium. When the thickness of the step is limited to the above-mentioned specific range, high volumetric energy density can be ensured while satisfying the deposition of metallic sodium.
  • the material forming the corrugated or zigzag step coating includes a second binder and ceramic particles.
  • the mass ratio of the binder and ceramic particles is (3-7):(7-3) (for example, 3:7, 4:6, 5:5, 6:4, 7:3 ). That is, based on the total weight of the binder and ceramic particles, the weight content of the binder is 30wt%-70wt%, and the weight content of the ceramic particles is 70wt%-30wt%.
  • the second binder includes, but is not limited to: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), water-based acrylic Resin, polyvinyl alcohol, polyvinyl butyral, polyurethane, fluorinated rubber, carboxymethylcellulose (CMC), polyacrylic acid (PAA).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • NBR nitrile-butadiene rubber
  • water-based acrylic Resin polyvinyl alcohol, polyvinyl butyral, polyurethane, fluorinated rubber, carboxymethylcellulose (CMC), polyacrylic acid (PAA).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR st
  • the ceramic particles include, but are not limited to, aluminum oxide (Al 2 O 3 ), boehmite ( ⁇ -AlOOH), silicon dioxide (SiO 2 ), silicon carbide (SiC), magnesium oxide (MgO) ), zirconium oxide (ZrO 2 ).
  • the corrugated or zigzag step coating can be achieved by moving extrusion coating or moving spray coating.
  • the current collector substrate includes, but is not limited to: copper foil, perforated copper foil, nickel foil, aluminum One or more of foil, perforated aluminum foil, stainless steel foil, titanium foil, nickel foam and copper foam.
  • the thickness of the current collector substrate is 5 ⁇ m-20 ⁇ m (eg, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 13 ⁇ m, 15 ⁇ m, 20 ⁇ m).
  • a second aspect of the disclosure provides a sodium metal battery.
  • the negative electrode-less sodium metal battery includes the current collector described in the first aspect of the disclosure.
  • the sodium metal battery has no negative electrode, that is, the sodium metal battery does not include a negative electrode sheet.
  • the sodium metal battery further includes a positive electrode sheet, a separator and an electrolyte.
  • the use of the negative electrode-less sodium metal battery is not particularly limited and can be used for various known uses.
  • the battery core of the negative-electrode-less sodium metal battery may be a laminated structure formed by stacking a current collector, a separator, and a positive electrode sheet in sequence, or it may be a stacked structure by stacking a current collector, a separator, and a positive electrode sheet in order and then rolling.
  • the positive electrode sheet may be a conventional positive electrode sheet in the art.
  • the positive electrode sheet includes a positive electrode current collector and an active material layer; the active material layer is coated on the surface of the positive electrode current collector; the active material layer includes an active material layer. substance.
  • the active material in the positive electrode sheet includes one or more of Prussian blue materials, polyanionic materials, and transition metal layered oxides.
  • the transition metal layered oxide is selected from NaCoO 2 , Na 2/3 [Cu 1/3 Mn 2/3 ]O 2 , Na 2/3 [Fe 1/3 Mn 2/3 ] O 2 , Na 2/3 [Li 1/3 Ni 2/3 ]O 2 , Na [Ni 0.5 Co 0.5 ]O 2 , Na 7/9 [Cu 2/9 Fe 1/9 Mn 2/3 ]O 2 , Na 2/3 [Li 1/3 Mn 1/2 Ti 1/6 ]O 2 , Na[Ni 0.5 Fe 0.5 ]O 2 , Na[Co 0.5 Fe 0.5 ]O 2 , Na[Ni 1/3 Fe 1 /3 Mn 1/3 ]O 2 and Na[Cu 1/9 Ni 2/9 Fe 1/3 Mn 1/3 ]O 2 .
  • the chemical formula of the Prussian blue material is A x M[Fe(CN) 6]y , where A is an alkali metal cation, M is a transition metal cation, 1 ⁇ x ⁇ 2, 0.9 ⁇ y ⁇ 1.
  • the Prussian blue material also contains crystal water.
  • a specifically can be Li, Na, K, Rb, Cs or Fr.
  • M may be one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr and Mo.
  • the Prussian blue material is selected from LiFe 2 (CN) 6 , LiCoFe(CN) 6 , LiMnFe(CN) 6 , NaFe 2 (CN) 6 , KFe 2 (CN) 6 , NaCuFe(CN) 6.
  • LiFe 2 (CN) 6 LiCoFe(CN) 6 , LiMnFe(CN) 6 , NaFe 2 (CN) 6 , KFe 2 (CN) 6 , NaCuFe(CN) 6.
  • NaNiFe(CN) 6 Na 2 Fe 2 (CN) 6
  • Na 2 MnFe(CN) 6 Na 2 CoFe(CN) 6
  • Na 2 NiFe(CN) 6 Na 2 NiFe(CN) 6 .
  • the chemical formula of the polyanionic material is A' x' M' y' (X n' O m ) z F w , where A' is Li or Na, and M' is a transition of a variable valence state
  • A' is Li or Na
  • M' is a transition of a variable valence state
  • metal ions is P, S, V or Si, and x' ⁇ 1, y'>0, z ⁇ 1, w ⁇ 0, the values of n' and m comply with the principle of charge conservation.
  • M' is Ti, Fe or Mn.
  • the polyanionic material is selected from one of NaFePO 4 , Na 3 V 2 (PO 4 ) 3 , Na 2 MnP 2 O 7 , Na 2 FeP 2 O 7 and Na 2 FePO 4 F or Various.
  • the Prussian blue material has a median particle diameter D v 50 of 1 ⁇ m to 15 ⁇ m (for example, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m).
  • the median particle size can be measured using a laser particle size analyzer.
  • the median particle diameter D v 50 of the polyanionic material is 1 ⁇ m to 10 ⁇ m (eg, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m).
  • the median particle size can be measured using a laser particle size analyzer.
  • the positive electrode sheet is used in a sodium metal battery without anode.
  • the active material layer in the positive electrode sheet further includes a second conductive agent and a third binder.
  • the second conductive agent includes, but is not limited to: carbon-based materials, metal-based materials, and conductive polymers.
  • the carbon-based material is selected from one or more of natural graphite, artificial graphite, graphene, carbon black, acetylene black, Ketjen black and carbon fiber.
  • the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, and silver.
  • the conductive polymer is a polyphenylene derivative.
  • the third binder includes, but is not limited to: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), nitrile rubber (NBR), water-based acrylic Resin, polyvinyl alcohol, polyvinyl butyral, polyurethane, fluorinated rubber, carboxymethylcellulose (CMC), polyacrylic acid (PAA).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • water-based acrylic Resin water-based acrylic Resin
  • polyvinyl alcohol polyvinyl butyral
  • polyurethane fluorinated rubber
  • CMC carboxymethylcellulose
  • PAA polyacrylic acid
  • the weight content of the active material is 75wt% to 98wt% (for example, 75wt%, 80wt%, 82wt%, 85wt%, 90wt%, 95wt% , 96wt%, 98wt%)
  • the weight content of the second conductive agent is 1wt% ⁇ 15wt% (for example, 1wt%, 2wt%, 5wt%, 10wt%, 15wt%)
  • the third binder has The weight content is 1 to 10 wt% (for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%).
  • the weight content of the active material is 82wt% ⁇ 96wt%
  • the weight content of the second conductive agent is 2wt% ⁇ 10wt%
  • the The weight content of the third binder is 2wt% to 8wt%.
  • the positive electrode current collector includes, but is not limited to, one or more of aluminum foil, carbon-coated aluminum foil, perforated aluminum foil, stainless steel foil, and polymer substrate covered with conductive metal.
  • the positive electrode sheet can be prepared according to conventional methods in the art. Usually, the active material and optional second conductive agent and third binder are dispersed in a solvent (such as NMP) to form a uniform positive electrode slurry. The positive electrode slurry is coated on the current collector and dried through processes such as Finally, the positive electrode sheet is obtained.
  • a solvent such as NMP
  • the separator may be a conventional separator in the art.
  • the separator may be a polypropylene separator (PP), a polyethylene separator (PE), a polypropylene/polyethylene double-layer composite film (PP/PE), a polypropylene/polyethylene separator.
  • PP polypropylene separator
  • PE polyethylene separator
  • PP/PE polypropylene/polyethylene double-layer composite film
  • PI polyimide electrospun separator
  • PET polyethylene terephthalate non-woven separator
  • the separator plays an isolation role between the positive electrode sheet and the current collector.
  • any lower limit can be combined with any upper limit to form an unexpressed range; and any lower limit can be combined with other lower limits to form an unexpressed range, and likewise any upper limit can be combined with any other upper limit to form an unexpressed range.
  • every point or individual value between the endpoints of a range is included in the range.
  • each point or single value may serve as a lower or upper limit on its own in combination with any other point or single value or with other lower or upper limits to form a range not expressly recited.
  • This Group I example is used to illustrate the current collector and anode-free sodium metal battery of the present disclosure including a carbon material embedded with sodium-philic particles.
  • the single-cavity structures mentioned in the Examples and Comparative Examples are prepared using a silicon-based template method, and the porosity of the carbon particles can be adjusted by adjusting the concentration of the template.
  • the irregular porous structures mentioned in the examples and comparative examples are prepared using a soft template method, such as using the cationic surfactant cetyltrimethylammonium bromide as a template in a carbon-based precursor, An irregular porous structure is formed during the high-temperature carbonization process.
  • the regular porous structure rules mentioned in the Examples and Comparative Examples are prepared by using a hard template method, such as closely packed polystyrene beads and silica beads as template agents, and the template agents are removed after carbonization. Carbon particles with an ordered pore structure can be obtained.
  • a hard template method such as closely packed polystyrene beads and silica beads as template agents
  • the preparation method of the sodium-philic particles mentioned in the Examples and Comparative Examples is as follows:
  • Gold and silver metal elements are soaked in salt solution combined with solution reduction method
  • Zn, Bi, Sb, and Sn metal elements are prepared by soaking in salt solution combined with thermal reduction method. Carbon particles with hollow structure and/or porous structure are dispersed in the metal salt solution, filtered, dried, and then heated at high temperature in a reducing atmosphere. Heat treatment prepares elemental metal particles embedded in a porous carbon pore structure;
  • ZnO is prepared by soaking in a salt solution combined with heat treatment. Carbon particles with hollow structures and/or porous structures are dispersed in a metal salt solution, filtered and dried, and then heat treated at high temperature in an oxygen atmosphere to prepare a porous carbon pore structure embedded in it. of ZnO nanoparticles.
  • the particle size of the generated sodium-philic particles is controlled by the concentration of the metal salt or the reaction time.
  • the embedded sodium-philic particles obtained in step (1) Carbon materials with hollow structure and/or porous structure, conductive agent carbon black (Super P), binder styrene-butadiene rubber (SBR), thickener sodium carboxymethylcellulose (CMC), mix the powder evenly Add an appropriate amount of deionized water, stir thoroughly to form a uniform slurry, apply the slurry on aluminum foil, and then dry, roll, and cut to obtain a current collector.
  • Carbon materials with hollow structure and/or porous structure Carbon materials with hollow structure and/or porous structure, conductive agent carbon black (Super P), binder styrene-butadiene rubber (SBR), thickener sodium carboxymethylcellulose (CMC), mix the powder evenly Add an appropriate amount of deionized water, stir thoroughly to form a uniform slurry, apply the slurry on aluminum foil, and then dry, roll, and cut to obtain a current collector.
  • Super P conductive agent carbon black
  • SBR binder styrene-butadiene rubber
  • ethylene carbonate (EC), propylene carbonate (PC), and diethyl carbonate (DEC) at a mass ratio of 0.5:1.5:1.5, adding a concentration of 1.0mol/L sodium hexafluorophosphate (NaPF 6 ), stir evenly, then add 1.0wt% sodium nitrate (NaNO 3 ), continue stirring fully, and obtain an electrolyte.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Example I1 for the specific process.
  • the difference is the type, particle size and weight content of the sodium-philic particles, the structure, particle size and porosity of the carbon particles with a hollow structure and/or porous structure, and the coating thickness.
  • the specific details are See Table 1.
  • the metal nanoparticles in Comparative Example I3 are dispersed in a solid nanostructure and are prepared by dispersing a metal salt in a carbon material precursor and performing simultaneous heat treatment and carbonization reduction.
  • a metal salt for example, zinc acetate solution can be dispersed in polyacrylonitrile slurry and heat treated in a reducing atmosphere to prepare a composite material in which metallic zinc nanoparticles are distributed in solid carbon materials.
  • place ethylene carbonate (EC), propylene carbonate (PC) and diethyl carbonate (DEC) are mixed according to the mass ratio of 0.5:1.5:1.5, add sodium hexafluorophosphate (NaPF 6 ) with a concentration of 1 mol/L, stir evenly, and then add 1wt% sodium nitrate (NaNO 3 ), continue to stir thoroughly and obtain the electrolyte.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Example II1 the difference is that the morphology of the step coating is different, as shown in Table 2.
  • the sodium metal battery without negative electrode at 25°C, charge it to the upper limit voltage (4.0V) at a constant current of 0.5C, then charge it at a constant voltage of 4.0V until the current is 0.05C, and let it stand for 5 minutes; then charge it at a constant current of 0.5C Discharge until the voltage is 2.0V, and the recorded discharge capacity is the discharge capacity of the first cycle; the Coulombic efficiency of the first cycle is the ratio of the specific discharge capacity and the specific charge capacity of the first cycle.
  • a corrugated or zigzag step coating of a certain thickness can form a reserved space on the surface of the current collector substrate, slow down the large volume changes caused by the repeated deposition/dissolution process of metallic sodium to the battery core, and stabilize the battery. core structure to improve the cycle stability of the battery.
  • the important thing is that the corrugated or zigzag step shape design can make the overall thickness of the battery core uniform, avoid the structural distortion caused by the reserved steps, improve the structural stability of the battery core in the reserved space, and help further improve Electrochemical performance of anode-free sodium metal batteries.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

La présente divulgation concerne un collecteur de courant et une batterie au sodium-métal comprenant le collecteur de courant. Le collecteur de courant comprend un substrat de collecteur de courant et un revêtement disposé sur au moins une surface latérale du substrat de collecteur de courant, le revêtement comprenant un matériau de carbone enrobé de particules sodiophiles, et/ou un revêtement ondulé ou dentelé. Dans la présente divulgation, par le revêtement d'un substrat de collecteur de courant avec un matériau de carbone enrobé de particules sodiophiles, le collecteur de courant est doté des caractéristiques d'un faible potentiel de nucléation du sodium-métal ; et/ou un espace réservé est obtenu au moyen de la conception d'un revêtement ondulé ou dentelé, de sorte que l'énorme changement de volume qui se produit pour une cellule de batterie pendant le processus de performance de dépôt/dissolution du sodium-métal peut être amélioré, la structure de la cellule de batterie est stabilisée, et la stabilité de cycle, l'efficacité coulombique et la durée de vie de la batterie sont améliorées.
PCT/CN2023/093317 2022-05-10 2023-05-10 Collecteur de courant et batterie au sodium-métal WO2023217191A1 (fr)

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