WO2024065576A1 - 钠离子电池及包含其的用电装置 - Google Patents

钠离子电池及包含其的用电装置 Download PDF

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WO2024065576A1
WO2024065576A1 PCT/CN2022/123008 CN2022123008W WO2024065576A1 WO 2024065576 A1 WO2024065576 A1 WO 2024065576A1 CN 2022123008 W CN2022123008 W CN 2022123008W WO 2024065576 A1 WO2024065576 A1 WO 2024065576A1
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sodium
ion battery
sodium ion
negative electrode
nanoparticles
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PCT/CN2022/123008
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English (en)
French (fr)
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秦猛
官英杰
杨惠玲
赵玉珍
温严
黄起森
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宁德时代新能源科技股份有限公司
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Priority to PCT/CN2022/123008 priority Critical patent/WO2024065576A1/zh
Publication of WO2024065576A1 publication Critical patent/WO2024065576A1/zh

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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the present application relates to the technical field of sodium batteries, and in particular to a sodium ion battery and an electrical device comprising the same.
  • Sodium-ion battery is a secondary battery that mainly relies on the movement of sodium ions between the positive and negative electrodes to work: during charging, Na + escapes from the positive electrode, passes through the diaphragm and embeds into the negative electrode, so that the positive electrode is in a high-potential sodium-poor state and the negative electrode is in a low-potential sodium-rich state; the discharge process is the opposite, Na + escapes from the negative electrode, passes through the diaphragm and is re-embedded in the positive electrode material, restoring the positive electrode to a sodium-rich state.
  • sodium-ion batteries Compared with lithium-ion batteries, sodium-ion batteries have the advantages of better safety performance, wide sources, and low costs. However, their larger ion mass and ion radius cause the energy density of sodium-ion batteries to be lower than that of lithium-ion batteries, which has hindered their development to a certain extent.
  • the present application is made in view of the above-mentioned problems, and its purpose is to provide a sodium ion battery and an electrical device including the same.
  • a first aspect of the present application provides a sodium ion battery, which comprises a positive electrode sheet, a separator and a negative electrode current collector, wherein the separator is arranged between the positive electrode sheet and the negative electrode current collector, and a coating is arranged on the surface of the negative electrode current collector, wherein the coating comprises a carbon material, and the carbon material comprises carbon nanotubes.
  • a second aspect of the present application provides an electrical device comprising at least one of the sodium ion batteries described in the first aspect.
  • FIG1 is a schematic diagram of a sodium ion battery according to an embodiment of the present application.
  • FIG2 is an exploded view of the sodium ion battery according to one embodiment of the present application shown in FIG1 ;
  • FIG3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG5 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG4 ;
  • FIG6 is a schematic diagram of an electrical device using a sodium ion battery as a power source according to an embodiment of the present application
  • FIG. 7 is a photograph of a disassembled negative electrode of the sodium ion secondary battery of Example 1 after charge and discharge.
  • range disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range.
  • the range defined in this way can be inclusive or exclusive of end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60-120 and 80-110 is listed for a specific parameter, it is understood that the range of 60-110 and 80-120 is also expected.
  • the numerical range "a-b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" represents that all real numbers between "0-5" have been fully listed herein, and "0-5" is just the abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the “include” and “comprising” mentioned in this application represent open-ended or closed-ended expressions.
  • the “include” and “comprising” may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • the main scheme is to set a carbon material layer on the surface of the negative electrode current collector, and deposit the sodium metal deposited during the charge and discharge process on the carbon material layer (surface).
  • the presence of the carbon material can inhibit the generation of sodium dendrites to a certain extent, the effect is limited. In the long-term charge and discharge cycle, sodium dendrites are still prone to appear.
  • the method when the method is implemented, it is necessary to pre-deposit a sodium metal layer on the surface of the carbon material layer (the thickness of the pre-deposited sodium metal layer is usually about 1 ⁇ m) to form a sodium-rich surface similar to the negative electrode of the sodium metal battery.
  • the thickness of the pre-deposited sodium metal layer is usually about 1 ⁇ m
  • an example of the present application provides a sodium ion battery, which includes a positive electrode sheet, a separator and a negative electrode current collector, wherein the separator is arranged between the positive electrode sheet and the negative electrode current collector, and the surface of the negative electrode current collector is provided with a coating, wherein the coating includes a carbon material, and the carbon material includes carbon nanotubes.
  • the above-mentioned sodium ion battery on the basis of omitting the negative electrode active material layer, selects carbon nanotubes as carbon materials, and utilizes the pipe structure of the carbon nanotubes to deposit the sodium metal layer on at least one of the inner wall of the tube, the outer wall of the tube, and the surface of the negative electrode current collector.
  • the carbon nanotubes suppress the generation of sodium dendrites by reducing the overpotential of sodium metal deposition (i.e., the nucleation overpotential, reducing the nucleation energy barrier of sodium metal deposition), and more importantly, can suppress the growth of sodium dendrites through its pipe structure and limiting effect, so as to effectively enhance the inhibitory effect on the generation of sodium dendrites, and at the same time, can also stabilize the SEI film on the surface of the carbon nanotubes, and improve the cycle performance of the sodium ion battery. At the same time, there is no need to set up an additional sodium metal layer, which truly reduces the cost of the sodium ion battery and improves the energy density of the sodium ion battery.
  • the overpotential of sodium metal deposition i.e., the nucleation overpotential, reducing the nucleation energy barrier of sodium metal deposition
  • the carbon material is carbon nanotubes.
  • a sodium metal layer is formed on at least one of the inner wall of the carbon nanotube, the outer wall of the carbon nanotube, and the surface of the negative electrode current collector.
  • the sodium metal layer is formed during the charge and discharge process of the sodium ion battery.
  • the charge and discharge process may include the charge and discharge process during the formation treatment, or the charge and discharge process during use.
  • the thickness of the sodium metal layer is P, 0 ⁇ P ⁇ 400nm; optionally, the thickness of the sodium metal layer is 150 ⁇ P ⁇ 300nm. Different from the additional sodium metal layer in the negative electrode of the existing sodium ion battery, the sodium metal layer is formed after the first charge and discharge and has a thinner thickness.
  • the thickness of the sodium metal layer includes but is not limited to: 150nm, 160nm, 165nm, 171nm, 175nm, 180nm, 185nm, 188nm, 192nm, 200nm, 202nm, 205nm, 208nm, 210nm, 211nm, 215nm, 220nm, 222nm, 227nm, 232nm, 235nm, 240nm, 260nm, 280nm, 300nm, or within the range of any two of the above values.
  • the specific surface area of the carbon nanotubes is ⁇ 500m 2 /g. Further, the specific surface area of the carbon nanotubes is 500-1500m 2 /g. Further, the specific surface area of the carbon nanotubes is 750-1000m 2 /g.
  • suitable gaps can be provided for the deposition of the sodium metal layer, so that the sodium metal layer is evenly distributed on the inner wall and outer wall of the tube.
  • the specific surface area of the carbon nanotubes includes but is not limited to: 500m 2 /g, 520m 2 /g, 540m 2 /g, 560m 2 /g, 600m 2 /g, 640m 2 /g, 660m 2 /g, 680m 2 / g, 730m 2 /g, 740m 2 /g, 750m 2 /g, 755m 2 /g, 760m 2 /g, 770m 2 /g, 800m 2 /g, 820m 2 /g, 850m 2 /g, 890m 2 /g, 920m 2 /g, 950m 2 /g, 980m 2 /g, 990m 2 /g, 995m 2 /g, 1000m 2 /g, 1200m 2 /g, 1250m 2 / g
  • the molecular weight of the present invention is 1000 m 2 /g, 1200 m 2 /g, 1400m
  • the diameter of the carbon nanotube is 0.5nm to 50nm. Further, the diameter of the carbon nanotube is 10nm to 40nm, which is conducive to the deposition of the sodium metal layer on the inner wall of the tube. Specifically, the diameter of the carbon nanotube includes but is not limited to: 0.5nm, 3nm, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 30nm, 35nm, 38nm, 40nm, 42nm, 45nm, 50nm, or is within the range of any two of the above values.
  • a number of metal nanoparticles are attached to the carbon nanotubes. This can provide a large number of nucleation sites for the deposition of the sodium metal layer. It is understandable that "on the carbon nanotubes" includes the inner wall and the outer wall of the carbon nanotubes. Further, a number of metal nanoparticles are attached to the inner wall of the carbon nanotubes. This can effectively induce the sodium metal layer to preferentially deposit on the inner wall of the carbon nanotubes, avoid the growth of sodium metal dendrites on the surface of the carbon material layer, and further inhibit the formation of sodium dendrites. It is understandable that a number refers to two or more, including but not limited to: 2, 3, 4, 10, 60, 100, 500 or more.
  • the metal in the metal nanoparticles is a metal that can form an alloy with sodium.
  • the “metal that can form an alloy with sodium” means that the metal can undergo an electrochemical alloying reaction with sodium during the charging process, thereby effectively inhibiting the growth of sodium dendrites.
  • the metal nanoparticles include one or more of Au nanoparticles, Ag nanoparticles, Bi nanoparticles, Sn nanoparticles, Co nanoparticles, Ni nanoparticles, Mg nanoparticles and Zn nanoparticles.
  • the particle size of the metal nanoparticles is at least 0.2nm smaller than the tube diameter of the carbon nanotubes. In this way, an appropriate space is left to avoid affecting the deposition of the sodium metal layer. Furthermore, the particle size of the metal nanoparticles is 0.2nm to 10nm smaller than the tube diameter of the carbon nanotubes. Furthermore, the particle size of the metal nanoparticles is 1nm to 5nm smaller than the tube diameter of the carbon nanotubes.
  • the value of the particle size of the metal nanoparticles smaller than the tube diameter of the carbon nanotubes includes but is not limited to: 0.2nm, 0.5nm, 0.8nm, 1nm, 2nm, 3nm, 4nm, 4.5nm, 4.8nm, 5nm, 5.5nm, 6nm, 7nm, 8nm, 9nm, 9.5nm, 10nm, or within the range of any two of the above values.
  • the particle size of the metal nanoparticles is 0.3nm to 40nm. Further, the particle size of the metal nanoparticles is 8nm to 35nm. Specifically, the particle size of the metal nanoparticles includes but is not limited to: 0.3nm, 1nm, 3nm, 5nm, 7nm, 8nm, 9nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 25nm, 30nm, 33nm, 34nm, 35nm, 36nm, 38nm, 40nm, or within the range of any two of the above values.
  • the mass of the metal nanoparticles is M1
  • M1:M2 0.03-0.07.
  • the value of M1:M2 includes but is not limited to: 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, or within the range of any two of the above values.
  • the test method of M1:M2 can be: punch the negative electrode plate into a small disc, and then perform trace element analysis-inductively coupled plasma emission spectrometry test and CHNS element analysis test.
  • the thickness of the coating is 0.5 ⁇ m to 15 ⁇ m.
  • the thickness of the coating includes but is not limited to: 0.5 ⁇ m, 0.7 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, or within the range of any two of the above values.
  • the material of the coating also includes a binder.
  • the binder includes a polymer binder.
  • the binder may include at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • SBR styrene-butadiene rubber
  • PAA polyacrylic acid
  • PAAS sodium polyacrylate
  • PAM polyacrylamide
  • PVA polyvinyl alcohol
  • SA sodium alginate
  • PMAA polymethacrylic acid
  • CMCS carboxymethyl chitosan
  • the weight ratio of the binder in the coating is 0-30% by weight, based on the total weight of the coating. Further, the weight ratio of the binder in the coating is 0.5-10% by weight, based on the total weight of the coating.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • copper foil may be used as the metal foil.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be formed by forming a metal material on a polymer material substrate.
  • the metal material includes but is not limited to copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.
  • the polymer material substrate includes but is not limited to polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) and other substrates.
  • the surface of the negative electrode current collector is not provided with negative electrode active materials
  • the negative electrode active materials may be hard carbon, soft carbon, sodium metal (here refers to the sodium metal pre-deposited on the surface of the negative electrode current collector (the thickness is usually about 1 ⁇ m), which is different from the sodium metal formed during the charge and discharge process in this application), tin oxide, cobalt vanadium sulfide, etc.
  • the negative electrode current collector has two surfaces opposite to each other in the thickness direction thereof, and the coating is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the coating can be prepared on the surface of the negative electrode current collector in the following manner: dispersing the above-mentioned components for preparing the coating, such as carbon nanotubes, a conductive agent, a binder and any other components in a solvent (such as deionized water) to form a slurry; coating the obtained slurry on the negative electrode current collector and performing a drying process.
  • a solvent such as deionized water
  • the sodium ion battery further includes an electrolyte, which conducts ions between the positive electrode sheet and the negative electrode current collector.
  • the electrolyte includes an electrolyte sodium salt and a solvent.
  • the solvent in the electrolyte includes an ether solvent.
  • Ether solvent molecules can construct a stable electrode/electrolyte interface on the surface of the negative electrode current collector, forming a stable solid electrolyte interface (SEI), and reducing electrochemical polarization.
  • the solvent of the electrolyte includes one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,3-dioxolane, tetrahydrofuran, methyltetrahydrofuran, diphenyl ether and crown ether.
  • the electrolyte sodium salt in the electrolyte includes one or more of sodium hexafluorophosphate, sodium difluorooxalatoborate, sodium tetrafluoroborate, sodium bisoxalatoborate, sodium perchlorate, sodium hexafluoroarsenate, sodium bis(fluorosulfonyl)imide, sodium trifluoromethylsulfonate and sodium bis(trifluoromethylsulfonyl)imide.
  • the molar concentration of the electrolyte sodium salt in the electrolyte is 0.5 mol/L to 8 mol/L. Further, the molar concentration of the electrolyte sodium salt in the electrolyte is 1 mol/L to 4 mol/L.
  • the electrolyte may also optionally include additives.
  • the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the positive electrode includes one of a sodium transition metal oxide positive electrode, a polyanion compound positive electrode, and a Prussian blue compound positive electrode.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer formed on at least a portion of the surface of the positive electrode current collector, wherein the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material may include at least one of a sodium transition metal oxide, a polyanionic compound, and a Prussian blue compound.
  • the present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials for sodium ion batteries may also be used.
  • the transition metal in the sodium transition metal oxide, may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce.
  • the sodium transition metal oxide is, for example, Na x MO 2 , wherein M is one or more of Ti, V, Mn, Co, Ni, Fe, Cr and Cu, and 0 ⁇ x ⁇ 1.
  • the polyanionic compound can be a class of compounds having sodium ions, transition metal ions and tetrahedral (YO 4 ) n- anion units.
  • the transition metal can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce;
  • Y can be at least one of P, S and Si;
  • n represents the valence state of (YO 4 ) n- .
  • the polyanionic compound may also be a compound having sodium ions, transition metal ions, tetrahedral (YO 4 ) n- anion units and halogen anions.
  • the transition metal may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce;
  • Y may be at least one of P, S and Si, and n represents the valence state of (YO 4 ) n- ;
  • the halogen may be at least one of F, Cl and Br.
  • the polyanionic compound may also be a compound having sodium ions, tetrahedral (YO 4 ) n- anion units, polyhedral units (ZO y ) m+ and optional halogen anions.
  • Y may be at least one of P, S and Si, and n represents the valence state of (YO 4 ) n- ;
  • Z represents a transition metal, and may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce, and m represents the valence state of (ZO y ) m+ ;
  • the halogen may be at least one of F, Cl and Br.
  • the polyanionic compound is, for example, at least one of NaFePO4, Na3V2(PO4)3 (sodium vanadium phosphate, abbreviated as NVP), Na4Fe3(PO4)2 ( P2O7 ) , NaM'PO4F ( M ' is one or more of V, Fe, Mn and Ni) and Na3 ( VOy ) 2 ( PO4 ) 2F3-2y ( 0 ⁇ y ⁇ 1 ).
  • the Prussian blue compound may be a compound having sodium ions, transition metal ions and cyanide ions (CN - ).
  • the transition metal may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce.
  • the Prussian blue compound is, for example, Na a Me b Me' c (CN) 6 , wherein Me and Me' are each independently at least one of Ni, Cu, Fe, Mn, Co and Zn, 0 ⁇ a ⁇ 2, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1.
  • the positive electrode active material layer may further include a conductive agent to improve the conductivity of the positive electrode.
  • a conductive agent to improve the conductivity of the positive electrode.
  • the present application does not specifically limit the type of the conductive agent, and it may be selected according to actual needs.
  • the conductive agent may be one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphite, graphene, and carbon nanofibers.
  • the positive electrode active material layer may further include a binder to firmly bond the positive electrode active material and the optional conductive agent to the positive electrode current collector.
  • a binder to firmly bond the positive electrode active material and the optional conductive agent to the positive electrode current collector.
  • the present application does not specifically limit the type of binder, and it can be selected according to actual needs.
  • the binder may be at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer (EVA), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), sodium alginate (SA), polymethacrylic acid (PMA) and carboxymethyl chitosan (CMCS).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • EVA ethylene-vinyl acetate copolymer
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • SA sodium alginate
  • PMA polymethacrylic acid
  • CMCS carboxymethyl chitosan
  • the positive electrode current collector can be a conductive carbon sheet, a metal foil, a carbon-coated metal foil, a porous metal plate or a composite current collector, wherein the conductive carbon material of the conductive carbon sheet can be one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphite, graphene and carbon nanofibers, and the metal material of the metal foil, the carbon-coated metal foil and the porous metal plate can be independently selected from at least one of copper, aluminum, nickel and stainless steel.
  • the composite current collector can be a composite current collector formed by a metal foil and a polymer base film.
  • the positive electrode current collector is, for example, one or more of copper foil, aluminum foil, nickel foil, stainless steel foil, stainless steel mesh and carbon-coated aluminum foil, preferably aluminum foil.
  • the positive electrode sheet can be prepared according to conventional methods in the art. Usually, the positive electrode active material and optional conductive agent and binder are dispersed in a solvent (such as N-methylpyrrolidone, referred to as NMP) to form a uniform positive electrode slurry, which is then coated on the positive electrode current collector, and then dried and cold pressed to obtain a positive electrode sheet.
  • a solvent such as N-methylpyrrolidone, referred to as NMP
  • the present application has no particular limitation on the type of the diaphragm, and any known porous structure diaphragm with good chemical stability and mechanical stability can be selected.
  • the material of the diaphragm can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the diaphragm can be a single-layer film or a multi-layer composite film without particular limitation.
  • the materials of each layer can be the same or different without particular limitation.
  • the thickness of the separator is 6 ⁇ m to 40 ⁇ m, and optionally 12 ⁇ m to 20 ⁇ m.
  • the sodium ion battery can be prepared according to conventional methods in the art. Specifically, the positive electrode sheet, the separator, and the negative electrode current collector are stacked in order, and the separator is placed between the positive electrode sheet and the negative electrode current collector to play an isolating role, to obtain a battery core, or the battery core can be obtained by winding; the battery core is placed in an outer package, and an electrolyte is injected and sealed to obtain a sodium ion battery.
  • An example of the present application also provides a method for manufacturing the sodium ion battery as described above, comprising the following steps:
  • the coating material includes a carbon material, and the carbon material includes carbon nanotubes;
  • the negative electrode current collector having the coating formed thereon is compounded with a separator and a positive electrode sheet.
  • the sodium ion battery is subjected to at least one charge and discharge process to form a sodium metal layer on at least one of the inner wall and outer wall of the carbon nanotube and the surface of the negative electrode current collector.
  • the charging and discharging process may include the charging and discharging process during formation treatment, and may also include the charging and discharging process during use.
  • the outer packaging of the sodium ion battery can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery can also be a soft package, such as a bag-type soft package.
  • the material of the soft package can be plastic, and as the plastic, polypropylene, polybutylene terephthalate, and polybutylene succinate can be listed.
  • FIG1 is a sodium ion battery 5 of a square structure as an example.
  • the outer package may include a shell 51 and a cover plate 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the electrolyte is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the sodium ion battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • sodium ion batteries can be assembled into a battery module.
  • the number of sodium ion batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG3 is a battery module 4 as an example.
  • a plurality of sodium ion batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, they may also be arranged in any other manner. Further, the plurality of sodium ion batteries 5 may be fixed by fasteners.
  • the battery module 4 may further include a housing having a housing space, and the plurality of sodium ion batteries 5 are accommodated in the housing space.
  • the battery modules described above may also be assembled into a battery pack.
  • the battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
  • FIG. 4 and FIG. 5 are battery packs 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the sodium ion battery, battery module, or battery pack provided in the present application.
  • the sodium ion battery, battery module, or battery pack can be used as a power source for the electrical device, and can also be used as an energy storage unit for the electrical device.
  • the electrical device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • a sodium ion battery, a battery module or a battery pack can be selected according to its usage requirements.
  • FIG6 is an example of an electric device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or a battery module may be used.
  • Another example device may be a mobile phone, a tablet computer, a laptop computer, etc. Such a device is usually required to be thin and light, and a sodium ion battery may be used as a power source.
  • 10wt% polyvinylidene fluoride binder was fully dissolved in N-methylpyrrolidone, and 10wt% carbon black conductive agent and 80wt% positive electrode active material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 were added to prepare a uniformly dispersed slurry.
  • the slurry was evenly coated on the surface of aluminum foil and then transferred to a vacuum drying oven for complete drying. The obtained electrode sheet was rolled and then punched to obtain a positive electrode sheet.
  • slurry According to the total mass percentage of the slurry, 4wt% carbon nanotube material and 1.6wt% polymer binder sodium carboxymethyl cellulose are added to water and stirred into a uniform slurry. The slurry is coated on the surface of copper foil and then transferred to a vacuum drying oven for complete drying to form a carbon nanotube coating, which is then punched to obtain a negative electrode sheet.
  • sodium hexafluorophosphate sodium salt was dissolved in an organic solvent of ethylene glycol dimethyl ether and stirred evenly to obtain an electrolyte having a sodium hexafluorophosphate sodium salt concentration of 1.5 mol/L, ie, the electrolyte of Example 1.
  • Polypropylene film was used as the separator.
  • the positive electrode sheet, separator and negative electrode sheet are stacked in order, so that the separator is between the positive electrode sheet and the negative electrode current collector to play a role of isolation, and the electrolyte is added to assemble into a laminated battery.
  • Examples 2 to 37 and Comparative Example 2 are similar to those of Example 1. Those skilled in the art can obtain Examples 2 to 37 and Comparative Example 2 with the parameters in Table 1 by changing the types of metal nanoparticles, the specific surface area of the carbon nanotubes, the thickness of the carbon nanotube coating, and the electrolyte solvent.
  • the preparation method of the negative electrode current collector containing metal nanoparticles in Examples 2 to 37 is: according to the total mass percentage of the slurry, 4wt% (M2) carbon nanotube material and 1.6wt% polymer binder sodium carboxymethyl cellulose, and 0.2wt% (M1) metal nanoparticles are added to water and stirred into a uniform slurry, the slurry is coated on the surface of the copper foil, and then transferred to a vacuum drying oven for complete drying to form a carbon nanotube coating, and then punched to obtain a negative electrode sheet.
  • M2 4wt%
  • M1 metal nanoparticles
  • Comparative Example 1 is to use only copper foil without preparing carbon nanotube coating thereon.
  • the carbon nanotube is replaced by graphite.
  • Example 1 the prepared sodium ion battery was charged to 100 ⁇ A at a constant current of 0.1 C at 25° C., and the most negative potential obtained in the process was recorded as the overpotential.
  • the smaller the overpotential the smaller the nucleation barrier of Na metal deposition, and the easier it is for Na metal to deposit.
  • Example 1 the prepared sodium ion secondary battery is charged to 3.7V at a constant current of 1/3C at 25°C, and then charged at a constant voltage of 3.7V until the current drops to 0.05C to obtain the first charging capacity (Cc1); then discharged to 2.5V at a constant current of 1/3C to obtain the first discharge capacity (Cd1), and the coulombic efficiency of the sodium ion battery is calculated according to the following formula.
  • Example 1 the sodium ion battery is charged to 3.7V at a constant current of 1C at 25°C, then charged at a constant voltage of 3.7V until the current drops to 0.05C, and then discharged to 2.5V at a constant current of 1C to obtain the first cycle discharge capacity (Cd1); the charging and discharging are repeated to the nth cycle, and the discharge capacity of the sodium ion battery after n cycles is obtained, which is recorded as Cdn, and the sodium ion battery capacity retention rate is calculated according to the following formula:
  • Capacity retention rate discharge capacity after n cycles (Cdn) / first cycle discharge capacity (Cd1).
  • the sodium ion battery after 100 cycles was disassembled in an argon atmosphere glove box (H 2 O ⁇ 0.1ppm, O 2 ⁇ 0.1ppm), and the surface morphology of the negative electrode was visually observed to determine whether sodium dendrites were generated. If there were no white spots on the negative electrode, it was determined that there were no sodium dendrites; if there were sporadic white spots on the negative electrode, it was determined that the sodium dendrites were slight; if there were dense white spots on the negative electrode, it was determined that the sodium dendrites were severe.

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Abstract

本申请涉及一种钠离子电池及包含其的用电装置。其包含正极片、隔膜以及负极集流体，所述隔膜设置于所述正极片和所述负极集流体之间，所述负极集流体的表面设置有涂层，所述涂层包括碳材料，所述碳材料包括碳纳米管。该钠离子电池能够有效提升钠枝晶的抑制作用，提升循环性能。同时，无需额外设置负极活性材料层，降低钠离子电池的成本，提升钠离子电池的能量密度。

Description

钠离子电池及包含其的用电装置 技术领域
本申请涉及钠电池技术领域，尤其涉及一种钠离子电池及包含其的用电装置。
背景技术
钠离子电池是一种二次电池，主要依靠钠离子在正极和负极之间移动来工作：充电时，Na +从正极脱出，穿过隔膜嵌入负极，使正极处于高电势的贫钠态，负极处于低电势的富钠态；放电过程则与之相反，Na +从负极脱出，穿过隔膜重新嵌入到正极材料中，使正极恢复到富钠态。
与锂离子电池相比较，钠离子电池具有更好的安全性能、来源广泛、成本低等优势，但是其较大的离子质量和离子半径造成钠离子电池的能量密度低于锂离子电池，一定程度阻碍了其发展。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种钠离子电池及包含其的用电装置。
本申请的第一方面提供了一种钠离子电池，其包含正极片、隔膜以及负极集流体，所述隔膜设置于所述正极片和负极集流体之间，所述负极集流体的表面设置有涂层，所述涂层包括碳材料，所述碳材料包括碳纳米管。
本申请的第二方面提供了一种用电装置，包括第一方面所述的钠离子电池中的至少一种。
附图说明
图1是本申请一实施方式的钠离子电池的示意图；
图2是图1所示的本申请一实施方式的钠离子电池的分解图；
图3是本申请一实施方式的电池模块的示意图；
图4是本申请一实施方式的电池包的示意图；
图5是图4所示的本申请一实施方式的电池包的分解图；
图6是本申请一实施方式的钠离子电池用作电源的用电装置的示意图；
附图标记说明：
1、电池包；2、上箱体；3、下箱体；4、电池模块；5、钠离子电池；51、壳体；52、电极组件；53、盖板；6、用电装置；
图7是充放电后的实施例1的钠离子二次电池的负极拆解后的照片。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的钠离子电池及包含其的用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选 是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
目前，为了进步降低电池的成本、提升电池的能量密度，在锂离子电池领域开发出了一类无负极电池，即其负极中不包含传统的负极活性材料层。但是，在钠离子电池领域关于无负极电池的研究较少。若直接省略钠离子电池负极中的负极活性材料层，充放电过程中，沉积于负极集流体上的钠金属将会产生较为严重的钠枝晶，电池的循环性能差。
有方法提供一种钠离子电池的负极极片，其省略了负极活性材料层，主要方案在于通过在负极集流体的表面设置一层碳材料层，并使充放电过程中沉积的钠金属沉积在碳材料层上(表面)，虽然碳材料的存在能够一定程度抑制钠枝晶的产生，但是效果有限，在长时间的充放电循环中，依然容易出现钠枝晶。并且，该方法在具体实施时，均需要在碳材料层的表面预先沉积一层钠金属层(预先沉积的钠金属层厚度通常为1μm左右)形成类似于钠金属电池负极的富钠表面，同时需要采用表面含有氧基团的碳材料，以保证钠金属在碳材料层表面沉积的均匀性，减少钠枝晶的出现。如此无疑又增加了钠离子电池的成本、降低了电池的能量密度，且由于钠金属十分活泼，预先沉积纳金属层在实际生产中存在较大安全隐患，对厂房湿度及环境要求苛刻，增加工艺成本。
基于此，本申请一示例提供一种钠离子电池，其包含正极片、隔膜以及负极集流体，所述隔膜设置于所述正极片和负极集流体之间，所述负极集流体的表面设置有涂 层，所述涂层包括碳材料，所述碳材料包括碳纳米管。
上述钠离子电池，在省略了负极活性材料层的基础上，选择碳纳米管作为碳材料，利用碳纳米管的管道结构，使钠金属层沉积于其管内壁、管外壁以及负极集流体的表面中的至少一处。如此，碳纳米管一方面通过降低钠金属沉积的过电势(即成核过电位，降低钠金属沉积的成核能垒)抑制钠枝晶的产生，更重要的是可以通过其管道结构和限位作用抑制钠枝晶的生长，如此有效提升对钠枝晶产生的抑制作用，同时还可以稳固碳纳米管表面的SEI膜，提升钠离子电池的循环性能。同时，无需额外设置钠金属层，真正意义上降低钠离子电池的成本，提升钠离子电池的能量密度。
在其中一些示例中，所述碳材料为碳纳米管。
在其中一些示例中，所述碳纳米管的管内壁、管外壁以及所述负极集流体的表面中的至少一处形成有钠金属层。
在其中一些示例中，所述钠金属层是钠离子电池在充放电过程中形成的。不作限制地，所述充放电过程可以包括化成处理时的充放电过程，也可以包括使用时的充放电过程。
在其中一些示例中，所述钠金属层的厚度为P，0<P≤400nm；可选地，所述钠金属层的厚度为150≤P≤300nm。区别于现有钠离子电池负极中额外设置钠金属层，所述钠金属层形成于第一次充放电后，厚度较薄。具体地，所述钠金属层的厚度包括但不限于：150nm、160nm、165nm、171nm、175nm、180nm、185nm、188nm、192nm、200nm、202nm、205nm、208nm、210nm、211nm、215nm、220nm、222nm、227nm、232nm、235nm、240nm、260nm、280nm、300nm，或者位于上述任意两个数值的范围内。
在其中一些示例中，所述碳纳米管的比表面积为≥500m 2/g。进一步地，所述碳纳米管的比表面积为500～1500m 2/g。更进一步地，所述碳纳米管的比表面积为750～1000m 2/g。通过合理控制所述碳纳米管的比表面积，可以为钠金属层的沉积提供适宜的空隙，使钠金属层在其管内壁、管外壁均匀分布。具体地，所述碳纳米管的比表面积包括但不限于：500m 2/g、520m 2/g、540m 2/g、560m 2/g、600m 2/g、640m 2/g、660m 2/g、680m 2/g、730m 2/g、740m 2/g、750m 2/g、755m 2/g、760m 2/g、770m 2/g、800m 2/g、820m 2/g、850m 2/g、890m 2/g、920m 2/g、950m 2/g、980m 2/g、990m 2/g、995m 2/g、1000m 2/g、1200m 2/g、1250m 2/g、1300m 2/g、1400m 2/g、1460m 2/g、1500m 2/g， 或者位于上述任意两个数值的范围内。
在其中一些示例中，所述碳纳米管的管径为0.5nm～50nm。进一步地，所述碳纳米管的管径为10nm～40nm如此有利于钠金属层在其管内壁的沉积。具体地，所述碳纳米管的管径包括但不限于：0.5nm、3nm、5nm、8nm、10nm、12nm、15nm、18nm、20nm、22nm、25nm、30nm、35nm、38nm、40nm、42nm、45nm、50nm，或者位于上述任意两个数值的范围内。
另外，在其中一些示例中，所述碳纳米管上附着有若干个金属纳米颗粒。如此能够为钠金属层的沉积提供大量的成核位点。可以理解地，“碳纳米管上”包括所述碳纳米管的管内壁和管外壁。进一步地，所述碳纳米管的管内壁上附着有若干个金属纳米颗粒。如此能够有效诱导钠金属层在碳纳米管管内壁优先沉积，避免钠金属枝晶在碳材料层表面的生长，进一步抑制钠枝晶的形成。可以理解地，若干个是指两个或以上，包括但不限于：2个、3个、4个、10个、60个、100个、500个或以上。
在其中一些示例中，所述金属纳米颗粒中的金属为能够与钠形成合金的金属。所述“能够与钠形成合金的金属”是指在充电过程中该金属能够与钠发生电化学合金化反应，进而有效抑制钠枝晶生长。
进一步地所述金属纳米颗粒包括Au纳米颗粒、Ag纳米颗粒、Bi纳米颗粒、Sn纳米颗粒、Co纳米颗粒、Ni纳米颗粒、Mg纳米颗粒和Zn纳米颗粒中的一种或多种。
在其中一些示例中，所述金属纳米颗粒的粒径较所述碳纳米管的管径小至少0.2nm。如此留出适当的空间，避免影响钠金属层的沉积。进一步地，所述金属纳米颗粒的粒径较所述碳纳米管的管径小0.2nm～10nm。更进一步地，所述金属纳米颗粒的粒径较所述碳纳米管的管径小1nm～5nm。具体地，所述金属纳米颗粒的粒径较所述碳纳米管的管径小的数值包括但不限于：0.2nm、0.5nm、0.8nm、1nm、2nm、3nm、4nm、4.5nm、4.8nm、5nm、5.5nm、6nm、7nm、8nm、9nm、9.5nm、10nm，或者位于上述任意两个数值的范围内。
在其中一些示例中，所述金属纳米颗粒的粒径为0.3nm～40nm。进一步地，所述金属纳米颗粒的粒径为8nm～35nm。具体地，所述金属纳米颗粒的粒径包括但不限于：0.3nm、1nm、3nm、5nm、7nm、8nm、9nm、10nm、12nm、14nm、16nm、18nm、20nm、25nm、30nm、33nm、34nm、35nm、36nm、38nm、40nm，或者位于上述任意两个数值的范围内。
在其中一些示例中，在所述涂层中，所述金属纳米颗粒的质量为M1，所述碳纳米管的质量为M2，M1:M2＝0.01～0.1。如此有利于钠金属层的均匀沉积。进一步地，M1:M2＝0.03～0.07。具体地，M1:M2的值包括但不限于：0.01:1、0.02:1、0.03:1、0.04:1、0.05:1、0.06:1、0.07:1、0.08:1、0.09:1、0.1:1，或者位于上述任意两个数值的范围内。其中M1:M2的测试方法可为：将负极极片冲小圆片，然后进行微量元素分析-电感耦合等离子体发射光谱法测试和CHNS元素分析测试。
在其中一些示例中，所述涂层的厚度为0.5μm～15μm。通过合理控制涂层的厚度，一方面为钠金属沉积提供足够的成核点位，减少钠枝晶的生长，另一方面提升电池的能量密度。进一步地，所述涂层的厚度为0.5μm～5μm。具体地，所述涂层的厚度包括但不限于：0.5μm、0.7μm、1μm、1.5μm、2μm、3μm、4μm、4.5μm、5μm、5.5μm、6μm、7μm、8μm、9μm、10μm、12μm、15μm，或者位于上述任意两个数值的范围内。
在其中一些示例中，所述涂层的材料还包括粘结剂。可选地，所述粘结剂包括聚合物粘结剂。不作限制地，所述粘结剂可包括丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。所述粘结剂在所述涂层中的重量比为0-30重量％，基于所述涂层的总重量计。进一步地，所述粘结剂在所述涂层中的重量比为0.5-10重量％，基于所述涂层的总重量计。
在其中一些示例中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料形成在高分子材料基材上而形成。其中，金属材料包括但不限于铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等，高分子材料基材包括但不限于聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等基材。
在其中一些示例中，所述负极集流体的表面不设有负极活性材料，负极活性材料可举例如硬碳、软碳、钠金属(此处指预先在负极集流体表面沉积的钠金属(厚度通常为1μm左右)，区别于本申请中在充放电过程中形成的钠金属)、氧化锡、钴钒硫化物等。
另外可以理解地，负极集流体具有在其自身厚度方向相对的两个表面，所述涂层设置在负极集流体相对的两个表面中的任意一者或两者上。
在其中一些示例中，可以通过以下方式在负极集流体的表面制备所述涂层：将上述用于制备涂层的组分，例如碳纳米管、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成浆料；将所得到的浆料涂覆在负极集流体上，进行干燥工序。
在其中一些示例中，所述钠离子电池还包括电解液。电解液在正极片和负极集流体之间起到传导离子的作用。
在其中一些示例中，所述电解液包括电解质钠盐和溶剂。
在其中一些示例中，所述电解液中的溶剂包括醚类溶剂。醚类溶剂分子可以在负极集流体的表面构建稳定的电极/电解液界面，形成稳定的固态电解质界面(SEI)，减小电化学极化。进一步地，所述电解液的溶剂包括乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、1,3-二氧环戊烷、四氢呋喃、甲基四氢呋喃、二苯醚和冠醚中的一种或多种。
在其中一些示例中，所述电解液中的电解质钠盐包括六氟磷酸钠、二氟草酸硼酸钠、四氟硼酸钠、双草酸硼酸钠、高氯酸钠、六氟砷酸钠、双(氟磺酰)亚胺钠、三氟甲基磺酸钠和双(三氟甲基磺酰)亚胺钠中的一种或多种。
在其中一些示例中，所述电解液中的电解质钠盐的摩尔浓度为0.5mol/L～8mol/L。进一步地，所述电解液中的电解质钠盐的摩尔浓度为1mol/L～4mol/L。
在其中一些示例中，所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
在其中一些示例中，所述正极包括钠过渡金属氧化物正极、聚阴离子型化合物正极和普鲁士蓝类化合物正极中的一种。
具体地，正极片包括正极集流体及形成于所述正极集流体的至少部分表面上的正极活性物质层，所述正极活性物质层包括正极活性物质，所述正极活性物质可以包括钠过渡金属氧化物、聚阴离子型化合物和普鲁士蓝类化合物中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作钠离子电池正极活性材料的传统公知的材料。
作为本申请可选的技术方案，钠过渡金属氧化物中，过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种。钠过渡金属氧化物例如为Na xMO 2，其中M为Ti、V、Mn、Co、Ni、Fe、Cr及Cu中的一种或几种，0＜x≤1。
作为本申请可选的技术方案，聚阴离子型化合物可以是具有钠离子、过渡金属离子及四面体型(YO 4) n-阴离子单元的一类化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种；Y可以是P、S及Si中的至少一种；n表示(YO 4) n-的价态。
聚阴离子型化合物还可以是具有钠离子、过渡金属离子、四面体型(YO 4) n-阴离子单元及卤素阴离子的一类化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种；Y可以是P、S及Si中的至少一种，n表示(YO 4) n-的价态；卤素可以是F、Cl及Br中的至少一种。
聚阴离子型化合物还可以是具有钠离子、四面体型(YO 4) n-阴离子单元、多面体单元(ZO y) m+及可选的卤素阴离子的一类化合物。Y可以是P、S及Si中的至少一种，n表示(YO 4) n-的价态；Z表示过渡金属，可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种，m表示(ZO y) m+的价态；卤素可以是F、Cl及Br中的至少一种。
聚阴离子型化合物例如是NaFePO 4、Na 3V 2(PO4) 3(磷酸钒钠，简称NVP)、Na 4Fe 3(PO 4) 2(P 2O 7)、NaM’PO4F(M’为V、Fe、Mn及Ni中的一种或几种)及Na 3(VO y) 2(PO 4) 2F 3-2y(0≤y≤1)中的至少一种。
普鲁士蓝类化合物可以是具有钠离子、过渡金属离子及氰根离子(CN -)的一类化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种。普鲁士蓝类化合物例如为Na aMe bMe’ c(CN) 6，其中Me及Me’各自独立地为Ni、Cu、Fe、Mn、Co及Zn中的至少一种，0＜a≤2，0＜b＜1，0＜c＜1。
作为本申请可选的技术方案，正极活性物质层还可以包括导电剂，以改善正极的导电性能。本申请对导电剂的种类不做具体限制，可以根据实际需求进行选择。作为示例，导电剂可以为超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨、石墨烯及碳纳米纤维中的一种或几种。
作为本申请可选的技术方案，正极活性物质层还可以包括粘结剂，以将正极活性物质和可选的导电剂牢固地粘结在正极集流体上。本申请对粘结剂的种类不做具体限制，可以根据实际需求进行选择。作为示例，粘结剂可以为聚偏氟乙烯(PVDF)、聚四 氟乙烯(PTFE)、聚丙烯酸(PAA)、聚乙烯醇(PVA)、乙烯-醋酸乙烯酯共聚物(EVA)、丁苯橡胶(SBR)、羧甲基纤维素(CMC)、海藻酸钠(SA)、聚甲基丙烯酸(PMA)及羧甲基壳聚糖(CMCS)中的至少一种。
作为本申请可选的技术方案，正极集流体可以采用导电碳片、金属箔材、涂炭金属箔材、多孔金属板或复合集流体，其中导电碳片的导电碳材质可以为超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨、石墨烯及碳纳米纤维中的一种或几种，金属箔材、涂炭金属箔材和多孔金属板的金属材质各自独立地可以选自铜、铝、镍及不锈钢中的至少一种。复合集流体可以为金属箔材与高分子基膜复合形成的复合集流体。
作为本申请可选的技术方案，正极集流体例如为铜箔、铝箔、镍箔、不锈钢箔、不锈钢网及涂炭铝箔中的一种或几种，优选采用铝箔。
可以按照本领域常规方法制备上述正极片。通常将正极活性物质及可选的导电剂和粘结剂分散于溶剂(例如N-甲基吡咯烷酮，简称为NMP)中，形成均匀的正极浆料，将正极浆料涂覆在正极集流体上，经烘干、冷压后，得到正极片。
另外，本申请对隔膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔膜。
在其中一些示例中，隔膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在其中一些示例中，所述隔膜的厚度为6μm～40μm，可选为12μm～20μm。
可以按照本领域常规方法制备上述钠离子电池。具体地，将上述正极片、隔膜、负极集流体按顺序堆叠好，使隔膜处于正极片与负极集流体之间起到隔离的作用，得到电芯，也可以是经卷绕后得到电芯；将电芯置于外包装中，注入电解液并封口，得到钠离子电池。
本申请一示例还提供如上所述钠离子电池的制作方法，包括如下步骤：
将涂层的材料与溶剂混合，制备浆料；所述涂层的材料包括碳材料，所述碳材料包括碳纳米管；
将所述浆料涂覆于负极集流体的表面，干燥形成涂层；
将形成有所述涂层的负极集流体与隔膜、正极片复合。
在一些实施方式中，将所述钠离子电池进行至少一次充放电过程，于所述碳纳米管的管内壁、管外壁以及所述负极集流体的表面中的至少一处形成钠金属层。
不作限制地，所述充放电过程可以包括化成处理时的充放电过程，也可以包括使用时的充放电过程。
在一些实施方式中，钠离子电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对钠离子电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的钠离子电池5。
在一些实施方式中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。钠离子电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，钠离子电池可以组装成电池模块，电池模块所含钠离子电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块4。参照图3，在电池模块4中，多个钠离子电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个钠离子电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个钠离子电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图4和图5是作为一个示例的电池包1。参照图4和图5，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以 按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的钠离子电池、电池模块、或电池包中的至少一种。所述钠离子电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择钠离子电池、电池模块或电池包。
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对钠离子电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用钠离子电池作为电源。
实施例
为了使本申请所解决的技术问题、技术方案及有益效果更加清楚，以下将结合实施例和附图对本申请进行进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本申请及其应用的任何限制。基于本申请中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例都属于本申请保护的范围。
实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
一、制备实施例
制备实施例1
【正极片的制备】
将10wt％聚偏氟乙烯粘结剂充分溶解于N-甲基吡咯烷酮中，加入10wt％炭黑导电剂与80wt％正极活性材料Na 4Fe 3(PO 4) 2P 2O 7制成分散均匀的浆料。将浆料均匀涂敷 在铝箔表面，然后转移到真空干燥箱中完全干燥。将得到的极片进行辊压，然后进行冲切，得到正极片。
【负极片的制备】
按照浆料的总质量百分比计，将4wt％碳纳米管材料和1.6wt％聚合物粘结剂羧甲基纤维素钠加到水中搅拌成均匀的浆料，将浆料涂覆在铜箔表面上，然后转移到真空干燥箱中完全干燥，形成碳纳米管涂层，然后进行冲切，得到负极片。
【电解液的制备】
在氩气气氛手套箱中(H 2O<0.1ppm，O 2<0.1ppm)，将钠盐六氟磷酸钠溶解于有机溶剂乙二醇二甲醚中，搅拌均匀，得到六氟磷酸钠钠盐浓度1.5mol/L的电解液，即实施例1的电解液。
【隔膜】
以聚丙烯膜作为隔膜。
【钠离子电池组装】
将上述正极片、隔膜、负极片按顺序叠好，使隔膜处于正极片、负极集流体之间，起到隔离的作用，加入上述电解液组装成叠片电池。
实施例2～37、对比例2与实施例1的钠离子电池制备方法相似，本领域技术人员能够通过改变各金属纳米颗粒的种类、碳纳米管的比表面积、碳纳米管涂层的厚度和电解液溶剂等，能够得到如表1参数的实施例2～37、对比例2。
其中，实施例2～37包含金属纳米颗粒的负极集流体的制备方法为：按照浆料的总质量百分比计，将4wt％(M2)碳纳米管材料和1.6wt％聚合物粘结剂羧甲基纤维素钠、0.2wt％(M1)金属纳米颗粒加到水中搅拌成均匀的浆料，将浆料涂覆在铜箔表面上，然后转移到真空干燥箱中完全干燥，形成碳纳米管涂层，然后进行冲切，得到负极极片。
对比例1即仅采用铜箔，未在其上制备碳纳米管涂层。对比例2中将碳纳米管替换为石墨。
二、电池性能测试
1、过电势
以实施例1为例，将制得的钠离子电池在25℃下以0.1C的恒定电流充电至100μA， 过程中得到的最负电势记录为过电势，过电势越小，说明Na金属沉积的成核能垒越小，Na金属越容易沉积。
对比例以及其他实施例的测试过程同上。
2、库伦效率
以实施例1为例，将制得的钠离子二次电池在25℃下以1/3C的恒定电流充电至3.7V，之后以3.7V恒压充电至电流降到0.05C，得到首次充电容量(Cc1)；再以1/3C的恒定电流放电至2.5V，得到首次放电容量(Cd1)，并按照下式计算钠离子电池库伦效率。
钠离子电池库伦效率＝首次放电容量(Cd1)/首次充电容量(Cc1)
对比例以及其他实施例的测试过程同上。
另外，将进行前述充放电后的实施例1的钠离子二次电池的负极进行拆解并拍照，如图7所示，(a)图是从负极上剥离下来的钠金属层，(b)图是对应的负极，如此说明碳纳米管的管内壁、管外壁以及负极集流体的表面均形成有钠金属层。
3、容量保持率
以实施例1为例，将钠离子电池在25℃下以1C的恒定电流充电至3.7V，之后以3.7V恒压充电至电流降到0.05C，再以1C的恒定电流放电至2.5V，得到首圈放电容量(Cd1)；如此反复充放电至第n圈，得钠离子电池循环n圈后的放电容量，记为Cdn，并按照下式计算钠离子电池容量保持率：
容量保持率＝循环n圈后的放电容量(Cdn)/首圈放电容量(Cd1)。
对比例以及其他实施例的测试过程同上。
4、钠枝晶
将上述循环100圈后的钠离子电池在氩气气氛手套箱中(H 2O<0.1ppm，O 2<0.1ppm)进行拆解，目视观察负极极片表面形貌，确定是否有钠枝晶生成。负极极片无白点判定为钠枝晶情况无、负极极片有零星白点判定为钠枝晶情况轻微、负极极片有密密麻麻白点判定为钠枝晶情况严重。
测试结果详见表2。
表1
Figure PCTCN2022123008-appb-000001
Figure PCTCN2022123008-appb-000002
Figure PCTCN2022123008-appb-000003
Figure PCTCN2022123008-appb-000004
表2
Figure PCTCN2022123008-appb-000005
Figure PCTCN2022123008-appb-000006
由实施例1～36与对比例1～2之间的比较可知，实施例1～36的电池在无负极活性材料情况下，通过设置碳纳米管涂层能够避免钠枝晶的形成，同时具有优异的库伦效 率和循环性能。
由实施例1～9之间的比较可知，在碳纳米管的基础上引入金属纳米颗粒，能够有效降低过电势，进一步避免钠枝晶的形成，且具有更好的库伦效率和循环性能。
由实施例2、10～17之间的比较可知，在碳纳米管的比表面积≥500m 2/g的情况下，均能够避免钠枝晶的形成，当比表面积在500～1500m 2/g范围内时，库伦效率和循环性能较大于1500m 2/g时好，进一步地，当比表面积在750～950m 2/g范围内时，库伦效率和循环性能更佳。
由实施例2、18～28之间的比较可知，在碳纳米管的管径在0.5nm～50nm的情况下，均能够避免钠枝晶的形成，当比表面积在10nm～40nm范围内时，库伦效率和循环性能更佳。同时，在金属纳米颗粒的粒径在0.3nm～40nm的情况下，均能够避免钠枝晶的形成，当粒径在8nm～35nm范围内时，库伦效率和循环性能更佳。
由实施例2、29～32之间的比较可知，在碳纳米管涂层的厚度在0.5μm～15μm的情况下，均能够避免钠枝晶的形成，当厚度在0.5μm～5μm范围内时，库伦效率和循环性能更佳。
由实施例2、33～36之间的比较可知，在M1:M2＝0.01～0.1的情况下，均能够避免钠枝晶的形成，并有效降低过电势，当M1:M2＝0.03～0.07范围内时，库伦效率和循环性能更佳。
由实施例2、37之间的比较可知，采用醚类溶剂能够进一步提升库伦效率和循环性能。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (15)

  1. 一种钠离子电池，其包含正极片、隔膜以及负极集流体，所述隔膜设置于所述正极片和所述负极集流体之间，所述负极集流体的表面设置有涂层，所述涂层包括碳材料，所述碳材料包括碳纳米管。
  2. 根据权利要求1所述的钠离子电池，其特征在于，所述碳纳米管具有如下所示特征中的至少一项：
    (1)比表面积为≥500m 2/g；可选地，所述碳纳米管的比表面积为500～1500m 2/g；进一步可选地，所述碳纳米管的比表面积为750～1000m 2/g；
    (2)管径为0.5nm～50nm；可选地，管径为10nm～40nm。
  3. 根据权利要求1～2任一项所述的钠离子电池，其特征在于，所述碳纳米管上附着有若干个金属纳米颗粒。
  4. 根据权利要求3所述的钠离子电池，其特征在于，所述金属纳米颗粒具有如下所示特征中的至少一项：
    (1)所述金属纳米颗粒中的金属为能够与钠形成合金的金属；可选地，所述金属纳米颗粒包括Au纳米颗粒、Ag纳米颗粒、Bi纳米颗粒、Sn纳米颗粒、Co纳米颗粒、Ni纳米颗粒、Mg纳米颗粒和Zn纳米颗粒中的一种或多种；
    (2)所述金属纳米颗粒的粒径较所述碳纳米管的管径小至少0.2nm；可选地，所述金属纳米颗粒的粒径较所述碳纳米管的管径小0.2nm～10nm；进一步可选地，所述金属纳米颗粒的粒径较所述碳纳米管的管径小1nm～5nm；
    (3)所述金属纳米颗粒的粒径为0.3nm～40nm；可选地，所述金属纳米颗粒的粒径为8nm～35nm。
  5. 根据权利要求3或4所述的钠离子电池，其特征在于，在所述涂层中，所述金属纳米颗粒的质量为M1，所述碳纳米管的质量为M2，M1:M2＝0.01～0.1；可选地，M1:M2＝0.03～0.07。
  6. 根据权利要求1～5任一项所述的钠离子电池，其特征在于，所述涂层的厚度为0.5μm～15μm；可选地，所述涂层的厚度为0.5μm～5μm。
  7. 根据权利要求1～6任一项所述的钠离子电池，其特征在于，所述涂层的材料还包括粘结剂；可选地，所述粘结剂包括聚合物粘结剂；进一步可选地，所述粘结剂包括丁苯橡胶、聚丙烯酸、聚丙烯酸钠、聚丙烯酰胺、聚乙烯醇、海藻酸钠、聚甲基丙烯 酸和羧甲基壳聚糖中的一种或多种。
  8. 根据权利要求1～7任一项所述的钠离子电池，其特征在于，所述钠离子电池还包括电解液。
  9. 根据权利要求8所述的钠离子电池，其特征在于，所述电解液具有如下所示特征中的至少一项：
    (1)所述电解液中的溶剂包括醚类溶剂；可选地，所述电解液的溶剂包括乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、1,3-二氧环戊烷、四氢呋喃、甲基四氢呋喃、二苯醚和冠醚中的一种或多种；
    (2)所述电解液中的电解质钠盐包括六氟磷酸钠、二氟草酸硼酸钠、四氟硼酸钠、双草酸硼酸钠、高氯酸钠、六氟砷酸钠、双(氟磺酰)亚胺钠、三氟甲基磺酸钠和双(三氟甲基磺酰)亚胺钠中的一种或多种；
    (3)所述电解液中的电解质钠盐的摩尔浓度为0.5mol/L～8mol/L；可选地，所述电解液中的电解质钠盐的摩尔浓度为1mol/L～4mol/L。
  10. 根据权利要求1～9任一项所述的钠离子电池，其特征在于，所述碳纳米管的管内壁、管外壁以及所述负极集流体的表面中的至少一处形成有钠金属层。
  11. 根据权利要求10所述的钠离子电池，其特征在于，所述钠金属层是钠离子电池在充放电过程中形成的；可选地，所述充放电过程包括化成处理时的充放电过程。
  12. 根据权利要求10或11所述的钠离子电池，其特征在于，所述钠金属层的厚度为P，0<P≤400nm。
  13. 一种钠离子电池的制作方法，包括如下步骤：
    将涂层的材料与溶剂混合，制备浆料；所述涂层的材料包括碳材料，所述碳材料包括碳纳米管；
    将所述浆料涂覆于负极集流体的表面，干燥形成涂层；
    将形成有所述涂层的负极集流体与隔膜、正极片复合。
  14. 根据权利要求13所述的钠离子电池的制作方法，其特征在于，将所述钠离子电池进行至少一次充放电过程，于所述碳纳米管的管内壁、管外壁以及所述负极集流体的表面中的至少一处形成钠金属层；可选地，所述充放电过程包括化成处理时的充放电过程。
  15. 一种用电装置，其特征在于，包括权利要求1～12任一项所述的钠离子电池和 权利要求13～14任一项所述的制备方法制备得到的钠离子电池中的至少一种。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110817845A (zh) * 2019-11-19 2020-02-21 厦门大学 一种无定型中空碳纳米管及其制备方法
CN210224170U (zh) * 2019-04-17 2020-03-31 湖南立方新能源科技有限责任公司 一种钠离子电池
CN113437254A (zh) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 钠离子电池的负极极片、电化学装置及电子设备
CN113451546A (zh) * 2021-06-26 2021-09-28 宁德时代新能源科技股份有限公司 钠金属电池、电化学装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN210224170U (zh) * 2019-04-17 2020-03-31 湖南立方新能源科技有限责任公司 一种钠离子电池
CN110817845A (zh) * 2019-11-19 2020-02-21 厦门大学 一种无定型中空碳纳米管及其制备方法
CN113437254A (zh) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 钠离子电池的负极极片、电化学装置及电子设备
CN113451546A (zh) * 2021-06-26 2021-09-28 宁德时代新能源科技股份有限公司 钠金属电池、电化学装置
CN114709368A (zh) * 2021-06-26 2022-07-05 宁德时代新能源科技股份有限公司 钠离子电池的负极极片、电化学装置及电子设备

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