WO2016147607A1 - Anode pour des batteries au sodium-ion et au potassium-ion - Google Patents

Anode pour des batteries au sodium-ion et au potassium-ion Download PDF

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WO2016147607A1
WO2016147607A1 PCT/JP2016/001264 JP2016001264W WO2016147607A1 WO 2016147607 A1 WO2016147607 A1 WO 2016147607A1 JP 2016001264 W JP2016001264 W JP 2016001264W WO 2016147607 A1 WO2016147607 A1 WO 2016147607A1
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carbon
anode
ion
metal
sodium
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PCT/JP2016/001264
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English (en)
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Sean Vail
Yuhao Lu
Long Wang
Motoaki Nishijima
Jong-Jan Lee
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Sharp Kabushiki Kaisha
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Priority claimed from US14/656,808 external-priority patent/US9742027B2/en
Application filed by Sharp Kabushiki Kaisha filed Critical Sharp Kabushiki Kaisha
Priority to KR1020177022627A priority Critical patent/KR20170104574A/ko
Priority to CN201680015368.2A priority patent/CN107431204A/zh
Publication of WO2016147607A1 publication Critical patent/WO2016147607A1/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
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention generally relates to electrochemical batteries and, more particularly, to a carbonaceous anode for use with sodium-ion and potassium-ion batteries.
  • Na sodium
  • NIBs sodium-ion batteries
  • its application in commercial batteries is constrained by safety issues such as flammability, dendrite growth during charge/discharge, and a low melting point.
  • carbonaceous anodes have emerged as attractive candidates for NIBs.
  • carbonaceous materials have three allotropes, which are diamond, graphite, and buckminsterfullerene [NPL 1].
  • graphite and its disordered forms are both popular and practical anode materials.
  • Graphite has a typical layered structure into/from which lithium ions (Li + ) can reversibly intercalate/deintercalate. Due to the larger sizes of sodium ions (Na + ) and potassium ions (K + ) relative to lithium ions (Li + ), graphite with a small interlayer distance is not appropriate for sodium/potassium intercalation and, consequently, demonstrates a low capacity [NPL 2].
  • amorphous carbonaceous materials can be prepared. Depending on the degree of crystallinity, these materials can be further classified as either “soft carbon” (SC, graphitizable carbon) or “hard carbon” (HC, non-graphitizable carbon). Indeed, amorphous carbonaceous materials have demonstrated good performance as anodes in NIBs. Carbon black, a type of soft carbon, was reported as the anode material in NIBs for which sodium was shown to be reversibly inserted into its amorphous and non-porous structures [NPL 3], while its reversible capacity was ⁇ 200 milliampere hours per gram (mAh/g) between 0 V - 2 V (vs. Na/Na + ). Since the carbon black has almost negligible porosity, it is believed that its large external surface area facilitates the reaction with sodium. However, the large surface area is also detrimental in terms of a large irreversible capacity for the carbon black anode.
  • SC graphitizable carbon
  • HC non
  • Sodiation of a hard carbon electrode includes two distinct processes. At the high voltage range (slope region), Na + inserts into the parallel graphene layers. At the low voltage range (plateau region), Na + intercalates into the pores of hard carbon. However, noteworthy is the fact that the low voltage plateau is very close to 0 V vs. Na/Na + so that sodium electroplating on hard carbon electrode can proceed when high currents for HC sodiation are applied.
  • CE is directly related to the surface area of the carbon additives. More specifically, high surface areas for conductive carbon additives were correlated with appreciable irreversible capacities due to solid electrolyte interface (SEI) layer formation on the electrode. In addition, the diverse functional groups on the surfaces of these carbon additives can also contribute to both the high irreversible capacities and low corresponding CE for hard carbon electrode.
  • SEI solid electrolyte interface
  • a hard carbon anode for use with sodium-ion and potassium-ion batteries, the anode comprising: a conductive substrate; a carbon-composite material overlying the conductive substrate comprising: a hard carbon material; a conductive carbon material having a low surface area; a binder material; and, wherein a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • a method for fabricating a hard carbon anode for use in sodium-ion and potassium-ion batteries comprising: mixing a conductive carbon material having a low surface area, a hard carbon material, and a binder material; forming a carbon-composite material, defined herein as a mixture of two or more different materials, in which at least one material is a carbon material; and, coating the carbon-composite material on a conductive substrate.
  • an anode for use with sodium-ion and potassium-ion batteries, the anode comprising: a conductive substrate; a carbon-composite material overlying the conductive substrate comprising: a hard carbon material; a metal-containing material; a binder material; and, wherein a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • a method for fabricating an anode for use in sodium-ion and potassium-ion batteries comprising: mixing a metal-containing material, a hard carbon material, and binder material; forming a carbon-composite material, defined herein as a mixture of two or more different materials, in which at least one material is a carbon material; and, coating the carbon-composite material on a conductive substrate.
  • an anode for use with sodium-ion and potassium-ion batteries, the anode comprising: a conductive substrate; a carbon-composite material overlying the conductive substrate comprising a hard carbon material with a pyrolyzed polymer coating; a binder material; and, wherein a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • a method for fabricating an anode for use in sodium-ion and potassium-ion batteries comprising: providing a hard carbon material having a pyrolyzed polymer coating; mixing the hard carbon material having the pyrolyzed polymer coating with a binder material; forming a carbon-composite material, defined herein as a mixture of two or more different materials, in which at least one material is a carbon material; and, coating the carbon-composite material on a conductive substrate.
  • a sodium-ion or potassium-ion battery comprising: a transition metal hexacyanometallate (TMHCM) cathode; an electrolyte; an anode comprising: a conductive substrate; a carbon-composite material overlying the conductive substrate comprising: a hard carbon material; a conductive carbon material having a low surface area; a binder material; wherein a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material; and, an ion-permeable membrane separating the anode from the cathode.
  • THCM transition metal hexacyanometallate
  • a sodium-ion or potassium-ion battery comprising: a transition metal hexacyanometallate (TMHCM) cathode; an electrolyte; an anode comprising: a conductive substrate; a carbon-composite material overlying the conductive substrate comprising: a hard carbon material; a metal-containing material; a binder material; wherein a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material; and, an ion-permeable membrane separating the anode from the cathode.
  • THCM transition metal hexacyanometallate
  • a sodium-ion or potassium-ion battery comprising: a transition metal hexacyanometallate (TMHCM) cathode; an electrolyte; an anode comprising: a conductive substrate; a carbon-composite material overlying the conductive substrate comprising a hard carbon material with a pyrolyzed polymer coating; a binder material; wherein a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material; and, an ion-permeable membrane separating the anode from the cathode.
  • THCM transition metal hexacyanometallate
  • the present invention can provide a hard carbon electrode could be prepared for use in sodium-ion or potassium-ion batteries that demonstrated a large capacity at high currents, as well as high CE at the first cycle.
  • Fig. 1 is a diagram depicting a hard carbon anode for use with sodium-ion and potassium-ion batteries.
  • Fig. 2 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (1.1 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte.
  • Fig. 1 is a diagram depicting a hard carbon anode for use with sodium-ion and potassium-ion batteries.
  • Fig. 2 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (1.1 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte.
  • Fig. 1 is a diagram depicting a hard carbon ano
  • FIG. 3 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (2.1 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte.
  • Fig. 4 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (3.3 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte.
  • Fig. 4 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (3.3 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte
  • Fig. 5 is a graph depicting 0.2C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (1.2 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaClO 4 in EC/DEC electrolyte.
  • Fig. 6 is a flowchart illustrating the first method for fabricating a hard carbon anode for use in sodium-ion and potassium-ion batteries.
  • Fig. 7 depicts a second anode for use with sodium-ion and potassium-ion batteries.
  • Fig. 8 is a flowchart illustrating the second method for fabricating an anode for use in sodium-ion and potassium-ion batteries.
  • FIG. 9A depicts steps in a process to form a pyrolyzed polymer coating on a hard carbon material.
  • Fig. 9B depicts steps in a process to form a pyrolyzed polymer coating on a hard carbon material.
  • Fig. 10 depicts a third anode for use with sodium-ion and potassium-ion batteries.
  • Fig. 11 is a flowchart illustrating the third method for fabricating an anode for use in sodium-ion and potassium-ion batteries.
  • Fig. 12 is a partial cross-sectional view of a sodium-ion or potassium-ion battery.
  • Fig. 13 is a partial cross-section view of a first variation of a sodium-ion or potassium-ion battery.
  • Fig. 14 is a partial cross-sectional view of a second variation of a sodium-ion or potassium-ion battery.
  • CE coulombic efficiency
  • SEI solid electrolyte interface
  • the diverse functional groups of these additives can also contribute to both the high irreversible capacities and low CE of hard carbon electrode. Disclosed herein are methods to prepare a hard carbon electrode for sodium-ion and potassium-ion batteries that demonstrates a large capacity at high applied currents as well as high CE with small corresponding irreversible capacity at the first cycle.
  • the focus of the hard carbon (HC) electrode preparation is to introduce low surface area and electronically conductive additives to reduce electrode resistance, which at the same time, do not significantly increase irreversible capacity.
  • the strategies and associated method(s) for electrode preparation are not limited to hard carbon (HC) electrode but can be extended to include a variety of alternative anodes made from carbonaceous materials including graphite and soft carbon materials.
  • the “active” materials for the anode electrode include carbonaceous materials with particular emphasis on hard carbon materials. Conductive carbon materials with small surface areas are introduced into the HC electrode to replace large surface area materials such as carbon black.
  • metal-containing materials can be employed as the electronically conductive additives in the electrode. The metal-containing materials can be deposited or coated on either the HC materials or electrode. Metal-containing materials can be mixed with HC materials in the electrode, or the metal-containing materials can be deposited on the surfaces of HC materials. The HC materials can be dispersed into polymers, or effectively coated by polymers, and subsequently pyrolyzed to afford a conductive coating on the HC materials.
  • a first method for fabricating a hard carbon anode mixes a conductive carbon material having a low surface area, a hard carbon material, and a binder material.
  • a carbon-composite material is thus formed, where a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • the carbon-composite material is coated on a conductive substrate.
  • the binder material may, for example, be a polymer or a mixture of polymers.
  • the conductive carbon material has a surface area of less than 100 meters square per gram (m 2 /g). The binder material functions to “hold together” electrode materials and imparts structural and mechanical integrity to the electrode.
  • a second method for fabricating an anode, for use in sodium-ion and potassium-ion batteries mixes a metal-containing material, a hard carbon material, and binder material.
  • a carbon-composite material is this formed and coated on a conductive substrate.
  • the metal-containing material may include a transition metal, and may take the form of an elemental metal, metal hydroxide, metal oxide, or combinations thereof.
  • the metal-containing material excludes materials capable of forming an alloy with sodium and potassium, such as antimony (Sb) or tin (Sn), wherein an alloy is defined as a substance composed of two or more metals, or of a metal or metals with a nonmetal.
  • a third method for fabricating an anode, for use in sodium-ion and potassium-ion batteries provides a hard carbon material having a pyrolyzed polymer coating that is mixed with a binder material to form a carbon-composite material, which is coated on a conductive substrate.
  • the hard carbon material with the pyrolyzed polymer coating may be formed by dispersing a hard carbon material within a polymer material and performing a thermal treatment. As a result, the polymer is pyrolyzed, forming a pyrolyzed polymer coating over the hard carbon material.
  • reversible capacity is consumed during the first cycle to form a solid electrolyte interface (SEI) layer on an anode, which suppresses further electrolyte decomposition.
  • SEI solid electrolyte interface
  • the corresponding irreversible capacity is clearly correlated with the surface of area(s) of the entire electrode since the SEI layer completely covers the interface between anode and electrolyte.
  • Ketjenblack for example, has a surface area of ⁇ 1000 square meters per gram (m 2 /g) that gives rise to a large capacity loss (low coulombic efficiency) at the first cycle.
  • carbon black is often used as an electronically conductive additive to reduce the electrode resistance and polarization.
  • an HC anode was constructed with an electronically conductive network for use in sodium-ion or potassium-ion batteries, while maintaining a considerable coulombic efficiency.
  • Fig. 1 is a diagram depicting a hard carbon anode for use with sodium-ion and potassium-ion batteries.
  • the anode 100 comprises a conductive substrate 102, which may be a metal such as copper (Cu), aluminum (Al), or carbon-coated aluminum (CC-Al), for example.
  • a carbon-composite material 104 overlies the conductive substrate 102.
  • the carbon-composite material 104 comprises a hard carbon material 106, a conductive carbon material 108 having a low surface area, and a binder material 110.
  • a carbon-composite material is defined as a mixture of two or more different materials, in which at least one material is a carbon material.
  • the conductive carbon material 108 has a surface area of less than 100 meters square per gram (m 2 /g).
  • the binder material 110 is typically a polymer or mixture of polymers.
  • Method 1 Low Surface Area Carbonaceous Materials as Electronically Conductive Additives
  • conductive carbon materials with low surface areas can be employed as electrode additives to prepare the HC electrode.
  • the surface area of the conductive carbon materials can be 0 ⁇ 10 m 2 /g, 0 ⁇ 20 m 2 /g, 0 ⁇ 30 m 2 /g, 0 ⁇ 40 m 2 /g, 0 ⁇ 50 m 2 /g, 0 ⁇ 60 m 2 /g, 0 ⁇ 70 m 2 /g, 0 ⁇ 80 m 2 /g, 0 ⁇ 90 m 2 /g, or 0 ⁇ 100 m 2 /g.
  • the HC anode materials may be mixed with conductive carbon materials and binders to make the electrode.
  • binder candidates may be polytetrafluoroethylene (PTFE), polyvinylidene fluoride/difluoride (PVdF), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (Na-CMC), styrene-butadiene rubber (SBR), alginic acid, sodium alginate, and combinations thereof, although other binder materials may be used.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride/difluoride
  • CMC carboxymethyl cellulose
  • Na-CMC sodium carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • HC is a carbonaceous anode material used for illustrative purposes, suitable alternatives such as soft carbons and graphite are similarly possible.
  • HC electrodes were prepared using a slurry comprising HC, a low-surface area conductive carbon (surface area ⁇ 45 m 2 /g), and PVdF (KYNAR HSV900) to afford a composition consisting of HC (75 wt%), low-surface area conductive carbon material (20 wt%), and PVdF (5 wt%). The resulting slurry was coated onto Cu foil.
  • Coin cells were fabricated from the aforementioned electrodes with a sodium (Na) metal counter electrode, and a Na + -permeable membrane interposed between HC and Na electrodes, with 1M sodium hexafluorophosphate (NaPF 6 ) in ethylene carbonate-diethyl carbonate (EC-DEC) as the electrolyte.
  • NaPF 6 sodium hexafluorophosphate
  • EC-DEC ethylene carbonate-diethyl carbonate
  • Cycling was performed by maintaining the rates for both discharge and charge at 50 milliamperes per gram (mA/g) (0.2C, 5 cycles) ⁇ 100 (mA/g) (0.4C, 5 cycles) ⁇ 125 mA/g (0.5C, 10 cycles) ⁇ 250 mA/g (1C, 10 cycles) ⁇ 500 mA/g (2C, 10 cycles) ⁇ 1000 mA/g (4C, 10 cycles) ⁇ 50 mA/g (0.2C) thereafter between 2 V and 5 mV.
  • Fig. 2 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (1.1 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte.
  • Fig. 3 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (2.1 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte.
  • Fig. 4 is a graph depicting 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (3.3 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaPF 6 in EC/DEC electrolyte.
  • Fig. 5 is a graph depicting 0.2C, 0.5C, 1C, 2C and 4C rate discharge/charge curves for HC/Na half-cells (1.2 mg/cm 2 HC loading) cycled between 2 V and 0.005 V using 1M NaClO 4 in EC/DEC electrolyte.
  • Fig. 6 is a flowchart illustrating the first method for fabricating a hard carbon anode for use in sodium-ion and potassium-ion batteries. Although the method is depicted as a sequence of numbered steps for clarity, the numbering does not necessarily dictate the order of the steps. It should be understood that some of these steps may be skipped, performed in parallel, or performed without the requirement of maintaining a strict order of sequence. Generally however, the method follows the numeric order of the depicted steps. The method starts at Step 600.
  • Step 602 mixes a conductive carbon material having a low surface area, a hard carbon material, and a binder material.
  • Step 604 forms a carbon-composite material, defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • Step 606 coats the carbon-composite material on a conductive substrate.
  • the binder material may be a polymer or a mixture of polymers.
  • the conductive carbon material typically has a surface area of less than 100 m 2 /g.
  • Method 2 Metal-Containing Materials as Electronically Conductive Additives
  • the above-described conductive carbon materials can be substituted by metal-containing materials.
  • the surface area of the metal-containing materials can be 0 ⁇ 10 m 2 /g, 0 ⁇ 20 m 2 /g, 0 ⁇ 30 m 2 /g, 0 ⁇ 40 m 2 /g, 0 ⁇ 50 m 2 /g, 0 ⁇ 60 m 2 /g, 0 ⁇ 70 m 2 /g, 0 ⁇ 80 m 2 /g, 0 ⁇ 90 m 2 /g, 0 ⁇ 100 m 2 /g, 0 ⁇ 200 m 2 /g, 0 ⁇ 500 m 2 /g, or 0 ⁇ 1000 m 2 /g.
  • the HC material may be mixed with metal-containing materials and binders to make the electrode. A nonexhaustive list of potential binders was included in the previous section.
  • the metal-containing materials can be coated on, or be a component of a composite with HC materials.
  • a HC material may be dispersed in an aqueous solution containing a dissolved metal salt or metal complex during which metal ions are absorbed on the surface of the hard carbon material.
  • a chemical agent such as a base to increase the solution pH
  • the metal ions absorbed on HC are converted to the corresponding metal hydroxides and/or metal oxides, forming a composite of metal-containing material and HC.
  • a composite of Cu and HC can be used as an example. Accordingly, into an aqueous solution of copper(II) ions (Cu 2+ ) is dispersed a HC material.
  • Cu 2+ are absorbed onto the hard carbon surface.
  • An appropriate solution of sodium hydroxide (NaOH) or similar is used to adjust the solution pH to form a composite of HC and copper hydroxides/copper oxides.
  • the composite is used to fabricate an electrode with an appropriate binder.
  • the copper-containing materials in the hard carbon composite electrode are electrochemically reduced to metallic Cu, which consequently, forms a beneficial electronically conducting network within the HC electrode.
  • Fig. 7 depicts a second anode for use with sodium-ion and potassium-ion batteries.
  • the anode 700 comprises a conductive substrate 102, and a carbon-composite material 702 overlying the conductive substrate.
  • the carbon-composite material 702 comprises a hard carbon material 106, a metal-containing material 704, and a binder material 110.
  • a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • the binder material 110 may be a polymer or mixture of polymers.
  • the metal-containing material 704 has a surface area of less than 100 m 2 /g. In another aspect, the metal-containing material 704 includes a transition metal.
  • the metal-containing material 704 may take the form of elemental metals, metal hydroxides, metal oxides, or combinations thereof. Further, in some aspects the metal-containing material explicitly excludes materials capable of forming an alloy with sodium and potassium, where an alloy is defined as a substance composed of two or more metals, or of a metal or metals with a nonmetal.
  • Fig. 8 is a flowchart illustrating the second method for fabricating an anode for use in sodium-ion and potassium-ion batteries.
  • the method begins at Step 800.
  • Step 802 mixes a metal-containing material, a hard carbon material, and binder material.
  • the binder materials are typically a polymer or polymer mixture.
  • Step 804 forms a carbon-composite material, defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • Step 806 coats the carbon-composite material on a conductive substrate.
  • the metal-containing material typically has a surface area of less than 100 m 2 /g and may include a transition metal.
  • the metal-containing material may take the form of elemental metals, metal hydroxides, metal oxides, or combinations thereof.
  • the metal-containing material excludes materials capable of forming an alloy with sodium and potassium, as alloy is defined above.
  • Method 3 Polymer Composite with Pyrolysis Approach
  • HC materials are dispersed in a polymer to form a carbon-composite.
  • the carbon-composite is thermally treated in a furnace at a temperature range of 300 - 2000 o C, preferably under an inert atmosphere (pyrolysis), to afford a pyrolyzed polymer coating on the HC material that is subsequently mixed with appropriate binder to fabricate an electrode.
  • Appropriate polymer materials for forming the pyrolyzed polymer coating include polymers that may have covalent carbon-carbon bonds and may include natural and synthetic polymers.
  • Figs. 9A and 9B depict steps in a process to form a pyrolyzed polymer coating on a hard carbon material.
  • Hard carbon 106 is depicted as solid particles with a surface 900.
  • the HC particles 106 are wrapped by polymer 902 first, and then heat-treated under inert atmosphere conditions.
  • the resulting composite 904 has a surface 906.
  • the surface area reduction gives rise to a small capacity consumption during charge/discharge in SEI layer formation.
  • the pyrolyzed-polymer coated hard carbon material demonstrates a high coulombic efficiency and high capacity as it is used as an anode in sodium-ion and potassium-ion batteries.
  • Fig. 10 depicts a third anode for use with sodium-ion and potassium-ion batteries.
  • the anode 1000 comprises a conductive substrate 102 and a carbon-composite material 1002 overlying the conductive substrate.
  • the carbon-composite material 1002 comprises a hard carbon material 106 with a pyrolyzed polymer coating 904, and a binder material 110.
  • a carbon-composite material is defined herein as a mixture of two or more different materials, in which at least one material is a carbon material.
  • the binder material 110 may be a polymer or mixture of polymers.
  • Fig. 11 is a flowchart illustrating the third method for fabricating an anode for use in sodium-ion and potassium-ion batteries.
  • the method begins at Step 1100.
  • Step 1102 provides a hard carbon material having a pyrolyzed polymer coating.
  • Step 1104 mixes the hard carbon material having the pyrolyzed polymer coating with a binder material.
  • the binder material is a polymer or mixture of polymers.
  • Step 1106 forms a carbon-composite material, as defined above.
  • Step 1108 coats the carbon-composite material on a conductive substrate.
  • Step 1102a provides a polymer material.
  • Step 1102b disperses a hard carbon material within the polymer material.
  • Step 1102c performs a thermal treatment, for example, by heating to a temperature in the range of 300 to 2000 degrees C. In one aspect, the heating is performed in an inert atmosphere.
  • Step 1102d pyrolyzes the polymer.
  • hard carbon is common to all three scenarios and is a feature of all three strategies for forming anode electrodes with low surface area and high coulombic efficiency.
  • the anode electrode with HC material benefits from increased conductivity due to an electronically conductive network established by employing (1) conductive carbon materials with a low surface area, (2) metal-containing materials, or (3) pyrolyzed polymer coating on HC.
  • Method 1 HC plus conductive carbon
  • Method 3 pyrolyzed polymer coating
  • conductive carbon materials either physically added or formed as pyrolyzed polymer coating.
  • metal-containing approach of Method 2 there are two variations. In the first case, elemental metal particles are mixed with HC.
  • metal precursors are deposited (e.g., oxides) onto the surface of HC.
  • the metal oxide is electrochemically (and irreversibly) reduced to elemental metal materials (on HC surface).
  • the formed metal particles which form a conductive network within the HC electrode, improve the conductivity of the electrode due to the high intrinsic conductivity of metals.
  • Fig. 12 is a partial cross-sectional view of a sodium-ion or potassium-ion battery.
  • the battery 1200 comprises a transition metal hexacyanometallate (TMHCM) cathode 1202 and an electrolyte 1204.
  • THCM transition metal hexacyanometallate
  • IUPAC International Union of Pure and Applied Chemistry
  • a transition metal is defined as “an element whose atom has an incomplete d sub-shell, or which can give rise to cations with an incomplete d sub-shell.
  • transition metals are located in Groups 3 to 12 of the Periodic Table of Elements.
  • TMHCMs have a chemical formula corresponding to A x M1 n M2 m (CN) 6 .
  • d(H 2 O) in the discharged state where “A” is sodium (Na + ), potassium (K + ), or a combination of both; where M1 and M2 are transition metals; where x is in the range between greater than 0 to 4; where n is in the range of 0 to 2; where m is in the range of 0 to 2; and, where d is in the range of 1 to 6.
  • the electrolyte 1204 may be non-aqueous, a polymer, gel, or solid material.
  • the electrolyte may consist of a sodium and/or potassium salt dissolved in an organic solvent or mixture of organic solvents.
  • a nonexhaustive list of possible sodium and potassium salts include sodium or potassium hexafluorophosphate (NaPF 6 or KPF 6 ), sodium or potassium perchlorate (NaClO 4 or KClO 4 ), sodium or potassium tetrafluoroborate (NaBF 4 or KBF 4 ), and sodium or potassium bis(trifluoromethanesulfonyl) imide (NaTFSI or KTFSI).
  • organic solvents include ethylene carbonate (EC), diethyl carbonate (DEC), dimethylcarbonate (DMC), propylene carbonate (PC), and organic ethers.
  • the battery also comprises an anode 100.
  • the anode 100 comprises a conductive substrate 102, and a carbon-composite material 104 overlying the conductive substrate.
  • the carbon-composite material 104 comprises a hard carbon material 106, a conductive carbon material 108 having a low surface area, and a binder material 110.
  • a carbon-composite material 104 is defined as a mixture of two or more different materials, in which at least one material is a carbon material.
  • the anode 100 is shown as formed over a current collector 1206, which may for example be a conductive carbon material or metal.
  • the conductive substrate is the current collector.
  • An ion-permeable membrane 1208 separates the anode 100 from the cathode 1202.
  • the ion-permeable membrane 1208 permits sodium and potassium ions to pass between the anode 100 and cathode 1202 during the charging and discharging of the battery.
  • the ion-permeable membrane 1208 interposed between anode and cathode may be a polymer such as commercial materials available from Celgard.
  • an additional ion-permeable membrane may not be required since while these electrolytes function as ion-permeable membranes, they also serve to isolate anode from cathode.
  • Fig. 13 is a partial cross-section view of a first variation of a sodium-ion or potassium-ion battery.
  • This battery 1300 also comprises a TMHCM cathode 1302 and an electrolyte 1304.
  • the electrolyte 1304 may be non-aqueous, a polymer, gel, or solid material, as described above in the description of Fig. 12.
  • the anode 700 comprises a conductive substrate 102 and a carbon-composite material 702 overlying the conductive substrate.
  • This carbon-composite material 702 comprises a hard carbon material 106, a metal-containing material 704, and a binder material 110.
  • the anode 700 is shown as formed over a current collector 1306, which may for example be a conductive carbon material or metal.
  • An ion-permeable membrane 1308 separates the anode 700 from the cathode 1302.
  • Fig. 14 is a partial cross-sectional view of a second variation of a sodium-ion or potassium-ion battery.
  • the battery 1400 comprises a TMHCM cathode 1402 and an electrolyte 1404.
  • the electrolyte 1404 may be non-aqueous, a polymer, gel, or solid material, as described above.
  • the anode 1000 comprises a conductive substrate 102 and a carbon-composite material 1002 overlying the conductive substrate.
  • This carbon-composite material 1002 comprises a hard carbon material 106 with a pyrolyzed polymer coating 904, and a binder material 110.
  • the anode 1000 is shown as formed over a current collector 1406, which may for example be a conductive carbon material or metal.
  • An ion-permeable membrane 1408 separates the anode 1000 from the cathode 1402.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un premier procédé permettant de fabriquer une anode destinée à être utilisée dans des batteries au sodium-ion et au potassium-ion, ledit procédé consistant à mélanger un matériau à base de carbone conducteur ayant une faible superficie, un matériau à base de carbone dur et un liant. Un matériau composite à base de carbone est ainsi formé et recouvert sur un substrat conducteur. Un deuxième procédé permettant de fabriquer une anode destinée à être utilisée dans des batteries au sodium-ion et au potassium-ion mélange un matériau contenant un métal, un matériau à base de carbone dur et un liant. Un matériau composite à base de carbone est ainsi formé et recouvert sur un substrat conducteur. Un troisième procédé permettant de fabriquer une anode destinée à être utilisée dans des batteries au sodium-ion et au potassium-ion utilise un matériau à base de carbone dur ayant un revêtement polymère pyrolysé qui est mélangé avec un liant afin de former un matériau composite à base de carbone, qui est recouvert sur un substrat conducteur. L'invention concerne également des descriptions des anodes et des batteries formées par ces procédés décrits ci-dessus.
PCT/JP2016/001264 2015-03-13 2016-03-08 Anode pour des batteries au sodium-ion et au potassium-ion WO2016147607A1 (fr)

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CN201680015368.2A CN107431204A (zh) 2015-03-13 2016-03-08 钠离子和钾离子电池阳极

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RU2728286C1 (ru) * 2019-12-09 2020-07-29 Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" Способ приготовления и сборки аккумуляторной ячейки, состоящей из цианокомплексов переходных металлов в качестве катода, неграфитизируемого углерода в качестве анода и безводного электролита, для калий-ионных аккумуляторов

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CN108649181B (zh) * 2018-05-11 2020-06-23 浙江大学 一种无枝晶高循环寿命钾金属电极及其制备方法和应用
CN110400963B (zh) * 2018-05-14 2021-03-30 宁波致轻电池有限公司 一种金属钠或钠钾合金负极/硫化聚丙烯腈正极的二次电池及其制造方法
RU2731884C1 (ru) * 2020-01-29 2020-09-08 Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" Анод для калий-ионных аккумуляторов
GB202007627D0 (en) * 2020-05-21 2020-07-08 Faradion Ltd Carbon anode materials
CN117321799A (zh) * 2021-12-31 2023-12-29 宁德时代新能源科技股份有限公司 正极活性材料、包含其的钠离子二次电池及用电装置
CN114455609B (zh) * 2022-02-16 2023-04-07 温州大学碳中和技术创新研究院 循环稳定的低成本钠离子电池正极材料制备方法及应用

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