WO2013152814A1 - Batterie secondaire au sodium-ion, et matériau d'anode de batterie au sodium-ion - Google Patents

Batterie secondaire au sodium-ion, et matériau d'anode de batterie au sodium-ion Download PDF

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WO2013152814A1
WO2013152814A1 PCT/EP2012/065097 EP2012065097W WO2013152814A1 WO 2013152814 A1 WO2013152814 A1 WO 2013152814A1 EP 2012065097 W EP2012065097 W EP 2012065097W WO 2013152814 A1 WO2013152814 A1 WO 2013152814A1
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anode
carbon
ion battery
sodium ion
branches
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PCT/EP2012/065097
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English (en)
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Kun TANG
Joachim Maier
Robin J. WHITE
Maria-Magdalena TITIRICI
Markus Antonietti
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MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.
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Publication of WO2013152814A1 publication Critical patent/WO2013152814A1/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
    • H01M4/36—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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

  • a secondary sodium ion battery and a sodium ion battery anode material The present invention relates to a secondary sodium ion battery comprising a casing, an anode, a cathode, a separator arranged between the anode and the cathode, and an electrolyte.
  • the invention also relates to an anode material.
  • green technologies such as e.g. electric cars, and green power stations, e.g. solar powered power stations or wind parks etc.
  • the demand for electric storage capabilities is increasing substantially, in order to ensure that no energy shortages take place due to e.g. the intermittent nature of wind and the time and weather dependence of solar energy.
  • Lithium-based batteries are currently the technology of choice for developing renewable energy technology and electric vehicles due to their high energy density and low weight.
  • electrolytes should generally be Na- based aqueous electrolytes, since they can be made at low cost. Examples of possible aqueous electrolytes are stated to be Na 2 SO 4 , NaClO 4 , and NaOH.
  • graphite anode materials are the material of choice in lithium-ion batteries, it is stated that the same type of anode materials appear not to work as well in a sodium-ion battery because of the size of the sodium ions. It is in particular stated that a much lower amount of sodium ions is diffused into the graphite layers and that the electrochemical insertion of sodium into graphite is expected to occur below the sodium plating potential having the effect that the charging process cannot be observed using such a battery. It has therefore been established that only a small amount of sodium can intercalate to graphite, which is the dominant anode material in today's commercial lithium rechargeable batteries. Generally speaking it has been found that increasing the degree of graphitization results in decay of the sodium storage capacity.
  • the principal requirements for a material suitable as an anode material are the performance characteristics at the temperature at which the bat- teries operate, the weight of the material, the storage capacity of the material, the lifetime of the material as a battery, as well as its ability to withstand high charge and discharge rates, for example of better than C/5 and the number of charge and discharge cycles to which it can be subjected without serious loss of performance.
  • a battery for e.g. an electric car cannot be too heavy, because otherwise more of the power of the battery will be required to accelerate the car of heavier weight. Similarly such a battery needs to have a fast discharge rate, so that during high power peaks, e.g. on acceleration of the car, the car can draw sufficient power from the battery. In this connection it has been found for some materials that too high a discharge rate leads to a breakdown of the storage capability and a failure of the battery. Likewise a battery for an electric car that can only be charged at a low rate is not useful in practice because otherwise owners are unnecessarily restricted by long charge times.
  • a secondary sodium ion battery comprising, a casing, a carbon based anode, a sodium based cathode, a separator arranged between the anode and the cathode, and an anhydrous electrolyte
  • the anode material is a spongiform branched carbon material having branches of average cross-sectional di- ameters in a size range of 5 to 30 nm, wherein the branched carbon material has interconnected carbon branches and free standing carbon branches, the majority of the carbon branches having a length in the size range of 10 to 500 nm, the spongiform material having voids between the carbon branches, the voids forming an interconnected 3D porosity.
  • the interconnected hierarchical carbon structure of the anode ensures an efficient and continuous electron transport.
  • a very defined and large electrode/ electrolyte contact area of the anode offers a large number of active sites for charge-transfer reactions to take place.
  • the large interlayer spacing facilitates sodium ion transport and storage in the anode, which is especially important for the larger sodium ion in comparison to the relatively small lithium ion.
  • the abundance of sodium and its relatively low price make its compounds suitable cathode materials.
  • the carbon based sodium-ion battery anode of the present invention operates well with known types of sodium cathode materials, such as NaFePO 4 , NaVPO 4 F, Na 3 V 2 (PO4)2F3,
  • the cathode of the present invention can in principle be manufactured from any kind of sodium-based material provided that it is suitable for use in a sodium-based secondary battery.
  • the anhydrous electrolyte will generally be a sodium-based anhydrous electrolyte, such as Na2SO4, NaClO4, Na3PO4, and NaOH.
  • a typical electrolyte would be 1M NaClO4 in propylene carbonate.
  • the anode material has an interconnected 3D porosity.
  • the interconnected hierarchical structure ensures an efficient and continuous electron transport.
  • an interconnected 3D porosity brings about a large electrode/ electrolyte contact area which offers a large num- ber of active sites for charge-transfer reactions to take place, in comparison with normal graphite electrode material.
  • the 3D porosity forms passages in the carbon anode permitting the transport of sodium ions through the anode.
  • the majority of voids between the carbon branches forming the interconnected 3D porosity have cross-sectional dimensions (length, width and height) in the range of 10 to 200 nm.
  • the carbon branches have mesopo- rosity, i.e. pores smaller than said voids with the majority of said pores having maximum cross sectional dimensions in the size range of up to 10 nm.
  • Such a pore size due to the voids and the mesopores leads to a relatively large surface area in the range from 200 to 800 m 2 /g, preferably in the range from 220 to 600 m 2 /g and most preferably in a range from 240 to 480 m 2 /g.
  • the anode material has layers of said branched carbon material, with the layers having an interlayer spacing facilitating the transport of sodium ions in said anode material.
  • the anode material has a reversible capacity in the range from 150 to 300 mAhg 1 or higher at a current density of 50 mAg ! .
  • the spongiform branched carbon material is mixed with a binder (such as PVDF) carried by a metallic carrier, for example a foil of copper or titanium.
  • a sodium ion battery anode comprising a spongiform material and being a branched carbon material having branches of average cross-sectional diameters in a size range of 5 to 30 nm, wherein the branched carbon material has interconnected carbon branches and free standing carbon branches, the majority of the carbon branches having a length in the size range of 10 to 500 nm, the spongiform material having voids between the carbon branches, the voids forming an interconnected 3D porosity.
  • the carbon branches are formed by disordered nitrogen-doped carbon.
  • the resulting conducting 3D network formed by disordered nitrogen-doped carbon, has large interlayer spacings which facilitate the sodium ion transport and storage between graphene layers leading to a large capacity, long life cycle and excellent rate performance for such a battery material.
  • Such an interlayer spacing is greater than 0.4 nm which is large compared to the interlayer spacing of graphite of 0.34 nm and facilitates the sodium-ion transport and storage between the different layers.
  • the interlayer spacing is in the range of 0.4 nm to 2 nm and most preferably in the range of 0.4 to 1 nm.
  • the anode material has an interlayer spacing facilitating the transport of sodium ions.
  • Such an interlayer spacing facilitates sodium ion transport and storage between graphene layers, which is especially important for the larger sodium cation, because this requires more space to diffuse through such an electrode material in order to bring about a high capacity etc.
  • a synthesis process using the synthesis of monolithic nitrogen-doped carbon via the hydrothermal conversion of Glucose in the presence of protein additive e.g.
  • ovalbumin was used, whereby the protein acts as surface stabilising/ structure directing agent(s) to create a stable heteroatom(N) doped carbon scaffolds possessing co- continuous flexible porosity, tunable chemistry and structural size.
  • This unique hierarchical structure provides fast electron and sodium ion transport, which is reflected in a superior rate capability and a good cycle stability.
  • Fig. 1 a schematic illustration of a secondary sodium ion battery
  • Fig. 2 a HR-TEM image of carbogels produced at 750°C
  • Fig. 3 a HR-TEM image of carbogels produced at 900°C; a galvanostatic charge/ discharge curve at a current density of 200 mA/g; Fig. 5 a galvanostatic charge/ discharge curve for the first 10 cycles of the anode material of the present invention at a current density of 200 mA/g; Fig. 6 a current versus voltage plot for the anode material of the present invention; and
  • Fig. 7 a graph showing the rate capabilities of the anode material of the present invention.
  • Fig. 1 shows a schematic illustration of a secondary sodium ion battery 10 which is composed of a positive electrode (anode) 12, a negative electrode (cathode) 14, a separator 16, a casing 18 and an aqueous electrolyte 20.
  • the cathode 14 is made of a sodium-based cathode material and can be selected from the group including NaFePO4, NaVPO4F, Na 3 V 2 (PO4)2F3, Na 2 FePO 4 F, Na 3 V 2 (PO 4 )3 , Na x CoO 2 , P(EO) 8 NaCF 3 SO 3 , P 2 -Na x CoO 2 ,
  • the electrolyte 20 will generally be a sodium-based electrolyte, typically an anhydrous sodium-based electrolyte, such as Na 2 SO4, NaClO4, Na 3 PO4, NaOH etc.
  • the anode 12 is a carbon-based anode and e.g. glass fiber (GF/D) from Whatman can be used as the material for the separator 16.
  • the casing 18 can be composed of e.g. stainless steel or plastic.
  • the anode material 12 is a so-called carbogel anode material which is thermally treated during its manufacture.
  • the carbogel can be synthesized by mixing H 2 O (double distilled), D-glucose (99.5 % purity, by Sigma Aldrich ® ) and ovalbumin (lypholised powder, type V, 99.5 % purity, Sigma Aldrich ® ) at a ratio of 9 : 1 : 0.15 (w/w/ w) in a glass inlet (30 mL volume) sealed in a Teflon lined autoclave (45 mL volume) and placed in a laboratory oven preheated to 180°C and left for the desired reaction time (e.g. 5 hours).
  • H 2 O double distilled
  • D-glucose 99.5 % purity, by Sigma Aldrich ®
  • ovalbumin lypholised powder, type V, 99.5 % purity, Sigma Aldrich ®
  • the carbogel was then removed from the autoclave and washed extensively, firstly with 3 ⁇ 4O (double distilled) and secondly with ethanol (analytical grade) until the carbogel is saturated in alcohol.
  • the original supercritically dried carbogel was placed in a ceramic crucible and placed in a carbonization oven and heated to the desired temperature (e.g. 750°C, see results in Fig. 2, or 900°C, see results in Fig. 3) under an inert atmosphere, (i.e. N2/flow: 10 mLmin ) using a ramp and isothermal step of 4 hours respectively.
  • the samples were then allowed to cool to ambient conditions and removed from the oven prior to further analysis.
  • Fig. 2 shows a high resolution TEM image of heat-treated carbogels, which show an unusual coral-like continuous carbonaceous nano- architecture.
  • the Transmission Electron Microscopy (TEM) was carried out using a Zeiss EM912 Omega operated at an acceleration voltage of 120 kV.
  • the hyper-branched network has walls of disordered graphitic-like sheets composed of approximately 2 to 3 short carbon layers stacking locally in no preferential long range (> 100 nm) orientation.
  • Fig. 2 shows an interconnected branched structure 22 having branches 24, 26 of average cross-sectional diameters in the size range of 5 nm to 30 nm wherein the branched carbon material 22 has interconnected carbon branches 24 and free standing carbon branches 26, the in- terconnected carbon branches 24 and the free standing carbon branches 26 having a length in the size range of 10 to 500 nm.
  • the free standing branches 26 typically have a length in the range of lOnm to lOOnm.
  • the material shown in Fig. 2 has a high specific surface area (308 m 2 /g) composed of large continuous mesopores (interconnected branched structure having a mesopore size of approximately 3 nm) forming a transport architecture. Fabrication of such a porous system provides favourable
  • This mixed conducting 3D network is formed by disordered nitrogen-doped carbon and has large interlayer spacings which facilitate the sodium ion transport and storage between graphene layers leading to a large capacity, long life cycle and excellent rate performance (see Fig. 5 to 7).
  • the carbon branches are considered to have mesopo- rosity, i.e. pores smaller than said voids with the majority of said pores having maximum cross sectional dimensions in the size range of up to 10 nm.
  • the total pore size due to the voids and the mesopores leads to a relatively large surface area (BET surface area) which is most preferably in the range from 240 to 480 m 2 /g.
  • BET surface area surface area
  • reducing the BET surface area to values below the preferred range of 240 to 480 m 2 /g and indeed to below 200 m 2 /g reduces the storage capacity for sodium ions, which is negative, i.e. is unfavorable.
  • the reduction in the storage capacity can be accompanied by an increase in the conductivity and the ability to transport electrons through the electrode material, which can be favorable.
  • providing a surface area in the preferred claimed range of 240 to 480 m 2 /g maximizes the performance of the electrode in terms of the reversible capacity and the ability to quickly charge and discharge the electrode.
  • the interconnected hierarchical structure 22 ensures an efficient and con- tinuous electron transport.
  • the defined and large electrode/ electrolyte contact area (308 m 2 /g) offers a large number of active sites for charge- transfer reactions.
  • the large interlayer spacing (> 0.4 nm compared to 0.34 nm for graphite) facilitates sodium ion transport and storage between graphene layers, which is especially important for the larger sodium cati- on.
  • the walls of the branched structure 22 are very thin (having a thickness of less than 15 nm) which also guarantees a very short sodium diffusion distance, which plays a vital role in the rate performance.
  • the HR-TEM image of the carbongels produced at 900°C in Fig. 3 shows a similar branched network structure 22.
  • the material is also an interconnected continuous 3D porous material which has a large interlayer spacing (> 0.4 nm). It is expected that a large fraction of sodium storage between these graphene layers has a beneficial effect on the rate performance.
  • the disordered nitrogen carbon has large interlayer spacings which facilitate the sodium ion transport and storage between the graphene layers.
  • the disordered nitrogen doped carbon exhibits excellent electrochemical performance in sodium ion batteries 10, including large capacity, long cycle life and excellent rate performances.
  • Fig. 4 shows the 10 th cycle galvanostatic charge/ discharge curve for a secondary lithium ion battery 10. It can clearly be seen that the material has a maximum capacity of 200 mAhg 1 and can be reliably recharged to this capacity after 10 cycles.
  • Figs. 5 to 7 depict further test results obtained using a battery 10 in accordance with the invention.
  • the battery 10 used to obtain the test results depicted in all of the Figs 4 to 7 two-electrode
  • Swagelok-type cells were used for test purposes. This reverses the anode and cathode and can be very confusing. For example, if one considers a lithium battery. In a practical cell, LiFePO4 is the cathode, and carbon is the anode, because the voltage of LiFePO4 is 3.5V and 0.3V for carbon. But in a half cell, lithium metal is used as an anode, since it has the lowest voltage 0V, then the carbon in the half cell becomes the cathode. It is similar in the sodium system. In the half cell, sodium metal is anode, and the carbon acts as cathode. But when the test system is
  • Na3V2(PO4)/ electrolyte/ carbon (corresponding to an example of an actual sodium-ion battery) the Na3V2(PO4b is the cathode and the carbon material is the anode.
  • the working electrode 12 was made by spreading the nitrogen doped material (2 mg/cm 2 ) onto a copper current collector (0.8 cm 2 ) and dried in a vacuum oven at 120 °C overnight. The cells were assembled in an argon- filled glove box. Sodium metal was utilized as counter electrode 14 and glass fiber (GF/D) from Whatman was used as a separator 16. The electrolyte 20 was 1 M NaClO4 in propylene carbonate. Cyclic voltammetry measurements were performed on a VoltaLab 80 electrochemical workstation at a scan rate of 0.1 mVs 1 . Charge-discharge (0.001 - 3V) tests were performed on an Arbin MSTAT battery test system under ambient temperature. In contrast to this Fig.
  • FIG. 5 shows a galvanostatic charge/ discharge curve for the first end cycles of the anode material 12 of the present invention. This shows the same charge/ discharge rates for the battery of Fig. 4. Like the battery of Fig. 4 a stable cycle performance is achieved with a highly reversible capacity at approximately 100 mAhg 1 in a cell between 0.5 and 2.5 V for the first ten cycles.
  • the electrode thickness of cur- rent commercial lithium ion batteries is typically selected to be 250 ⁇ . Depending on the application this size may be varied, e.g. within a non- limiting range of 10 to 400 ⁇ . For example, when materials are being tested for their suitability as battery electrode materials, these electrodes typically have a thickness in the range from 10 to 50 ⁇ , as is the case with the materials presented in this document.
  • Fig. 6 shows a current versus voltage graph for the anode material 12 of the present invention.
  • the current versus voltage graph was made at a scan rate of 0.2 mV/s. It shows the similar characteristics as for lithium just with different voltages.
  • Fig. 7 shows the excellent rate capability of the anode material 12, even at a high current density of 10 Ag - 1 .
  • the reversible capacity of 200 mAhg 1 at a current density of 50 mAg 1 is significant, and only a few reports achieved capacities more than 200 mAhg 1 for sodium anode materials, typically obtained at much lower current densities or at higher temperature than the room temperature required for the present anode material.
  • a good cycling performance of > 100 cycles has seldom been achieved in previous reports on anode materials for sodium ion bat- teries.
  • the reversible capacities at various discharge / charge rates are obtained at 168, 142, 120, 100 and 85 mAhg 1 at current densities of 0.2, 0.5, 1 , 2 and 5 Ag 1 respectively. Even at a very high current density of 10 Ag- 1 , a capacity of ⁇ 70 mAhg -1 . Such values are extremely high for sodium-ion based batteries at room temperature for the number of cycles performed.

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Abstract

La présente invention concerne une batterie secondaire au sodium-ion (10), comprenant un boîtier (18), une anode à base de carbone (12), une cathode à base de sodium (14), un séparateur (16) agencé entre l'anode (12) et la cathode (14), et un électrolyte anhydre (20). Le matériau d'anode (12) est un matériau de carbone ramifié spongiforme (22) ayant des ramifications (24, 26) de diamètre transversal moyen compris dans la gamme de taille allant de 5 à 30 nm. Le matériau de carbone ramifié (24, 26) comporte des ramifications de carbone (24) et des ramifications de carbone sur pied libres (26) interconnectées, la majorité des ramifications de carbone (24, 26) présentant une longueur se situant dans une gamme de taille allant de 10 à 500 nm. Le matériau spongiforme comporte des vides entre les ramifications de carbone, les vides formant une porosité tridimensionnelle interconnectée. L'invention concerne en outre un matériau d'anode de batterie au sodium-ion.
PCT/EP2012/065097 2012-04-12 2012-08-02 Batterie secondaire au sodium-ion, et matériau d'anode de batterie au sodium-ion WO2013152814A1 (fr)

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CN104795560A (zh) * 2014-07-21 2015-07-22 中国科学院物理研究所 一种富钠p2相层状氧化物材料及其制备方法和用途
WO2015119887A1 (fr) * 2014-02-04 2015-08-13 Nivo Systems, Inc. Composites à ossature ouverte, procédés de production et d'utilisation de tels composites
CN105006565A (zh) * 2015-08-18 2015-10-28 湖南丰日电源电气股份有限公司 一种铅-锂杂交二次电池
CN105375008A (zh) * 2015-11-13 2016-03-02 武汉理工大学 层状Na3V2(PO4)3@rGO纳米复合材料及其制备方法和应用
CN108987711A (zh) * 2018-07-19 2018-12-11 中南大学 一种球形钠离子电池正极四元材料及其制备方法
JP2019501497A (ja) * 2015-12-25 2019-01-17 清▲華▼大学深▲セン▼研究生院 ナトリウムイオン電池の電極材料及びその製造方法
CN111504914A (zh) * 2020-04-07 2020-08-07 九江学院 一种固态电池的原位测试装置

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CN104795560B (zh) * 2014-07-21 2017-05-31 中国科学院物理研究所 一种富钠p2相层状氧化物材料及其制备方法和用途
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JP2019501497A (ja) * 2015-12-25 2019-01-17 清▲華▼大学深▲セン▼研究生院 ナトリウムイオン電池の電極材料及びその製造方法
CN108987711A (zh) * 2018-07-19 2018-12-11 中南大学 一种球形钠离子电池正极四元材料及其制备方法
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