WO2006033069A2 - Energy storage device - Google Patents

Energy storage device Download PDF

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Publication number
WO2006033069A2
WO2006033069A2 PCT/IB2005/053061 IB2005053061W WO2006033069A2 WO 2006033069 A2 WO2006033069 A2 WO 2006033069A2 IB 2005053061 W IB2005053061 W IB 2005053061W WO 2006033069 A2 WO2006033069 A2 WO 2006033069A2
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Prior art keywords
electrochemical cell
cell according
tio
tiθ2
electrode
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PCT/IB2005/053061
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French (fr)
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WO2006033069A3 (en
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Marketa Zukalova
Martin Kalbac
Ladislav Kavan
Ivan Exnar
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High Power Lithium Sa
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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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/02—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof using combined reduction-oxidation reactions, e.g. redox arrangement or solion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • 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
    • 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 invention relates to an energy storage device comprising a positive electrode, a negative electrode and an electrolyte. At least one electrode being made of metal oxide.
  • the current Li-ion batteries are based on Li-insertion or Li-intercalation into suitable host structures, such as graphite or solid transition metal oxides '.
  • the basic unit of a battery is an electrochemical cell with a positive electrode, a negative electrode and an electrolyte, the whole contained within a casing. Other components such as separators or gasket are also included.
  • the charging/discharging rate is controlled by the diffusion of Li + ions into/from the crystal lattice of the host.
  • An alternative to the bulk charge accommodation is the surface charge storage in a supercapacitor, and there are also hybrid devices, in which one electrode works as the bulk charge storage medium (Li 4 TIjOi 2 spinel) and the second electrode as the surface charge storage medium (active carbon) 2 .
  • TiO 2 (B) is a metastable monoclinic modification of titanium dioxide. It was first synthesized in 1980 by Marchand et al. 3>4 from a layered titanate K 2 Ti 4 Og by K + ZH + ion exchange followed by calcination. TiO 2 (B) >8 and "monoclinic TiO 2 " (apparently TiO 2 (B)) 9 were traced during the synthesis of titania nanotubes by hydrothermal treatment of TiO 2 in NaOH medium. By tuning of the temperature and concentration of NaOH, either titanate nanotubes or TiO 2 (B) nanowires were synthesized selectively 8 .
  • TiO 2 (B) can equally be called "freudenbergite modification Of TiO 2 ", but this name is not common.
  • the density of TiO 2 (B) is 3.64- 3.76 g/cm 3 , 4 ' 15 ' 18 i.e. it is smaller than that of anatase, rutile or brookite.
  • TiO 2 (B) The electronic structure of TiO 2 (B) was calculated by Nuspl et al. 19 .
  • TiO 2 (B) is n-type semiconductor with a band gap of 3 - 3.22 eV 20>21 , which is similar to that of rutile and anatase. Due to its open structure, TiO 2 (B) accommodate hydrogen via electrochemical reduction of inserted protons, and this hydrogen can be extracted photoelectrochemically in visible light 21 .
  • TiO 2 (B) accommodates Li + to form Li x TiO 2 (B).
  • This application is claimed in French Patent Application FR 2 482 787.
  • the insertion coefficient x was found 0.75-0.85 by the reaction with n-butyl-lithium and x « 0.5 - 0.75 by electrochemistry 4 - 22"25 , The electrochemical reversibility of lithium insertion was, reportedly, not very good 4 .
  • the TiO 2 (B) lattice has parallel infinite channels, in which Li + can be accommodated, without any significant distortion of the structure 19 .
  • the diffusion control of Li 1 storage in a bulk crystal can be traced by methods, such as cyclic voltammetry 33 and chronoamperometry " 4 , which employ concepts and principles translated, essentially, from the solution electrochemistry.
  • This philosophy provides useful physical parameters, such as diffusion coefficients Of Li + in a solid. For instance, the Li 4 Ti 5 O] 2 (spinel) 35 and TiO 2 (anatase) 33>34 have been successfully treated by this methodology.
  • Electrochemical capacitors can be divided into two subcategories: (i) double-layer capacitors in which the interfacial capacitance at the electrode/electrolyte interface can be modelled as two parallel sheets of charge; and (H)
  • the present invention relates to certain solid host structures that could accumulate Li in a process, which is not controlled by the diffusion inside the solid, but the material behaves like a pseudocapacitive charge-storage medium.
  • a pseudocapacitor charge transfer between the electrolyte and the electrode occurs over a wide potential range as a result of oxidation/reduction reactions between the electrode and the electrolyte.
  • Pseudocapacitors are being developed for high-pulse power applications.
  • the present invention provides an electrochemical cell which may be used in a portable electronic devices, EV or HEV, while at least one of the electrodes comprise a solid host structure, which is not limited kinetically by the diffusion of Li inside the solid.
  • An example of such electrode materials is TiO 2 (B).
  • Sample A 3.5g of amorphous TiO 2 was autoclaved in 100 mL of 10 M NaOH at 250 0 C for 48 hours, then washed with H 2 O and autoclaved in 0.1 M HNO 3 at 200 0 C for 2.5 hours. The dried sample was then calcined at 500 0 C for 1 hour.
  • Sample B 1O g of amorphous TiO 2 was mixed with 7.78 g of Cs 2 COs (Aldrich) and mortared carefully. The mixture was then decarbonated at 800 0 C for 4 hours, mortared again and annealed at 800 0 C in a crucible with a tight for 24 hours twice, with grinding at the interval. The product was then mortared and ion-exchanged with I N HCl for 4 x 24 hours at vigorous stirring with the fresh acid every 24 hours. The amount of IN HCl was
  • Sample C This material was prepared according to the original synthetic protocol of TiO 2 (B) 3 .
  • PKP04090 was annealed at 1000 0 C for 2 days.
  • the product was mortared and hydrolyzed with 0.4 N HNO3 for 3 days at vigorous stirring with the fresh acid every 24 hours.
  • 1 g of the powder corresponded to 100 mL of 0.4 N HNO 3 .
  • the sample was dried in air at ambient temperature, then under vacuum overnight and calcined at 500 0 C for 30 min.
  • Powder sample was dispersed in aqueous medium into viscous paste according to the previously developed methods 28"32 .
  • the powder (0.3 g) was mixed under stirring or gentle mortaring with 0.8 mL of 10 % aqueous solution of acety lacetone. Subsequently, 0.8 mL of 4 % aqueous solution of hydroxypropylcellulose (Aldrich, MW 100,000) was added and finally 0.4 mL of 10 % aqueous solution of Triton-XIOO (Fluka). Before use, the prepared slurry was homogenized by stirring. If the slurry was too viscous, it was further diluted by water.
  • Titanium grid (5 x 15 mm, Goodfellow) was used as the electrode support. Electrodes were prepared by dip-coating, the coated area was ca. 5 x 5 mm. The prepared electrodes were dried in air, and finally calcined in air at 450 0 C for 30 min. The amount of active electrode material was between 0.2 to 0.7 mg. Blank experiments confirmed that a bare Ti grid had negligible electrochemical charge capacity compared to that of the active material. Alternatively, the slurry was also deposited on a sheet of conducting glass (F-doped SnO 2 , TEC 8 from Libbey-Owens-Ford, 8 ⁇ /square) using a doctor-blading technique 32 .
  • F-doped SnO 2 , TEC 8 from Libbey-Owens-Ford, 8 ⁇ /square
  • the sheet of conducting glass had dimensions: 3 x 5 x 0.3 cm 3 .
  • a Scotch-tape at both edges of the support (0.5 cm) defined the film thickness and left part of the support uncovered for electrical contact.
  • the film was finally calcined for 30 min in air at 450 0 C. After cooling down to room temperature, the sheet was cut into ten electrodes 1.5 x 1 cm 2 in size; the geometric area of the TiO 2 film was 1 x 1 cm 2 .
  • Electrochemical measurements were carried out in an one-compartment cell using an Autolab Pgstat-30 (Ecochemie) controlled by the GPES-4 software.
  • the reference and auxiliary electrodes were from Li metal, hence, potentials are referred to the Li/Li + (IM) reference electrode.
  • LiN(CF 3 SO 2 ) 2 (Fluorad HQ 115 from 3M) was dried at 130°C/l mPa.
  • Ethylene carbonate (EC) and 1,2-dimethoxyethane (DME) were dried over the 4A molecular sieve (Union Carbide).
  • the electrolyte solution 1 M LiN(CF 3 SO 2 )T + EC/DME (1/1 by volume) contained 15-40 ppm H 2 O as determined by Karl Fischer titration (Metrohm 684 coulometer). All operations were carried out under argon in a glove box. Raman spectra were excited by an Ar ⁇ laser at 2.41 eV (Innova 305, Coherent) and recorded on a T-64000 spectrometer (Instruments, SA).
  • Fig. 1 shows Raman spectra of the prepared materials.
  • Sample A is apparently a mixture of anatase and TiO 2 (B), but the spectra of samples B and C can be assigned to pure TiO 2 (B) 8>13 ' 14 .
  • the formation of pure TiO 2 (B) in sample B (Fig. 1) is surprising.
  • the employed synthetic protocol should, actually, lead to the orthorhombic lepidocrocite-like protonic titanate, H x Ti 2-v / 4 ⁇ /4 O 4 .
  • This species is characterized by ideally flat sheets of edge-sharing TiOo octahcdra 36"38 , which should convert directly into anatase 1O ' U , without the intermediate crystallization of TiO 2 (B).
  • Nanocrystalline anatase TiO 2 (Bayer) provided mixtures of TiO 2 (B) and anatase or pure anatase in the final product, but the synthesis starting from amorphous TiO 2 (see Experimental Section) lead, unexpectedly, to pure TiO 2 (B).
  • Fig. 2 shows cyclic voltammograms of samples A and B.
  • the voltammogram of sample A exhibits a pair of cathodic/anodic peaks at 1.75 & 1.95 V (formal potential 1.85 V), which are characteristic for Li-insertion into anatase lattice 28>29 . 32>3j . 39 - 43 > ⁇ e h ave previously denoted this pair of peaks as "A-peaks" 28 .
  • the voltammogram shows two pairs of peaks with formal potentials of 1.52 and 1.59 V vs. Li/LF, respectively, denoted Sl and S2, respectively 28 .
  • Fig. 3 demonstrates the behavior of S-peaks in phase-pure sample B at varying scan rates.
  • the peak currents were normalized with respect to the peak current at the slowest scan (0.1 mV/s) and plotted against the scan rate (inset in Fig. 3). Hence, the currents scale with the first power of scan rate, which is typical for capacitive charging:
  • n number of electrons
  • A is the electrode area
  • c is the maximum concentration Of Li + (or Ti 3+ ) in the accumulation layer
  • D is diffusion coefficient and the other symbols have their usual meaning.
  • Fig. 4B confirms that this dependence can be fitted to experimental points for v ⁇ « 2 mV/s. (For higher scan rates, the fit is still good, but the experimental points show systematic negative deviation, due to uncompensated iR drop of the cell).
  • the behavior described by Eq. 2 is typical for Li-insertion into "ordinary" anatase lattice 26 - 29 - 32 . 33>39 - 42 _ ⁇ ne / a v m dependence was even found the for Li-insertion into titania nanosheets derived from lepidocrocite-like titanate 44 .
  • Li + can be very mobile inside these channels by easy hoping between occupied and unoccupied sites 19 . All these channels are structurally equivalent, and also the structure of Li 0 ⁇ TiO 2 (B) is assumed to have only crystallographically equivalent sites occupied by Li + l ⁇ > . Nevertheless, there are further vacant sites up to the stoichiometry of LiTiO 2 (B) 19 . All these sites are pseudo-octahedral with a coordination number 5 (LiOs) 19 ' 25 , while two kinds of these sites are detectable by 7 Li-NMR 25 .
  • LiOs coordination number 5
  • Figure 1 Raman spectra of the prepared materials [A] Sample prepared by hydrothermal growth [B] sample prepared from amorphous TiO 2 [C] sample prepared from H 2 Ti 4 Og-H 2 O (bronze). Spectra B and C are assignable to monoclinic TiO 2 (B), spectrum [A] shows also the anatase peaks (marked by arrows) in addition to TiO 2 (B). The Raman intensities of samples A and B are multiplied by a factor of 10 and 4, respectively. Spectra are offset for clarity.
  • Figure 2 Cyclic voltammograms in IM LiN(CF 3 SO 2 ) 2 + EC/DME (1:1, v:v); scan rate 0.1 mV/s.
  • Sample prepared by hydrothermal growth [B] sample prepared from from amorphous TiO 2 .
  • Figure 3 Cyclic voltammograms of sample B in IM LiN(CF 3 SO 2 ) 2 + EC/DME (1 :1, v:v); scan rale 0.1 - 1.2 mV/s (in 0.1 mV/s steps for plots from bottom to top).
  • Inset displays the normalized peak current, i/ioi, where ⁇ ' oi is the peak current at the slowest scan (0.1 mV/s).
  • Figure 4 Cyclic voltammograms of sample A in IM LiN(CF 3 SO 2 ) 2 + EC/DME (1 :1, v:v); scan rate 0.1 - 1.0 mV/s (in 0.1 mV/s steps for plots from bottom to top).
  • Inset displays the absolute values of normalized peak current, i/ioi, where ⁇ oi is the peak current at the slowest scan (0.1 mV/s). Circles: anodic peak at ca. 2 V; crosses: cathodic peak at ca. 1.5 V, squares: cathodic peak at ca. 1.6 V. References

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Abstract

High-energy and high power-density pseudocapacitive energy storage device is based on transition metal oxides having solid host structure with open parallel channels accessible to electrolyte ions. Examples of such structures are TiO2(B), VO2(B), FeV3O8 and AlNbO4. The energy storage is achieved by a pseudocapacitive process, which is not controlled by the diffusion of Li in the solid. The same material/process can be also used for hydrogen storage.

Description

Energy storage device
Field of the invention
The invention relates to an energy storage device comprising a positive electrode, a negative electrode and an electrolyte. At least one electrode being made of metal oxide.
State of the art
The current Li-ion batteries are based on Li-insertion or Li-intercalation into suitable host structures, such as graphite or solid transition metal oxides '. The basic unit of a battery is an electrochemical cell with a positive electrode, a negative electrode and an electrolyte, the whole contained within a casing. Other components such as separators or gasket are also included. The charging/discharging rate is controlled by the diffusion of Li+ ions into/from the crystal lattice of the host. An alternative to the bulk charge accommodation is the surface charge storage in a supercapacitor, and there are also hybrid devices, in which one electrode works as the bulk charge storage medium (Li4TIjOi2 spinel) and the second electrode as the surface charge storage medium (active carbon) 2.
TiO2(B) is a metastable monoclinic modification of titanium dioxide. It was first synthesized in 1980 by Marchand et al. 3>4 from a layered titanate K2Ti4Og by K+ZH+ ion exchange followed by calcination. TiO2(B) >8 and "monoclinic TiO2" (apparently TiO2(B)) 9 were traced during the synthesis of titania nanotubes by hydrothermal treatment of TiO2 in NaOH medium. By tuning of the temperature and concentration of NaOH, either titanate nanotubes or TiO2(B) nanowires were synthesized selectively 8. The structure of hydrothermally grown nanotubes has been a subject of considerable confusion in the past, but recent studies point at the layered titanate, H2Ti3θ7 as the main constituent of these nanotubes 7>8. An alternative suggestion was that the hydrothermally grown titanate nanotubes are composed of orthorohombic lepidocrocite-like species, HxTi2-x/4ϋχ/4θ4.H2θ (x « 0.7, π = vacancy) 10, which transforais directly to anatase by heating 10>H. However, this work was criticized by others 7, and the sole presence of monoclinic titanates (trititanates) seems to explain the hydrothermal synthesis of nanotubes satisfactorily 7'12. Since the H2Ti3O7 can be thermally dehydrated to TiO2(B) 7>13>14 ; the existence of TiO2(B) nanotubes is supported, too 7.
TiO2(B) was even found in nature by Banfϊeld et al. 15. Its crystal structure was first determined by Marchand et al. 3. The structure was further refined by theoretical methods 16, by X-ray '3 and neutron diffraction 14. TiO2(B) has monoclinic unit cell (space group ClIm) with a = 1.21787 nm, b = 0.37412 nm, c = 0.65249 nm, β = 107.054° 14. The structure is isotypic to that of NaxTiO2 (bronze), x = 0.2, where the name "TiO2(B)" comes from. The same crystal structure is also represented by the mineral NaoFeaTigOiδ (freudenbergite) 17. Hence, TiO2(B) can equally be called "freudenbergite modification Of TiO2", but this name is not common. The density of TiO2(B) is 3.64- 3.76 g/cm3, 4'15'18 i.e. it is smaller than that of anatase, rutile or brookite.
The electronic structure of TiO2(B) was calculated by Nuspl et al. 19. TiO2(B) is n-type semiconductor with a band gap of 3 - 3.22 eV 20>21, which is similar to that of rutile and anatase. Due to its open structure, TiO2(B) accommodate hydrogen via electrochemical reduction of inserted protons, and this hydrogen can be extracted photoelectrochemically in visible light 21.
TiO2(B) accommodates Li+ to form LixTiO2(B). This application is claimed in French Patent Application FR 2 482 787. The insertion coefficient x was found 0.75-0.85 by the reaction with n-butyl-lithium and x « 0.5 - 0.75 by electrochemistry 4-22"25, The electrochemical reversibility of lithium insertion was, reportedly, not very good 4. Recently, high electrochemical capacity (x - 0.82, i.e. 275 mAh/g) was reported for hydrothermal Iy grown TiO2(B) nanowires, which were superior to the bulk TiO2(B) 8. A comparative theoretical study of Li-insertion into anatase and TiO2(B) points at beneficial properties of the latter 19. The TiO2(B) lattice has parallel infinite channels, in which Li+ can be accommodated, without any significant distortion of the structure 19. The diffusion control of Li1 storage in a bulk crystal can be traced by methods, such as cyclic voltammetry 33 and chronoamperometry "4, which employ concepts and principles translated, essentially, from the solution electrochemistry. This philosophy provides useful physical parameters, such as diffusion coefficients Of Li+ in a solid. For instance, the Li4Ti5O]2 (spinel) 35 and TiO2 (anatase) 33>34 have been successfully treated by this methodology.
Summary of the invention
Electrochemical capacitors can be divided into two subcategories: (i) double-layer capacitors in which the interfacial capacitance at the electrode/electrolyte interface can be modelled as two parallel sheets of charge; and (H)
The present invention relates to certain solid host structures that could accumulate Li in a process, which is not controlled by the diffusion inside the solid, but the material behaves like a pseudocapacitive charge-storage medium. In a pseudocapacitor charge transfer between the electrolyte and the electrode occurs over a wide potential range as a result of oxidation/reduction reactions between the electrode and the electrolyte. Pseudocapacitors are being developed for high-pulse power applications.
The inventors of the present patent application have surprisingly discovered that this pseudocapacitive energy storage can accumulate Li much faster then the process of ordinary lithium insertion or intercalation. Consequently, the power density of such device is much higher. Compared to double-layer capacitive energy storage, our invention provides much higher energy density. A consequent requirement of any electrochemical cell is that it should have both high power and high energy densities. In the state of the art batteries, only one of these requirements has been achieved at reasonable cost, but not both. Thus, the present invention provides an electrochemical cell which may be used in a portable electronic devices, EV or HEV, while at least one of the electrodes comprise a solid host structure, which is not limited kinetically by the diffusion of Li inside the solid. An example of such electrode materials is TiO2(B).
EXPERIMENTAL SECTION
Materials
The precursor, X-ray amorphous TiO2, was prepared by precipitation of the aqueous solution of K2TiF6 (Aldrich) with ammonium hydroxide solution (25wt.%, Fhika). The product was washed with H2O and dried, SBET = 584 m2/g. The concentration of K was negligible in the product, as indicated by ESCA and AAS analyses. Alternatively, the amorphous TiO2 (SBET = 518 m2/g) was prepared by hydrolysis of titanium ethoxide at O0C as described elsewhere 31.
Sample A: 3.5g of amorphous TiO2 was autoclaved in 100 mL of 10 M NaOH at 2500C for 48 hours, then washed with H2O and autoclaved in 0.1 M HNO3 at 2000C for 2.5 hours. The dried sample was then calcined at 5000C for 1 hour.
Sample B: 1O g of amorphous TiO2 was mixed with 7.78 g of Cs2COs (Aldrich) and mortared carefully. The mixture was then decarbonated at 8000C for 4 hours, mortared again and annealed at 8000C in a crucible with a tight for 24 hours twice, with grinding at the interval. The product was then mortared and ion-exchanged with I N HCl for 4 x 24 hours at vigorous stirring with the fresh acid every 24 hours. The amount of IN HCl was
100 mL per 1 g of product. The dried sample was finally calcined at 5000C for 1 hour.
The product's surface area was SBET = 34.6 nrVg.
Sample C: This material was prepared according to the original synthetic protocol of TiO2(B) 3. An intimate mixture of 20 g KNO3 (Aldrich) and 31.6 g of TiO2 (Bayer,
PKP04090) was annealed at 10000C for 2 days. The product was mortared and hydrolyzed with 0.4 N HNO3 for 3 days at vigorous stirring with the fresh acid every 24 hours. 1 g of the powder corresponded to 100 mL of 0.4 N HNO3. The sample was dried in air at ambient temperature, then under vacuum overnight and calcined at 5000C for 30 min. The product's surface area was SBET = 9.7 m2/g.
Preparation of electrodes
Powder sample was dispersed in aqueous medium into viscous paste according to the previously developed methods 28"32. The powder (0.3 g) was mixed under stirring or gentle mortaring with 0.8 mL of 10 % aqueous solution of acety lacetone. Subsequently, 0.8 mL of 4 % aqueous solution of hydroxypropylcelulose (Aldrich, MW 100,000) was added and finally 0.4 mL of 10 % aqueous solution of Triton-XIOO (Fluka). Before use, the prepared slurry was homogenized by stirring. If the slurry was too viscous, it was further diluted by water. Titanium grid (5 x 15 mm, Goodfellow) was used as the electrode support. Electrodes were prepared by dip-coating, the coated area was ca. 5 x 5 mm. The prepared electrodes were dried in air, and finally calcined in air at 450 0C for 30 min. The amount of active electrode material was between 0.2 to 0.7 mg. Blank experiments confirmed that a bare Ti grid had negligible electrochemical charge capacity compared to that of the active material. Alternatively, the slurry was also deposited on a sheet of conducting glass (F-doped SnO2, TEC 8 from Libbey-Owens-Ford, 8 Ω/square) using a doctor-blading technique 32. The sheet of conducting glass had dimensions: 3 x 5 x 0.3 cm3. A Scotch-tape at both edges of the support (0.5 cm) defined the film thickness and left part of the support uncovered for electrical contact. The film was finally calcined for 30 min in air at 4500C. After cooling down to room temperature, the sheet was cut into ten electrodes 1.5 x 1 cm2 in size; the geometric area of the TiO2 film was 1 x 1 cm2.
Methods
Electrochemical measurements were carried out in an one-compartment cell using an Autolab Pgstat-30 (Ecochemie) controlled by the GPES-4 software. The reference and auxiliary electrodes were from Li metal, hence, potentials are referred to the Li/Li+ (IM) reference electrode. LiN(CF3SO2)2 (Fluorad HQ 115 from 3M) was dried at 130°C/l mPa. Ethylene carbonate (EC) and 1,2-dimethoxyethane (DME) were dried over the 4A molecular sieve (Union Carbide). The electrolyte solution, 1 M LiN(CF3SO2)T + EC/DME (1/1 by volume) contained 15-40 ppm H2O as determined by Karl Fischer titration (Metrohm 684 coulometer). All operations were carried out under argon in a glove box. Raman spectra were excited by an Arτ laser at 2.41 eV (Innova 305, Coherent) and recorded on a T-64000 spectrometer (Instruments, SA).
RESULTS AND DISCUSSION
Fig. 1 shows Raman spectra of the prepared materials. Sample A is apparently a mixture of anatase and TiO2(B), but the spectra of samples B and C can be assigned to pure TiO2(B) 8>13'14. The formation of pure TiO2(B) in sample B (Fig. 1) is surprising. The employed synthetic protocol should, actually, lead to the orthorhombic lepidocrocite-like protonic titanate, HxTi2-v/4αχ/4O4. This species is characterized by ideally flat sheets of edge-sharing TiOo octahcdra 36"38, which should convert directly into anatase 1O'U, without the intermediate crystallization of TiO2(B). Commercial nanocrystalline anatase TiO2 (Bayer) provided mixtures of TiO2(B) and anatase or pure anatase in the final product, but the synthesis starting from amorphous TiO2 (see Experimental Section) lead, unexpectedly, to pure TiO2(B).
Fig. 2 shows cyclic voltammograms of samples A and B. The voltammogram of sample A exhibits a pair of cathodic/anodic peaks at 1.75 & 1.95 V (formal potential 1.85 V), which are characteristic for Li-insertion into anatase lattice 28>29.32>3j.39-43 > ψe have previously denoted this pair of peaks as "A-peaks" 28. In addition to that, the voltammogram shows two pairs of peaks with formal potentials of 1.52 and 1.59 V vs. Li/LF, respectively, denoted Sl and S2, respectively 28. The notation came from our assumption that these S-peaks could be assigned to the surface-confined process in titania nanosheets 2S or in "amorphous phase" 26'27. However, this assumption needs revision in view of the new facts accumulated here. The sole features assignable to S-peaks occur in both samples B and C, which are pure TiO2(B). This generates a logical conclusion that the S-peaks at ] .52 and 1.59 V are, actually, signatures of TiO2(B). The Li-storage capacity (Li/Ti = x) at the slowest voltammetric scan (0.1 mV/s) was 0.53 (sample A), 0.68 (sample B). These capacities are comparable to those reported for galvanostatic charging of bulk TiO2(B) (x « 0.5- 0.75) 4'22'25 but smaller than the values obtained for galvanostatic charging of TiO2(B) nanowires (x = 0.82) 8. Also from theoretical arguments, the Li-insertion beyond the x = 0.5 becomes rather difficult 19.
Fig. 3 demonstrates the behavior of S-peaks in phase-pure sample B at varying scan rates. The peak currents were normalized with respect to the peak current at the slowest scan (0.1 mV/s) and plotted against the scan rate (inset in Fig. 3). Apparently, the currents scale with the first power of scan rate, which is typical for capacitive charging:
i = dQ/dt = C dE/άt = Cv, ( 1 )
Q is the voltammetric charge and άElάt the scan rate, v. However, sole capacitive double- layer charging (Eq. 1) should give featureless voltammogram (ideally rectangle assuming C invariant of potential). The peak structure with small peak-to-peak splitting (ca. 50-100 mV at v = 0.1 mV/s) points at a surface-confined charge transfer process, which can be considered faradaic pseudocapacitance. The found Li-storage capacity (x « 0.5-0.7) considerably exceed the "ordinary" capacity of the TiO2 surface assuming solely the double-layer plus the faradaic pseudocapacitance of surface states 39. Consequently, this behavior is specific for the TiO2(B), and we may suggest that its open structure with freely accessible channels 19 is responsible for this unusually fast Li-charging of a TiO2(B) crystal.
The different mechanism of Li-storage in TiO2(B) and anatase is explicitly demonstrated on sample A (Fig. 4) which is a mixture of both phases. The plot of peak currents against the scan rate is shown on chart B (Fig. 4). In order to analyze this dependence in broader interval of v, we selected here the cathodic S-peaks and anodic A-peaks, which are better resolved at faster charging (cf. also Fig. 3). (However, the conclusions are generally valid for both cathodic and anodic peaks). Apparently, the A-peaks scale with square root of the scan rate, v, as it is expected for diffusion controlled irreversible kinetics 33'4j:
I i I = 0.4958nFAc (DmiFv/RT)m (2)
where n is number of electrons, A is the electrode area, c is the maximum concentration Of Li+ (or Ti3+) in the accumulation layer (c = 0.024 moi/cm3 for x = 0.5; cf. Eq. 1), D is diffusion coefficient and the other symbols have their usual meaning. Fig. 4B confirms that this dependence can be fitted to experimental points for v <« 2 mV/s. (For higher scan rates, the fit is still good, but the experimental points show systematic negative deviation, due to uncompensated iR drop of the cell). The behavior described by Eq. 2 is typical for Li-insertion into "ordinary" anatase lattice 26-29-32.33>39-42_ τne / a v m dependence was even found the for Li-insertion into titania nanosheets derived from lepidocrocite-like titanate 44.
Li-insertion into pure TiO2(B) was previously studied mostly by galvanostatic chronopotentiometry s-22-24. This technique is less suitable for the detection and analysis of the S-peaks. However, by derivatization of the chronopoteniometric curve and plotting of dx/άE vs. E, two pairs of cathodic/anodic peaks at ca. 1.5 and 1.6 V can be traced 24. Zachau-Christiansen et al. 24 have suggested that these peaks indicate two ordered superstructures with x = 0.33 and x = 0.5. Such peaks are virtually identical to our S- peaks. Also we may note that the S-peak at 1.6 V is stronger than the S-peak at 1.5 V (Fig. 2), i.e. the first formed superstructure (at 1.6 V) is slightly more populated by Li than the superstructure formed at 1.5 V. However, none of the previous electrochemical studies on TiO2(B) 4>5-8-19'22>24-25 mentioned the pseudocapacitive nature of charging.
The fact that Li is accommodated in TiO2(B) via pseudocapacitive process recalls the idea of fast transport of Li"1" in parallel channels of TiO2(B) lattice 1<3. Li+ can be very mobile inside these channels by easy hoping between occupied and unoccupied sites 19. All these channels are structurally equivalent, and also the structure of Li0^TiO2(B) is assumed to have only crystallographically equivalent sites occupied by Li+ lξ>. Nevertheless, there are further vacant sites up to the stoichiometry of LiTiO2(B) 19. All these sites are pseudo-octahedral with a coordination number 5 (LiOs) 19'25, while two kinds of these sites are detectable by 7Li-NMR 25.
Figure captions
Figure 1: Raman spectra of the prepared materials [A] Sample prepared by hydrothermal growth [B] sample prepared from amorphous TiO2 [C] sample prepared from H2Ti4Og-H2O (bronze). Spectra B and C are assignable to monoclinic TiO2(B), spectrum [A] shows also the anatase peaks (marked by arrows) in addition to TiO2(B). The Raman intensities of samples A and B are multiplied by a factor of 10 and 4, respectively. Spectra are offset for clarity.
Figure 2: Cyclic voltammograms in IM LiN(CF3SO2)2 + EC/DME (1:1, v:v); scan rate 0.1 mV/s. [A] Sample prepared by hydrothermal growth [B] sample prepared from from amorphous TiO2.
Figure 3: Cyclic voltammograms of sample B in IM LiN(CF3SO2)2 + EC/DME (1 :1, v:v); scan rale 0.1 - 1.2 mV/s (in 0.1 mV/s steps for plots from bottom to top). Inset displays the normalized peak current, i/ioi, where ι'oi is the peak current at the slowest scan (0.1 mV/s).
Figure 4: Cyclic voltammograms of sample A in IM LiN(CF3SO2)2 + EC/DME (1 :1, v:v); scan rate 0.1 - 1.0 mV/s (in 0.1 mV/s steps for plots from bottom to top). Inset displays the absolute values of normalized peak current, i/ioi, where ϊoi is the peak current at the slowest scan (0.1 mV/s). Circles: anodic peak at ca. 2 V; crosses: cathodic peak at ca. 1.5 V, squares: cathodic peak at ca. 1.6 V. References
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Claims

Claims
1. Electrochemical cell comprising at least one electrode made of a metal oxide suitable for Li accommodation via a pseudocapacitive process.
2. Electrochemical cell according to claim 1 having a power density higher than commercial Li-ion batteries, utilizing Li-accommodation via a process controlled by the diffusion inside the solid, and the energy density higher than commercial supercapacitors where the charge storage occurs at the surface.
3. Electrochemical cell according to claim 1 or 2 comprising at least one electrode from a Tiθ2(B), which is suitable for Li accommodation via a pseudocapacitive process.
4. Electrochemical cell according to claim 3, where Tiθ2(B) is active material for the negative electrode.
5. Electrochemical cell according to claim 3. where the negative electrode is made from Tiθ2(B) and is combined with positive electrode like LiCoθ2, LiMn2θ4, LiFePOφ LiNiC^.
6. Electrochemical cell according to claim 3 having an energy density higher by a factor of 1.16 compared with similar cell using T1O2 (anatase).
7. Electrochemical cell according to claim 3 having an energy density of at least
420 milliwatt-hour per gram ( 420mWh/g).
8. Electrochemical cell according to claim 3 having a peak power density higher by a factor of 2 compared with the cell using T1O2 (anatase) at the scan rate of 2 mV/s.
9. Electrochemical cell according to claim 3 having a peak power density of at least 20 Watt per gram ( >20W/g).
10. Hydrogen storage device comprising at least one electrode made of a metal oxide.
11. Hydrogen storage device according to claim 10 comprising at least one electrode made of Tiθ2(B).
12. Pseudocapacitor comprising at least one electrode made of Tiθ2(B).
13. . Use of an electrode made of Tiθ2(B) in a pseudocapacitor.
14. Electrochemical cell according to claim 1 having an electrode of metal oxide comprising current collector, binder and conducting additives.
15. Synthetic method providing phase-pure Ti(>>(B) from amorphous Tiθ2 and
CS2CO3 via solid state reaction, Cs+/H+ exchange and thermal dehydratation.
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JP2011048977A (en) * 2009-08-26 2011-03-10 Toshiba Corp Active material for battery, nonaqueous electrolyte battery, and battery pack
WO2011116788A1 (en) 2010-03-25 2011-09-29 Saint Petersburg State University Layered titanates
JP5017492B2 (en) * 2009-05-28 2012-09-05 株式会社東芝 Non-aqueous electrolyte battery active material, non-aqueous electrolyte battery and battery pack
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EP1870949A1 (en) * 2006-06-20 2007-12-26 Commissariat A L'energie Atomique Lithium-ion battery comprising TiO2-B as active material of the negative electrode
US8724293B2 (en) 2006-10-20 2014-05-13 Ishihara Sangyo Kaisha, Ltd. Storage device
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US8647774B2 (en) 2009-05-28 2014-02-11 Kabushiki Kaisha Toshiba Non-aqueous electrolytic batteries containing an active material including a monoclinic B-type titanium composite oxide
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US9150425B2 (en) 2009-08-26 2015-10-06 Kabushiki Kaisha Toshiba Active material for battery, non-aqueous electrolyte battery and battery pack
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122 Ep: pct application non-entry in european phase