WO2019121567A1 - Electrochemical energy storage device - Google Patents
Electrochemical energy storage device Download PDFInfo
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- WO2019121567A1 WO2019121567A1 PCT/EP2018/085313 EP2018085313W WO2019121567A1 WO 2019121567 A1 WO2019121567 A1 WO 2019121567A1 EP 2018085313 W EP2018085313 W EP 2018085313W WO 2019121567 A1 WO2019121567 A1 WO 2019121567A1
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- WIPO (PCT)
- Prior art keywords
- energy storage
- storage device
- electrochemical energy
- electrode
- electrochemical
- Prior art date
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- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000003990 capacitor Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- -1 polytetrafluorethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000010955 niobium Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- SINKDKBDOQKXDM-UHFFFAOYSA-N manganese;tetrahydrate Chemical compound O.O.O.O.[Mn] SINKDKBDOQKXDM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the invention relates to an electrochemical energy storage device, in particular an electrochemical capacitor. Furthermore, the invention relates to the use of certain poly cationic compounds in such electrochemical energy storage devices.
- Electrochemical capacitors play an intermediate role between traditional electrostatic capacitors and batteries in terms of energy density and power density.
- Electrochemical capacitors can generally be divided into one of two subcategories: double-layer capacitors in which the interfacial capacitance at the electrode/electrolyte interface can be modeled as two parallel sheets of charge; and pseudocapacitor devices in which charge transfer between the electrolyte and the electrode occurs over a wide potential range, and is the result of primary, secondary, and tertiary oxidation/reduction reactions between the electrode and the electrolyte.
- These types of electrochemical capacitors are, for example, developed for high-pulse power applications.
- US 5,392,191 describes a multi-face anode material for an aqueous electrochemical capacitor, having at least one amorphous phase and having the formula: TM a O b X c , wherein TM is a transition metal selected from Y, Zr, Ti, Hf, Nb, and Sc; O is oxygen, X is a halogen modifier element; and a is between 0.1 and 3.0, b is between 1.0 and 7.0, and c is between 0.0 and 5.0.
- TM is a transition metal selected from Y, Zr, Ti, Hf, Nb, and Sc
- O oxygen
- X is a halogen modifier element
- a is between 0.1 and 3.0
- b is between 1.0 and 7.0
- c is between 0.0 and 5.0.
- US 2017/0084401 Al discloses a hybrid electrochemical energy storage device which can be a pseudocapacitor with a cathode having a coated activated carbon powder which is coated with metal oxides, metal nitrides, metal sulfites, metal phosphates, polymers, and ion conducting or solid electrolytes.
- the metal oxides may be selected among classic pseudocapacitor materials, such as Ru0 2 , Mn0 2 , etc.
- Ni(OH) 2 are limited by high costs, low capacities or limited potential windows, respectively.
- oxygen- vacancy-mediated redox pseudocapacitance for a nanostructured lanthanum-based perovskite, namely LaMnCfi.
- the present inventors found that a certain class of polycationic compounds solves the above problems. It was found that these compounds exhibit a large energy density, a high surface oxygen diffusion coefficient and an oxygen deficiency which makes them useful as pseudocapacitors in electrochemical energy storage devices.
- the present invention therefore relates to an
- electrochemical energy storage device comprising
- a first electrode comprising a polycationic compound of the Formula
- M 1 is a metal of IUPAC Group 3
- M 2 is V, Nb or Ta
- M 3 is Cr, Mo or W
- M 4 is Ca, Sr or Ba, a is 0.8 to 1,
- c 0 to 0.2
- e 0 to 0.2
- electrolyte wherein the electrolyte is in ionic contact with the first electrode and the second electrode.
- the present invention relates to the use of the above polycationic compounds in an electrochemical energy storage device, preferably an electrochemical capacitor.
- the invention relates to a method of manufacturing an electrochemical energy storage device, preferably an electrochemical capacitor, which comprises mixing the above polycationic compound with a carbonaceous material and optionally a binder material to obtain an electrode.
- the electrochemical energy storage device of the present invention comprised a first electrode, a second electrode and an electrolyte which is in ionic contact with the two electrodes.
- the first electrode comprises a polycationic compound of the formula
- M 1 is a metal of IUPAC Group 3
- M 2 is V, Nb or Ta
- M 3 is Cr, Mo or W
- M 4 is Ca, Sr or Ba
- a 0.8 to 1
- c 0 to 0.2
- e 0 to 0.2
- M 1 is a metal of IUPAC Group 3, i.e. Sc, Y, and the lanthanides and actinides.
- M 1 is a lanthanide metal, more preferably Ce.
- M 2 is V, Nb or Ta, preferably Nb.
- M 3 is Cr, Mo or W.
- M 4 is Ca, Sr or Ba.
- a 0.8 to 1
- b 0.8 to 1
- e 0 to 0.2
- c 0 to 0.2
- d is 4 and 0 ⁇ delta ⁇ 0.33.
- the first electrode comprises CeNb0 4+deita ⁇
- delta is defined as above.
- the polycationic compounds used in the invention can be prepared by usual methods known to a person skilled in the art.
- a suitable method is, for example, a solid stat reaction using manual grinding in acetone of suitable metal oxides, thermogravimetrically essayed or thermally pre-treated, and weighted in stoichiometric proportions. After decarbonation at l000°C for 12 h, the intermediate mixtures are ground, pressed into pellets and heated in air at different temperatures for 12 h before being slowly cooled down to obtain the monophasic oxide materials. Another method is described in the examples below.
- the first electrode may further include carbonaceous electronic
- conductivity enhancing materials These materials are provided to facilitate the flow of current generated by the material during the electrochemical reactions.
- Suitable carbonaceous materials are, for example, carbon black, graphite, carbon nanotubes and mixtures thereof.
- the carbonaceous material may be present in the first electrode in an amount of, for example, up to 40 wt.% of the total amount of the polycationic compound, the carbonaceous material and, if present, any binder material.
- the first electrode may also include a binder material to promote adhesion of the material.
- binder material examples include
- the binder material may be present in the first electrode in an amount of, for example, up to 20 wt.% based on the total weight of the polycationic compound, the
- any electrode suitable for an electrochemical energy storage device may be used.
- the second electrode can be a platinum electrode.
- the electrochemical energy storage device of the invention furthermore comprises an electrolyte which is in ionic contact with the two electrodes.
- the electrolyte may be an aqueous electrolyte, such as an alkaline electrolyte, an acid electrolyte or a neutral electrolyte.
- the electrolyte is an aqueous electrolyte having a pH in the range of from 5 to 9, preferably in the range of from 6 to 8, and most preferably of about 7.
- the electrolyte comprises an alkali metal salt, such as an alkali metal nitrate or an alkali metal hydroxide, for example LiNCF, NaNCF, KNO 3 , LiOH, NaOH, KOH, or any mixtures thereof.
- an alkali metal salt such as an alkali metal nitrate or an alkali metal hydroxide, for example LiNCF, NaNCF, KNO 3 , LiOH, NaOH, KOH, or any mixtures thereof.
- a particularly preferred electrolyte comprises 5M L1NO 3 and has a pH of about 7.
- the electrochemical energy storage device according to the invention may further comprise a separator positioned between the first electrode and the second electrode and in ionic contact with the electrolyte.
- a separator may be fabricated of a number of separator materials as are known in the art. Specific examples of such separators include porous cellulose, porous silica, glass wool, glass fiber, polypropylene, and combinations thereof.
- the electrochemical energy storage device according to the invention is an electrochemical capacitor.
- the invention furthermore relates to the use of the above defined polyactionic compounds in an electrochemical energy storage device, preferably an electrochemical capacitor.
- the invention also relates to a method of manufacturing an electrochemical energy storage device, preferably an electrochemical capacitor, which comprises mixing a polycationic compound as defined above with a carbonaceous material and optionally a binder material to obtain an electrode. Such electrode may then be used in an electrochemical energy storage device, such as an electrochemical capacitor.
- Figure 1 shows a cycle life up to 8000 cycles and a capacity of about 20 F/g for CeNb0 4+deita (Example 1).
- Figure 2 shows a cycling behavior for LaMnCh (Comparative Example) between 0.3 V and 0.8 V, which was conducted at a rate of 10 mV. s 1 .
- the structure, morphology and chemical composition of the prepared nanoparticles of the polycationic compounds were characterized by X-ray diffraction (XRD, PANalytical X'Pert Pro with an X’Celerator detector and Cu Ka radiation), transmission electron microscopy (TEM, Hitachi H9000-NAR) and energy-dispersive X-ray analysis (EDX, Oxford Instrument).
- XRD X-ray diffraction
- TEM transmission electron microscopy
- EDX energy-dispersive X-ray analysis
- Oxford Instrument Oxford Instrument
- Brunauer-Emmett-T eller (BET) surface area measurements were performed with a Quantachrome Nova 4200e operated with nitrogen gas.
- the electrochemical performance was measured by cyclic voltammetry (CV) with a VMP3 galvanostat-potentiostat from Biologic run under ECLab software.
- the experiments were conducted in a 3 electrode cell assembly, using Ag/AgCl (3M NaCl) as the reference electrode, a platinum grid as the counter electrode, and 5M L1NO 3 as the electrolyte.
- Capacities of the electrodes were calculated by integrating the reductive part of the CVs.
- the voltammetric charge related to the presence of carbon black in the composite electrodes was subtracted prior to di vide by the width of the potential window to calculate the electrode capacitance.
- the capacitance was divided by the mass of active material to evaluate the specific capacitance of the powders.
- the volumetric capacitance was obtained by multiplying this value by the density that was calculated from the refined XRD lattice parameters.
- the working electrode was prepared as follows:
- the working electrodes were prepared by mixing 60 wt.% of the polycationic compound with 30 wt.% of "Superior Graphite" and 10 wt.% of PTFE. The mixture was homogenized in ethanol with magnetic stirring and heated to total evaporation of the solvent. The solid suspension was rolled manually to obtain a basis weight of about 5 to 10 mg/cm 2 . A 12 mm diameter sample was taken by punch and pressed between two stainless steel grids serving as a current collector under a pressure of 900 MPa.
- CeNb0 4 was synthesized by hydrothermal route starting from cerium nitrate in water and niobium chloride in ethanol. Precipitate was obtained by mixing these two solutions and adjusting the pH at 10 by ammonia addition. This precipitate was sealed in a polytetrafluoroethylene (PTFE)-lined autoclave which was maintained at at 240°C during 12 h before being centrifuged and washed sequentially in water and ethanol and then dried.
- PTFE polytetrafluoroethylene
- LaMnCF was synthesized by autocombustion route starting from lanthanum nitrate and manganese tetrahydrate.
- Gel was obtained by dehydration, followed by heat treatment at 300°C (10 h under air) before a heating treatment at 700°C during 5 hours, leading to a specific surface of 10 m 2 /g.
- Capacitance was measured below 30 pF/cm 2 which was attributed to electrochemical double layer capacitance and not pseudocapacitance.
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Abstract
The invention relates to an electrochemical energy storage device, in particular an electrochemical capacitor. Furthermore, the invention relates to the use of certain polycationic compounds in such electrochemical energy storage devices.
Description
Electrochemical energy storage device
CROSS-REFERENCE TO RELATED APPLICATION
The present application claims priority to European application No. 17306836.2 filed on December 19, 2017, the whole content of this application being incorporated herein by reference. Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
TECHNICAL FIELD OF THE INVENTION
The invention relates to an electrochemical energy storage device, in particular an electrochemical capacitor. Furthermore, the invention relates to the use of certain poly cationic compounds in such electrochemical energy storage devices.
BACKGROUND
Electrochemical capacitors play an intermediate role between traditional electrostatic capacitors and batteries in terms of energy density and power density.
Electrochemical capacitors can generally be divided into one of two subcategories: double-layer capacitors in which the interfacial capacitance at the electrode/electrolyte interface can be modeled as two parallel sheets of charge; and pseudocapacitor devices in which charge transfer between the electrolyte and the electrode occurs over a wide potential range, and is the result of primary, secondary, and tertiary oxidation/reduction reactions between the electrode and the electrolyte. These types of electrochemical capacitors are, for example, developed for high-pulse power applications.
As the chare and discharge rates of electrochemical capacitors are orders of magnitude faster than batteries, there have been considerable efforts to increase the energy density of pseudocapacitor materials. Metal oxides have gained significant interest owing to their reversible Faradaic surface reactions that allow for up to an order of magnitude greater energy storage than carbon-based electrochemical double-layer capacitors.
For example, US 5,392,191 describes a multi-face anode material for an aqueous electrochemical capacitor, having at least one amorphous phase and
having the formula: TMaObXc, wherein TM is a transition metal selected from Y, Zr, Ti, Hf, Nb, and Sc; O is oxygen, X is a halogen modifier element; and a is between 0.1 and 3.0, b is between 1.0 and 7.0, and c is between 0.0 and 5.0.
US 2017/0084401 Al discloses a hybrid electrochemical energy storage device which can be a pseudocapacitor with a cathode having a coated activated carbon powder which is coated with metal oxides, metal nitrides, metal sulfites, metal phosphates, polymers, and ion conducting or solid electrolytes. The metal oxides may be selected among classic pseudocapacitor materials, such as Ru02, Mn02, etc.
However, classic pseudocapacitor materials including Ru02, Mn02 and
Ni(OH)2 are limited by high costs, low capacities or limited potential windows, respectively.
In an effort to overcome these deficiencies, J.T. Mefford, et al. in Nature Materials, vol. 13, 2014, 726-732 investigate the mechanism of
oxygen- vacancy-mediated redox pseudocapacitance for a nanostructured lanthanum-based perovskite, namely LaMnCfi. The authors claim that this was the first example of anion-based intercalation pseudocapacitance as well as the first time that oxygen intercalation has been exploited for fast energy storage.
In view of the increasing power and energy demands for next-generation electronic devices, there is still a demand for improved energy storage devices. There is therefore a need for new pseudocapacitor materials exhibiting improved energy density, high operating voltage, and exceptional behavior in cycling. SUMMARY
The present inventors found that a certain class of polycationic compounds solves the above problems. It was found that these compounds exhibit a large energy density, a high surface oxygen diffusion coefficient and an oxygen deficiency which makes them useful as pseudocapacitors in electrochemical energy storage devices. The present invention therefore relates to an
electrochemical energy storage device, comprising
a first electrode comprising a polycationic compound of the Formula
Ma 1Mb 2Mc 3Me4Od Kleto
wherein
M1 is a metal of IUPAC Group 3,
M2 is V, Nb or Ta,
M3 is Cr, Mo or W,
M4 is Ca, Sr or Ba,
a is 0.8 to 1,
b is 0.8 to 1
c is 0 to 0.2,
e is 0 to 0.2,
a + e = 1,
b + c = 1,
d is 4, and
0 < delta < 0.33,
a second electrode; and
an electrolyte, wherein the electrolyte is in ionic contact with the first electrode and the second electrode.
Furthermore, the present invention relates to the use of the above polycationic compounds in an electrochemical energy storage device, preferably an electrochemical capacitor.
Furthermore, the invention relates to a method of manufacturing an electrochemical energy storage device, preferably an electrochemical capacitor, which comprises mixing the above polycationic compound with a carbonaceous material and optionally a binder material to obtain an electrode.
DETAILED DESCRIPTION
The electrochemical energy storage device of the present invention comprised a first electrode, a second electrode and an electrolyte which is in ionic contact with the two electrodes. The first electrode comprises a polycationic compound of the formula
Ma 1Mb 2Mc 3Me4Od Kleto
wherein
M1 is a metal of IUPAC Group 3,
M2 is V, Nb or Ta,
M3 is Cr, Mo or W,
M4 is Ca, Sr or Ba,
a is 0.8 to 1,
b is 0.8 to 1
c is 0 to 0.2,
e is 0 to 0.2,
a + e =1,
b + c = 1,
d is 4, and
0 < delta < 0.33.
M1 is a metal of IUPAC Group 3, i.e. Sc, Y, and the lanthanides and actinides. Preferably, M1 is a lanthanide metal, more preferably Ce.
M2 is V, Nb or Ta, preferably Nb.
M3 is Cr, Mo or W.
M4 is Ca, Sr or Ba.
In the above formula of the polycationic compound, a is 0.8 to 1, b is 0.8 to 1 , e is 0 to 0.2 and c is 0 to 0.2, provided that b + c = 1 and a + e = 1 , d is 4 and 0 < delta < 0.33.
In one embodiment 0 < c < 0.2.
In one embodiment, the first electrode comprises CeNb04+deita· In this compound, "delta" is defined as above.
The polycationic compounds used in the invention can be prepared by usual methods known to a person skilled in the art. A suitable method is, for example, a solid stat reaction using manual grinding in acetone of suitable metal oxides, thermogravimetrically essayed or thermally pre-treated, and weighted in stoichiometric proportions. After decarbonation at l000°C for 12 h, the intermediate mixtures are ground, pressed into pellets and heated in air at different temperatures for 12 h before being slowly cooled down to obtain the monophasic oxide materials. Another method is described in the examples below.
The first electrode may further include carbonaceous electronic
conductivity enhancing materials. These materials are provided to facilitate the flow of current generated by the material during the electrochemical reactions. Suitable carbonaceous materials are, for example, carbon black, graphite, carbon nanotubes and mixtures thereof.
The carbonaceous material may be present in the first electrode in an amount of, for example, up to 40 wt.% of the total amount of the polycationic compound, the carbonaceous material and, if present, any binder material.
The first electrode may also include a binder material to promote adhesion of the material. Examples of appropriate binder materials include
polytetrafluorethylene (Teflon), polyvinylidene difluoride (PVDF) and poly(vinylidene difluoride-co-hexafluoropropylene) (PVDF-HFP). The binder material may be present in the first electrode in an amount of, for example, up to 20 wt.% based on the total weight of the polycationic compound, the
carbonaceous material and the binder material.
As second electrode, any electrode suitable for an electrochemical energy storage device may be used. For example, the second electrode can be a platinum electrode.
The electrochemical energy storage device of the invention furthermore comprises an electrolyte which is in ionic contact with the two electrodes. The electrolyte may be an aqueous electrolyte, such as an alkaline electrolyte, an acid electrolyte or a neutral electrolyte. In a preferred embodiment, the electrolyte is an aqueous electrolyte having a pH in the range of from 5 to 9, preferably in the range of from 6 to 8, and most preferably of about 7.
In one embodiment, the electrolyte comprises an alkali metal salt, such as an alkali metal nitrate or an alkali metal hydroxide, for example LiNCF, NaNCF, KNO3, LiOH, NaOH, KOH, or any mixtures thereof. A particularly preferred electrolyte comprises 5M L1NO3 and has a pH of about 7.
In one embodiment, the electrochemical energy storage device according to the invention may further comprise a separator positioned between the first electrode and the second electrode and in ionic contact with the electrolyte. Such separator may be fabricated of a number of separator materials as are known in the art. Specific examples of such separators include porous cellulose, porous silica, glass wool, glass fiber, polypropylene, and combinations thereof.
In one embodiment, the electrochemical energy storage device according to the invention is an electrochemical capacitor.
The invention furthermore relates to the use of the above defined polyactionic compounds in an electrochemical energy storage device, preferably an electrochemical capacitor.
Finally, the invention also relates to a method of manufacturing an electrochemical energy storage device, preferably an electrochemical capacitor, which comprises mixing a polycationic compound as defined above with a carbonaceous material and optionally a binder material to obtain an electrode. Such electrode may then be used in an electrochemical energy storage device, such as an electrochemical capacitor.
The present invention will now be explained with reference to the following examples which are not intended as being limiting.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a cycle life up to 8000 cycles and a capacity of about 20 F/g for CeNb04+deita (Example 1).
Figure 2 shows a cycling behavior for LaMnCh (Comparative Example) between 0.3 V and 0.8 V, which was conducted at a rate of 10 mV. s 1.
EXAMPLES
For the following examples, the structure, morphology and chemical composition of the prepared nanoparticles of the polycationic compounds were characterized by X-ray diffraction (XRD, PANalytical X'Pert Pro with an X’Celerator detector and Cu Ka radiation), transmission electron microscopy (TEM, Hitachi H9000-NAR) and energy-dispersive X-ray analysis (EDX, Oxford Instrument). Brunauer-Emmett-T eller (BET) surface area measurements were performed with a Quantachrome Nova 4200e operated with nitrogen gas.
The electrochemical performance was measured by cyclic voltammetry (CV) with a VMP3 galvanostat-potentiostat from Biologic run under ECLab software. The experiments were conducted in a 3 electrode cell assembly, using Ag/AgCl (3M NaCl) as the reference electrode, a platinum grid as the counter electrode, and 5M L1NO3 as the electrolyte.
Capacities of the electrodes were calculated by integrating the reductive part of the CVs. The voltammetric charge related to the presence of carbon black in the composite electrodes was subtracted prior to di vide by the width of the potential window to calculate the electrode capacitance. Finally, the capacitance was divided by the mass of active material to evaluate the specific capacitance of the powders. The volumetric capacitance was obtained by multiplying this value by the density that was calculated from the refined XRD lattice parameters.
In each example, the working electrode was prepared as follows:
The working electrodes were prepared by mixing 60 wt.% of the polycationic compound with 30 wt.% of "Superior Graphite" and 10 wt.% of PTFE. The mixture was homogenized in ethanol with magnetic stirring and heated to total evaporation of the solvent. The solid suspension was rolled manually to obtain a basis weight of about 5 to 10 mg/cm2. A 12 mm diameter sample was taken by punch and pressed between two stainless steel grids serving as a current collector under a pressure of 900 MPa.
Example 1
CeNb04 was synthesized by hydrothermal route starting from cerium nitrate in water and niobium chloride in ethanol. Precipitate was obtained by mixing these two solutions and adjusting the pH at 10 by ammonia addition. This precipitate was sealed in a polytetrafluoroethylene (PTFE)-lined autoclave which
was maintained at at 240°C during 12 h before being centrifuged and washed sequentially in water and ethanol and then dried.
From the obtained powder an electrode was prepared (see previous section) and a cycling between -0.7 V and 0,9V was conducted at a rate of 20 mV. s 1.
The behavior is presented in Figure 1 showing a capacity of ~20 F/g and a good stability for 7000 cycles.
Comparative Example
LaMnCF was synthesized by autocombustion route starting from lanthanum nitrate and manganese tetrahydrate. Citric acid (AC) and ethylene glycol (EG) were added in the proportion [AC]/[Metallic Cations] = 3 and [EG]/[AC] = 2. Gel was obtained by dehydration, followed by heat treatment at 300°C (10 h under air) before a heating treatment at 700°C during 5 hours, leading to a specific surface of 10 m2/g.
From the obtained powder an electrode was prepared as explained above and a cycling between 0.3 V and 0.8 V was conducted at a rate of 10 mV. s 1.
The behavior is presented in Figure 2.
Capacitance was measured below 30 pF/cm2 which was attributed to electrochemical double layer capacitance and not pseudocapacitance.
Claims
1. An electrochemical energy storage device, comprising a first electrode comprising a polycationic compound of the Formula
Ma'Mb^Me ^a wherein
M1 is a metal of IUPAC Group 3,
M2 is V, Nb or Ta,
M3 is Cr, Mo or W,
M4 is Ca, Sr or Ba, a is 0.8 to 1, b is 0.8 to 1 c is 0 to 0.2, e is 0 to 0.2, a + e =1, b + c = 1, d is 4, and 0 < delta < 0.33, a second electrode; and an electrolyte, wherein the electrolyte is in ionic contact with the first electrode and the second electrode.
2. The electrochemical energy storage device according to claim 1, wherein M1 is a lanthanide metal, preferably Ce.
3. The electrochemical energy storage device according to claim 1 or 2, wherein M2 is Nb.
4. The electrochemical energy storage device according to any one of the preceding claims, wherein 0 < c < 0.2.
5. The electrochemical energy storage device according to any one of the preceding claims, wherein the polycationic compound comprises CeNb04+deita·
6. The electrochemical energy storage device according to any one of the preceding claims, wherein the first electrode further comprises a carbonaceous material, preferably carbon black, graphite, carbon nanotubes or mixtures thereof.
7. The electrochemical energy storage device according to any one of the preceding claims, wherein the first electrode further comprises a binder material, preferably a polymeric binder material, more preferably polytetrafluorethylene (Teflon), polyvinylidene difluoride (PVDF) or poly(vinylidene
difluoride-co-hexafluoropropylene) (PVDF-HFP).
8. The electrochemical energy storage device according to claim 6 or 7, wherein the carbonaceous material is present in an amount of up to 40 wt.% and the binder material is present in an amount of up to 20 wt.%, each based on the total weight of the polycationic compound, the carbonaceous material and the binder material.
9. The electrochemical energy storage device according to any one of the preceding claims, wherein the electrolyte is an aqueous electrolyte.
10. The electrochemical energy storage device according to claim 9, wherein the aqueous electrolyte has a pH in the range of from 5 to 9.
11. The electrochemical energy storage device according to any one of the preceding claims, further comprising a separator positioned between the first electrode and the second electrode and in ionic contact with the electrolyte.
12. The electrochemical energy storage device according to any one of the preceding claims, which is an electrochemical capacitor.
13. Use of a polycationic compound as defined in any one of claims 1 to 5 in an electrochemical energy storage device.
14. Use according to claim 13, wherein the electrochemical energy storage device is an electrochemical capacitor.
15. Method of manufacturing an electrochemical energy storage device, preferably an electrochemical capacitor, which comprises mixing a polycationic compound as defined in any one of claims 1 to 5 with a carbonaceous material and optionally a binder material to obtain an electrode.
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