KR20140023908A - Metal-free aqueous electrolyte energy storage device - Google Patents

Metal-free aqueous electrolyte energy storage device Download PDF

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KR20140023908A
KR20140023908A KR1020137025490A KR20137025490A KR20140023908A KR 20140023908 A KR20140023908 A KR 20140023908A KR 1020137025490 A KR1020137025490 A KR 1020137025490A KR 20137025490 A KR20137025490 A KR 20137025490A KR 20140023908 A KR20140023908 A KR 20140023908A
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cathode
anode
electrochemical
electrode
stack
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KR1020137025490A
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KR101823873B1 (en
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제이 휘태커
던 험프리스
웬주오 양
에드워드 린치-벨
알렉스 모하마드
에릭 웨버
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아퀴온 에너지 인코포레이티드
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Priority to US201161450774P priority Critical
Priority to US13/043,787 priority
Priority to US61/450,774 priority
Priority to US13/043,787 priority patent/US8298701B2/en
Application filed by 아퀴온 에너지 인코포레이티드 filed Critical 아퀴온 에너지 인코포레이티드
Priority to PCT/US2012/028228 priority patent/WO2012122353A2/en
Publication of KR20140023908A publication Critical patent/KR20140023908A/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/04Hybrid capacitors
    • H01G11/06Hybrid capacitors with one of the electrodes allowing ions or anions to be reversibly doped thereinto, e.g. lithium-ion capacitors [LICs]
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/10Multiple hybrid or EDL capacitors, e.g. arrays or modules
    • H01G11/12Stacked hybrid or EDL capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/66Current collectors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00Hybrid cells; Manufacture thereof
    • H01M12/005Hybrid cells; Manufacture thereof composed of a half-cell of the capacitor type and of a half-cell of the primary or secondary battery type
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/0257Cases, jackets or wrappings characterised by the material
    • H01M2/0277Insulating material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/06Arrangements for introducing electric connectors into or through cases
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/20Current conducting connections for cells
    • H01M2/22Fixed connections, i.e. not intended for disconnection
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/20Current conducting connections for cells
    • H01M2/22Fixed connections, i.e. not intended for disconnection
    • H01M2/26Electrode connections
    • H01M2/266Interconnections of several platelike electrodes in parallel, e.g. electrode pole straps or bridges
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/663Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/665Composites
    • H01M4/667Composites in the form of layers, e.g. coatings
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0002Aqueous electrolytes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

An electrochemical device comprising a housing and a stack of electrochemical cells within the housing. Each electrochemical cell includes an anode electrode, a cathode electrode, a separator and an electrolyte located between the anode electrode and the cathode electrode. The electrochemical device also includes a current collector located between neighboring electrochemical cells, an anode bus operably connected to the anodes of the electrochemical cells in the stack, and a cathode bus operably connected to the cathodes of the electrochemical cells in the stack. Include. The housing, anode electrode, cathode electrode, separator, anode bus and cathode bus are nonmetals.

Description

Metal-free aqueous electrolyte energy storage device {METAL-FREE AQUEOUS ELECTROLYTE ENERGY STORAGE DEVICE}

Related Applications

This application claims the priority of US patent application 61 / 450,774, filed March 9, 2011, and US patent application 13 / 043,787, filed March 9, 2011. The entirety of applications 61 / 450,774 and 13 / 043,787 are incorporated herein by reference.

FIELD OF THE INVENTION The present invention relates to aqueous batteries and hybrid energy storage devices, and more particularly to electrochemical storage devices without metal parts in contact with the aqueous electrolyte.

Small renewable energy harvesting and power generation technologies (such as solar arrays, wind turbines, microstirling engines, and solid oxide fuel cells) are on the rise, and medium-sized secondary (rechargeable) There is a corresponding strong need for energy storage capability. Batteries for these stationary applications typically store 1-50 kWh of energy (depending on the application) and have traditionally been based on Pb-acid compounds. Deep-cycle lead-acid cell banks are known to be assembled at distributed generation points and last for 1 to 10 years according to a typical duty cycle. Although these cells are sufficiently functional to support this application, severe use of intermediates and intermediates in environmentally clean lead and acids (Pb-acid technology is estimated to account for more than 100,000 tons of Pb emissions to the environment each year in the United States alone) Many are associated with the use of these cells, including significant degradation in performance when maintained at the charge of the battery or routinely cycled to deep levels of discharge, the need for routines to function to maintain performance, and the implementation of essential recycling programs. There are problems. There is a strong desire to replace Pb-acid compounds such as those used by the automotive industry. Unfortunately, the economic effects of alternative battery compounds make it a very ineffective option to this day.

Despite all the recent advances in battery technologies, there are still no inexpensive clean alternatives to Pb-acid compounds. This is largely due to the fact that Pb-acid batteries are significantly cheaper than other compounds ($ 200 / kWh) and are currently used to develop high-energy systems for transportation applications (inherently significantly more expensive than Pb-acid batteries). The emphasis is on.

An embodiment includes a housing; And a stack of electrochemical cells in the housing. Each electrochemical cell comprises an anode electrode; Cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And an electrolyte. The electrochemical device also includes a current collector located between neighboring electrochemical cells; An anode bus operably connected to the anodes of electrochemical cells in the stack; And a cathode bus operably connected to the cathodes of the electrochemical cells in the stack. The housing, anode electrode, cathode electrode, separator, anode bus and cathode bus are nonmetals. "Non-metal" in the context of this patent application means electrically conductive materials that are not made of pure metal or metal alloys. Examples of non-metallic materials include, but are not limited to, electrically conductive metal oxides or carbon.

Another embodiment relates to a method of making an electrochemical device. The method includes depositing a first nonmetal anode electrode; Stacking a first non-metal separator on the anode electrode; Depositing a first non-metal cathode electrode on the separator. The method also includes operatively connecting the first anode electrode to a nonmetal anode bus; And operatively connecting the first cathode electrode to the non-metal cathode bus.

An embodiment includes a housing; And a stack of electrochemical cells in the housing. Each electrochemical cell comprises an anode electrode; Cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And an electrolyte. The apparatus also includes a plurality of carbon cathode and anode current collectors, alternately located between neighboring electrochemical cells; And a plurality of tabs configured to connect to the electrical bus and operably connected to the plurality of carbon cathode and anode current collectors. The cathode electrode of the first electrochemical cell is in electrical contact with the first cathode current collector. The cathode electrode of the second electrochemical cell is in electrical contact with the first cathode current collector. The second electrochemical cell is located adjacent to the first side of the first electrochemical cell in the stack. The anode electrode of the first electrochemical cell is in electrical contact with the second anode current collector. The anode electrode of the third electrochemical cell is in electrical contact with the second anode current collector. The third electrochemical cell is located adjacent to the second side of the first electrochemical cell in the stack.

Yet another embodiment includes a housing; And a stack of electrochemical cells in the housing. Each electrochemical cell comprises a compressed granular anode electrode; A separator positioned between the anode electrode and the cathode electrode; And an electrolyte. The electrochemical device also includes a plurality of cathode and anode current collectors, alternately located between neighboring electrochemical cells. The cathode electrode of the first electrochemical cell is in electrical contact with the first cathode current collector. The cathode electrode of the second electrochemical cell is in electrical contact with the first cathode current collector. The second electrochemical cell is located adjacent to the first side of the first electrochemical cell in the stack. The anode electrode of the first electrochemical cell is in electrical contact with the second anode current collector. The anode electrode of the third electrochemical cell is in electrical contact with the second anode current collector. The third electrochemical cell is located adjacent to the second side of the first electrochemical cell in the stack.

Yet another embodiment includes a housing; And a plurality of stacks of electrochemical cells arranged side by side in a housing. Each electrochemical cell comprises an anode electrode; Cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And an electrolyte. The apparatus also includes a current collector located between neighboring electrochemical cells in each of the stacks. The separator of at least one cell includes a separator sheet that extends continuously between at least two of the plurality of stacks.

An embodiment includes a housing; And a stack of electrochemical cells in the housing. Each electrochemical cell comprises an anode electrode; Cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And an electrolyte. The electrochemical device also includes a graphite sheet located between neighboring electrochemical cells in the stack. Graphite sheets are current collectors for neighboring electrochemical cells.

Yet another embodiment includes an anode electrode comprising a plurality of individual anode electrode members separated by anode boundary regions; An electrochemical cell comprising a cathode electrode comprising a plurality of individual cathode electrode members separated by cathode boundary regions. The electrochemical cell also includes a separator located between the anode electrode and the cathode electrode; And an electrolyte. The electrolyte is located in the separator and in the anode electrode and cathode electrode boundary regions. In addition, at least 50% of the anode boundary regions are not aligned with the respective cathode boundary regions throughout the separator.

Yet another embodiment is directed to a method of making an electrochemical device having a stack of electrochemical cells. The method includes forming stack electrochemical cells; And pouring an electrically insulating polymer around the stack of electrochemical cells to form a solid insulating shell, or providing a preformed solid insulating shell around the stack of electrochemical cells.

Another embodiment relates to a method of making an electrochemical device. The method includes stacking an anode electrode comprising a plurality of individual anode electrode members separated by anode boundary regions; Depositing a separator on the anode electrode; And stacking a cathode electrode on the separator, the cathode electrode comprising a plurality of individual cathode electrode members separated by cathode boundary regions. At least 50% of the anode boundary regions are not aligned with the respective cathode boundary regions over the separator, and the plurality of anode electrode members and the plurality of cathode electrode members are arranged in an array of rows and columns.

Yet another embodiment relates to a secondary hybrid aqueous energy storage device. The secondary hybrid aqueous energy storage device comprises a housing; And a stack of electrochemical cells in the housing. Each electrochemical cell comprises an anode electrode; Cathode electrode; A separator positioned between the anode electrode and the cathode electrode; An electrolyte, and a graphite sheet located between neighboring electrochemical cells. The anode and cathode electrodes are 0.05 to 1 cm thick.

1 is a schematic diagram of a prismatic stack of electrochemical cells in accordance with an embodiment.
2 is a schematic diagram of details of a current collector sandwiched in accordance with an embodiment.
3 is a perspective view of an electrochemical device having a plurality of prismatic stacks of electrochemical cells in accordance with an embodiment.
4 is another perspective view of the embodiment shown in FIG.
5 is a perspective view of an electrochemical device having a single prismatic stack of electrochemical cells in accordance with an embodiment.
6 is a perspective view of the embodiment of FIG. 5 with the electrochemical cells removed for clarity.
FIG. 7 is a schematic side cross-sectional view showing details of the portion of the embodiment shown in FIG. 5. FIG.
8 is a plot of cell capacity versus cell potential in an embodiment.
9 is a schematic diagram of an electrochemical cell in accordance with an embodiment of the invention. The electrochemical cell may be stacked in a bipolar or prismatic stack configuration.
10 is a cross-sectional view of an electrochemical cell in which the anode electrode is composed of individual anode electrode members and the cathode electrode is composed of individual cathode electrode members in accordance with an embodiment. The electrochemical cell may be stacked in a bipolar or prismatic stack configuration.
11 is a schematic diagram of an electrochemical device including a bipolar stack of electrochemical cells in accordance with an embodiment of the invention.
12 (a) is a plot of accumulation capacity versus cell potential under charge and discharge conditions over 30 cycles. 12 (b) is a plot of cell charge and discharge capacity and efficiency as a function of cycle.

Embodiments of the invention relate to electrochemical energy storage systems such as primary and secondary batteries, and hybrid energy storage systems described below. While secondary hybrid aqueous energy storage systems described below are preferred embodiments of the invention, the invention includes ions from electrolytes, including aqueous and non-aqueous electrolyte containing batteries (eg, Li-ion batteries, etc.). Reversible ratio of cations on the surface of the electrode (double layer) and / or pseudocapacitance rather than by intercalating anodes and cathodes or electrolyte capacitors (eg, by intercalating alkali ions). It can be applied to any suitable electrochemical energy storage systems, such as capacitors or pseudocapacitor anode and cathode electrodes that store charge through a Faraday reaction.

Hybrid electrochemical energy storage systems of embodiments of the present invention include a pseudocapacitor electrode (eg, an anode) coupled to a bilayer capacitor or active electrode (eg, a cathode). In these systems, the capacitor or pseudocapacitor electrode stores charge via a reversible non-Faraday reaction of alkali cations on the surface of the electrode (dual layer) and / or pseudocapacitance, The active electrode undergoes a reversible Faraday reaction at the transition metal oxide that intercalates and deintercalates alkali cations similar to batteries.

An example of a Na-based system is a US patent filed on 4/3/09, which is incorporated herein by reference in its entirety, using a spinel structure LiMn 2 0 4 battery electrode, an activated carbon capacitor electrode, and an aqueous Na 2 SO 4 electrolyte. Application number 12 / 385,277. In this system, the negative anode electrode stores charge via a reversible non-Faraday reaction of Na-ions on the surface of the activated carbon electrode. Both cathode electrodes utilize a reversible Faraday reaction of Na-ion intercalate / deintercalate at spinel lambda-Mn 2 .

In an alternative system, the cathode electrode may comprise a non-intercalate (eg, non-alkali ion intercalate) Mn0 2 phase. Examples of non-intercalate phases of manganese dioxide include electrolyte manganese dioxide (EMD), alpha phase and gamma phase.

1 illustrates a prismatic stack 100P of electrochemical cells 102 in accordance with an embodiment. In this embodiment, each of the electrochemical cells 102 in the prismatic stack 100P is an anode electrode 104, a cathode electrode 106, and a separator located between the anode electrode 104 and the cathode electrode 106. 108). The electrochemical cells 102 also include an electrolyte located between the anode electrode 104 and the cathode electrode 106 (ie, impregnated with the separator and / or the electrodes). Each of the electrochemical cells 102 in the prismatic stack 100P may be mounted within the frame 112 (see FIGS. 9-10). Alternatively or in addition, the prismatic stack 100P may be enclosed within the housing 116 (see FIGS. 3-6). Additional features of the housing 116 are provided in more detail below with respect to the embodiments shown in FIGS. 3-6. Still other embodiments of electrochemical cells 102 are shown in FIGS. 9 and 10 and discussed in more detail below. Prismatic stack 100P also includes a plurality of carbon cathode current collectors 110a and carbon anode current collectors 110c located alternately between neighboring electrochemical cells 102. The current collectors may comprise any suitable form of electrically conductive carbon, such as exfoliated graphite, carbon fiber paper, or an inert substrate coated with a carbon material. Preferably, the current collectors comprise graphite having a density greater than 0.6 g / cm 3 .

In an embodiment, the prismatic stack 100P includes a plurality of electrically conductive contacts (eg, tabs) 120 operably connected to the plurality of carbon cathode and anode current collectors 110a, 110c. The electrically conductive contacts 120 may be fixed to one side of the cathode and anode current collectors 110a and 110c. Alternatively, as shown in FIG. 2, electrically conductive contacts 120 may be positioned between two carbon current collectors 110a or 110c to make a sandwich structure 110s. Preferably, prismatic stack 100P also includes two electrical buses 122a and 122c. One electrical bus 122a is electrically connected to the anode current collectors 110a in the prismatic stack 100P and one electrical bus 122c is electrically connected to the cathode current collectors 110c in the prismatic stack 100P. Connected. In an embodiment, the electrical connection from anode and cathode current collectors 110a, 110c to electrical buses 122a, 122c is through electrically conductive contacts 120. In this way, the electrochemical cells 102 in the stack 100P can be electrically connected in parallel.

In an embodiment, positive cathode bus 122c electrically connects cathode electrodes 106 of electrochemical cells 102 in stack 100P in parallel to the positive electrical output of the stack, and provides a negative anode bus ( 122a electrically connects anode electrodes 104 of electrochemical cells 102 in stack 100P in parallel to the negative electrical output of stack 100P.

In prismatic stack 100P, cathode current collector 110c may be positioned between neighboring electrochemical cells 102. That is, multiple pairs of electrochemical cells 102 are composed of "front-to-front" and "back-to-back". As an example, a first electrochemical cell 102 considers a prismatic stack 100P in the center of the stack 100P. In the first pair of cells 102, the first cathode current collector 110c is the cathode electrode 106 of the first electrochemical cell 102 in electrical contact with the first cathode current collector 110c and the second cathode current collector 110c. The cathode electrode 106 of the electrochemical cell 102 is also positioned in electrical contact with the first cathode current collector 110c. The second electrochemical cell 102 is located adjacent to the first (cathode) side of the first electrochemical cell in the prismatic stack 100P.

The third electrochemical cell 102 is located adjacent to the second (anode) side of the first electrochemical cell 102 in the prismatic stack 100P. The anode electrode 104 of the first electrochemical cell 102 is in electrical contact with the first anode current collector 110a and the anode electrode 104 of the third electrochemical cell 102 is the first anode current collector 110a. Electrical contact. The stack can continue in this way. Therefore, the resulting prismatic stack 100P alternates adjacent anode electrodes 104 and neighboring cathode electrodes 106, thereby stacking a plurality of stacked in pairs in front-to-front and back-to-back. It may include electrochemical cells 102.

Prismatic stack 100P may be described with respect to the axial direction. In the stack 100P shown in FIG. 1, the axial direction is parallel to the buses 122a and 122c. The electrochemical cells 102 in the stack 100P are stacked in an axial direction along the axis of the stack 100P. Each of the odd or even electrochemical cells 120 in the stack has a cathode electrode 106 facing the first end of the axis of the stack 100P and an anode electrode facing the opposite second end of the axis of the stack 100P. 104). Each of the other of the even or odd electrochemical cells 102 in the stack 100P has a cathode electrode 106 facing the second end of the axis of the stack 100P and a second opposite end of the axis of the stack 100P. It has an anode electrode 104 facing.

In an embodiment, prismatic stack 100P includes electrochemical cells 102 in which anode electrode 104 and / or cathode electrode 106 are made from pressed granular pellets. The anode electrode 104 and the cathode electrode 106 may be between 0.05 and 1 cm. Alternatively, anode electrode 104 and cathode electrode 106 are between 0.05 and 0.15 cm thick. The boundary regions between the pressed granule pellets may provide reservoirs for the electrolyte, as described in more detail below.

In an embodiment, the electrochemical cells 102 are secondary hybrid aqueous energy storage devices. In an embodiment, the cathode electrode 106 in operation reversibly intercalates alkali metal cations. The anode electrode 104 is in part with a capacitive electrode or an alkali metal cation on the surface of the anode electrode 104 which stores charge via a reversible non-Faraday reaction of alkali metal cations on the surface of the anode electrode 104. May include pseudocapacitive electrodes where charge transfer surface interaction occurs have. In an embodiment, the anode is a pseudocapacitive or electrochemical bilayer capacitive material that is electrically stable to less than -1.3 V relative to a typical hydrogen electrode (NHE). In an embodiment, cathode electrode 106 may comprise a doped or undoped cubic spinel λ-Mn0 2 -type material or a tetragonal material of NaMn 9 O 18 tunnel structure and anode electrode 104 comprises activated carbon. It may include. Alternatively, the cathode electrode may comprise a non-intercalate MnO 2 phase such as an electrolyte manganese dioxide (EMD), alpha or gamma phase.

Another embodiment of the invention is shown in FIGS. 3 and 4. In this embodiment, the electrochemical device 300 includes eight stacks 100P of electrochemical cells 102 in a 2x4 array. However, any number of stacks 100P can be included. For example, the electrochemical device 300 may include two stacks 100P in a 1x2 array, three stacks 100P in a 1x3 array, 12 stacks 100P in a 3x4 array, or 25 stacks in a 5x5 array. May include stacks 100P. The exact number of stacks 100P can be selected according to the end user's needs or power needs.

Electrochemical device 300 preferably includes a housing 116. In this embodiment, the housing 116 includes a base 116b and a plurality of sidewall members 116a. In an embodiment, the anode electrodes 104 and cathode electrodes 106 of the electrochemical cells 102 in each of the plurality of stacks 100P are exposed along their ends but are constrained by the housing 116. . Preferably, housing 116 provides pressure through each stack 100P, thereby securing the stacks 100P of electrochemical device 300. In an alternate embodiment, anode electrodes 104 and cathode electrodes 106 of electrochemical cells 102 in each of the plurality of stacks 100P are partially or completely covered and constrained along their ends. . This can be accomplished, for example, by mounting the anode electrodes 104 and cathode electrodes 106 of each cell 102 in the frame 112, as shown in FIG. 9. Other housing configurations may be used. For example, the housing 116 may include a base 116b and a single one sidewall member 116a, similar to a bell jar.

In this embodiment, the separator 108 and / or the anode current collector 110a and / or the cathode current collector 110c of the at least one electrochemical cell 102 are between at least two of the plurality of stacks 100P. Expand continuously. Preferably, separator 108, anode current collector 110a and cathode current collector 110c extend continuously between all stacks 100P in electrochemical device 300. In this way, the electrochemical device 300 can be manufactured easily and inexpensively. However, the cathode electrode 106 and anode electrode 104 of each cell 102 in the stacks of cells 100P preferably extend continuously to another cell 102 in another of the stacks 100P. I never do that. In an embodiment, the spaces between the electrodes 104, 106 of neighboring stacks 100P contain an electrolyte reservoir.

In an embodiment, the electrochemical device 300 includes a combined positive bus that electrically connects all positive outputs of the plurality of stacks and all negative outputs of the first end plate 122c and the plurality of stacks 100P. And a second end plate 122a and a combined sound bus that electrically connect them. Base 116b may also include external electrical contacts 124 that allow the electrochemical device 300 to be easily and quickly attached to a load.

In an embodiment, the electrochemical device 300 is the hybrid electrochemical device described above. Preferably in this embodiment, all the electrochemical cells 102 of the stacks 100P of the electrochemical cells 102 are hybrid electrochemical cells. As in the embodiments discussed above, the hybrid electrochemical cell 102 comprises a cathode electrode comprising a doped or undoped cubic spinel λ-MnO 2 -type material or a tetragonal material of NaMn 9 O 18 tunnel structure ( 106, and an anode electrode 104 comprising activated carbon and the electrolyte comprises an aqueous electrolyte containing sodium ions. As discussed below, other cathode and anode materials can be used. The device may comprise a secondary battery such as a Li-ion or Na-ion battery in alternative embodiments.

Another embodiment of the invention is shown in FIGS. 5 and 6. In this embodiment, as shown, the electrochemical device 500 includes a single prismatic stack 100P of electrochemical cells 102. One or more stacks may be used. A single prismatic stack 100P of electrochemical cells 102 is located within housing 116. The electrochemical device 500 includes an anode bus 122a and a cathode bus 122c. Each of the anodes 104 in the electrochemical cells 102 in the prismatic stack 100P is electrically connected to the anode bus 122a through the anode current collectors 110a. In this embodiment, the anodes 104 are connected in parallel. Similarly, each of the cathodes 106 in electrochemical cells 102 in prismatic stack 100P is electrically connected to cathode bus 122c through cathode current collectors 110c. In this embodiment, the cathodes 106 are connected in parallel. Preferably, anode current collectors 110a and cathode current collectors 110c are connected with conductive tabs 120 to their respective anode bus 122a and cathode bus 122c. Current collectors 110a, 110c are pressure / friction fits; Conductive electrochemically inert cured paint; Or a conductive electrochemically inert cured epoxy that can be operatively connected to the respective tabs 120 and / or the anode and cathode buses 122a and 122c. The electrochemical device 500 also includes external electrical contacts 124 to provide electricity to the external device or circuit in the electrochemical device 500. In an embodiment, external electrical contacts 124 are located over anode bus 122a and cathode bus 122c. Alternatively, the contacts may be located on the bottom or sides of the buses. Contacts may be located on the same or different sides of the device.

In an embodiment, typically with an electrolyte (ie, anode 104, cathode 106, separator 108, current collectors 110, buses 122, tabs 120, and housing 116), All components of the electrochemical device 500 that are in contact are made of non-metallic materials. In an embodiment, the current collectors 110, buses 122 and tabs 120 may be made of carbon in any suitable electrically conductive form. The buses and tabs may be made of graphite, carbon fiber, or a carbon-based conductive composite (eg, a polymer matrix containing carbon fiber or filler material). Housing 116 may be made of, but is not limited to, an electrochemically inert and electrically insulating polymer. Accordingly, electrochemical device 500 is corrosion resistant. If the buses 122 do not contact the electrolyte (ie, the tabs extend through the sealing material to the external buses), the buses may be made of metal. External electrical contacts 124 may be made of a metallic material. In the embodiment shown in FIG. 7, the buses 122 are hermetically located between the contacts 124 and the top of the buses 122 and the top of the prismatic stack 100P of the electrochemical cells 102. It is surrounded by the sealing ring 114. Sealing may include a polymer or epoxy material that does not pass electrolyte and oxygen, such as poly-based epoxy, glue, coke or melt sealing polymer. Buses 122 may be connected to contacts 124 by pressure provided by soldering, bolts, clamps, and / or sealing material. Accordingly, the external electrical contacts 124 can be isolated from the electrolyte, thereby making the external electrical contacts 124 made of a metallic material such as copper. In this way, only metal contacts or interconnects 124 protrude from the sealing 114 region of the housing 116.

8 is a plot of cell potential versus cell capacity of an embodiment of an electrochemical device 500. As can be seen in the plot, a high cell capacity, such as greater than 1200 mAh, for example for voltages of 0.5 V or less can be achieved.

9 illustrates an embodiment of an electrochemical cell 102. The electrochemical cell 102 includes an anode electrode 104, a cathode electrode 106 and a separator 108 between the anode electrode 104 and the cathode electrode 106. In addition, the electrochemical cell 102 includes an electrolyte positioned between the anode electrode 104 and the cathode electrode 106. In an embodiment, the separator 108 may be porous where the electrolyte is located in the pores. The electrolyte can be aqueous or non-aqueous. In addition, the electrochemical cell 102 may include a graphite sheet 110 serving as a current collector for the electrochemical cell 102. Preferably, the graphite sheet 110 increases the density. In an embodiment, the density of the graphite sheet 110 is greater than 0.6g / cm 3. The graphite sheet 110 can be made, for example, from exfoliated graphite. In an embodiment, the graphite sheet 110 may comprise one or more foil layers. Suitable materials for the anode electrode 104, the cathode electrode 106, the separator 108 and the electrolyte are discussed in more detail below.

The anode electrode 104, the cathode electrode 106, the separator 108 and the graphite sheet current collector 110 may be mounted in a frame 112 sealing each individual cell. The frame 112 is preferably made of an electrically insulating material, for example, an electrically insulating plastic or epoxy. The frame 112 may be made from preformed rings, poured epoxy, or a combination of both. In an embodiment, the frame 112 may include separate anode and cathode frames. In an embodiment, the graphite sheet current collector 110 may be configured to act as a sealing ring 114 on the frame 112. That is, the graphite sheet current collector 110 can extend into the grooves in the frame 112 so as to serve as the sealing ring 114. In this embodiment, the seal ring 114 prevents the electrolyte from flowing from one electrochemical cell 102 to the neighboring electrochemical cell 102. In alternative embodiments, a separate seal ring 114, such as a washer or gasket, may be provided so that the graphite sheet current collector is not performed as a sealing ring.

In an embodiment, the electrochemical cell is a hybrid electrochemical cell. That is, in operation the cathode electrode 106 reversibly intercalates alkali metal cations, and the anode electrode 104 is (1) through a reversible non-Faraday reaction of alkali metal cations on the surface of the anode electrode, or ( 2) a capacitive electrode that stores charge via a pseudocapacitive electrode where partial charge transfer surface interaction with alkali metal cations occurs on the surface of the anode electrode.

11 illustrates a bipolar stack 100B of electrochemical cells 102 in accordance with another embodiment. In contrast to conventional stacks of electrochemical cells that include separate anode side and cathode side current collectors, bipolar stack 100B has a cathode electrode 106 of one electrochemical cell 102 and a neighboring electrochemical cell 102. It acts as a single graphite sheet current collector 110 located between the anode electrodes 104. Thus, the bipolar stack 100B uses half as many current collectors as the typical stack of electrochemical cells.

In an embodiment, bipolar stack 100B is enclosed within outer housing 116 and conductive headers 118 are provided on the top and bottom of bipolar stack 100B. The headers 118 preferably include corrosion resistant current collecting metals, including, but not limited to, aluminum, nickel, titanium, and stainless steel. Preferably, pressure is applied to the bipolar stack 100B when assembled. Pressure helps to provide good seals to prevent electrolyte leakage.

In an embodiment, the electrochemical cell 102 is a secondary hybrid aqueous energy storage device. In this embodiment, anode electrode 104 and cathode electrode 106 may be 0.05-1 cm, such as 0.05-0.15 cm thick.

10 illustrates another embodiment of the invention. In this embodiment, the anode electrode 104 may comprise individual anode electrode members 104a separated by anode boundary regions 104b. In addition, cathode electrode 106 may include individual cathode electrode members 106a separated by cathode boundary regions 106b. As shown, anode electrode 104 includes two separate anode electrode members 104a and cathode electrode 106 includes three separate cathode electrode members 106a. However, this is for illustration only. The anode electrode 104 and the cathode electrode 106 may each include any number of individual anode electrode members 104a and individual cathode electrode members 106a. Further, in an embodiment, anode boundary regions 104b and cathode boundary regions 106b may include voids filled with electrolyte.

10 shows only a cross section in one dimension. The cross-sectional view in the orthogonal direction shows the anode electrode 104 and the cathode electrode 106 with the individual anode electrode members 104a and the individual cathode electrode members 106a. That is, the anode electrode 104 and the cathode electrode 106 may include a two-dimensional checkerboard pattern. That is, the individual anode electrode members 104a and the individual cathode electrode members 106a may be arranged in an array of rows and columns. Each of the individual anode electrode members 104a and the individual cathode electrode members 106a may be square or rectangular in shape, for example. In an embodiment, the inventors have provided different numbers of individual anode electrode members 104a and individual cathode electrode members 106a to the anode electrode 104 and the cathode electrode 106 due to the structure of the electrochemical cells 102. It has been found to improve integrity. In this embodiment, the anode rows and columns are offset from the cathode rows and columns. In an embodiment, at least 50%, such as 50-100%, including 75-95% of the anode boundary regions 104b, do not align with the respective cathode boundary regions 106b across the separator 108. Alternatively, anode electrode 104 and cathode electrode 106 may include the same number of separate anode electrode members 104a as individual cathode electrode members 106a. In alternative embodiments, the anode electrode 104 or cathode electrode 106 may comprise a single single sheet while the other electrode includes individual members of a checkerboard pattern.

In an embodiment, anode electrode members 104a and cathode electrode members 106a are made from rolled sheets or pressurized pellets of activated carbon and manganese oxide, respectively. Yet another embodiment comprises the steps of (1) stacking an anode electrode 104 comprising a plurality of individual anode electrode members 104a separated by anode boundary regions 104b, and (2) on the anode electrode 104. Stacking the separators 108 on; (3) Electrochemical of FIG. 10 comprising laminating cathode electrode 106 comprising a plurality of individual cathode electrode members 106a separated by cathode boundary regions 106b on separator 108. It is about how to make a device. In one aspect, at least 50% of the anode boundary regions 104b are not aligned with the respective cathode boundary regions 106b across the separator 108. The method may also include depositing a graphite sheet current collector 110 on the cathode electrode 106. Anode electrode members 104a and / or cathode electrode members 106b may be formed by cutting members 104a, 106a from a roll sheet of anode or cathode material, or by pressing pellets of anode or cathode material. have.

Yet another embodiment of the invention relates to a method of making a stack 100B, 100P of electrochemical cells 102. The method may include forming stack electrochemical cells and pouring an electrically insulating polymer around stacks 100B, 100P of electrochemical cells 102. The method may also include solidifying the polymer to form a solid insulating shell or frame 112. Alternatively, the method may include providing a preformed solid insulating shell 112 around the stack of electrochemical cells 102. The polymer may be epoxy or acrylic, but is not limited thereto.

The method may also include attaching the conductive end plate headers 118 shown in FIG. 11 to the top and bottom of the stack 110. The stack 110 and solid insulating shell or frame 112 may then be disposed within the hollow cylindrical shell or outer housing 116. The method also includes disposing the graphite sheet current collector 110 between adjacent electrochemical cells 102 in the stacks 100B, 100P of the electrochemical cells 102. In an embodiment, each electrochemical cell 102 in stacks 100B, 100P of electrochemical cells 102 includes an anode electrode 104 having an active anode region and a cathode electrode 106 having an active cathode region. . The graphite sheet current collector 110 may have a larger area than the active anode region and the active cathode region in order to act as a sealing as shown in FIG. 9.

Device components

Cathode

Several materials, including transition metal oxides, sulfides, phosphates, or fluorides, can be used as active cathode materials capable of reversible Na-ion intercalate / deintercalate. Materials suitable for use as active cathode materials in embodiments of the present invention preferably contain alkali atoms such as sodium, lithium, or both prior to use as active cathode materials. It is not necessary for the active cathode material to contain Na and / or Li in the formed state (ie, prior to use in an energy storage device). However, Na cations from the electrolyte must be able to be mixed into the active cathode material by intercalation during operation of the energy storage device. Accordingly, the materials that can be used as cathodes in the present invention do not necessarily contain Na in the formed state, but are reversible intercalate / deinterceptors of Na-ions during discharge / charge cycles of the energy storage device without large overpotential loss. Contains substances that can be culled.

In embodiments where the active cathode material contains alkali-atoms (preferably Na or Li) prior to use, some or all of these atoms are deintercalated during the first cell charge cycle. Alkali cations from the electrolyte (overwhelmingly Na cations) are re-intercalated during cell discharge. This is different from almost all hybrid capacitor systems that draw intercalated electrodes opposite to activated carbon. In most systems, the cations from the electrolyte are absorbed onto the anode during the charge cycle. At the same time, counter-anions such as hydrogen ions in the electrolyte intercalate in the active cathode material, thus preserving the charge balance in the electrolyte solution but reducing the ion concentration. During the discharge, the cations are released from the anode and the anions are released from the cathode, thereby preserving the charge balance in the electrolyte solution, but increasing the ion concentration. This is a different mode of operation from the devices in embodiments of the present invention in which hydrogen ions or other anions are preferably not intercalated in the cathode active material.

Suitable active cathode materials may have the following general formula during use: A x M y O z , A is Na or a mixture of Na with one or more of Li, K, Be, Mg, and Ca, x being used Previously within this range, including 0-1 and during use, within this range, including 0-10; M comprises any one or more transition metals; y is within this range, including 1 to 3; Preferably within the range of from 1.5 to 2.5; O is oxygen, z is within this range including 2 to 7; Preferably within the range of 3.5 to 4.5 inclusive.

In some active cathode materials with the general formula A x M y O z , the Na- ions reversibly intercalate / deintercalate during the discharge / charge cycle of the energy storage device. Thus, the x amount in the active cathode material formula changes while the device is in use.

In some active cathode materials with the general formula A x M y O z , A optionally comprises at least 50 at% of at least one of Na, K, Be, Mg, or Ca in combination with Li; M comprises any one or more transition metals; O is oxygen; x is in the range of 3.5 to 4.5 before use and in the range of 1 to 10 during use; y ranges from 8.5 to 9.5 and z ranges from 17.5 to 18.5. In these embodiments, A preferably comprises at least 51 at% Na, such as at least 75 at% Na, and 0 to 49 at% Li, K, Be, Mg, or Ca, such as 0 to 25 at% ; M comprises at least one of Mn, Ti, Fe, Co, Ni, Cu, V, or Sc; x is about 4 before use and is in the range of 0 to 10 during use; y is about 9; z is about 18.

In some active cathode materials with the general formula A x M y O z , A comprises Na, or a mixture of at least 80 atomic percent Na with one or more of Li, K, Be, Mg, and Ca. In these embodiments, x is preferably about 1 before use and in the range of 0 to 1.5 for use. In some preferred active cathode materials, M comprises at least one of Mn, Ti, Fe, Co, Ni, Cu, and V, and at least one of Al, Mg, Ga, In, Cu, Zn, (E.g., less than 20 at%, such as 0.1 to 10 at%; e.g., 3 to 6 at%).

Common classes of suitable active cathode materials include layered / quadratic NaMO 2 (Burnesite), cubic spinel based manganate (eg MO 2 , such as λ-MnO 2 based material, M is Mn, for example Prior to use, Li x M 2 O 4 (1 ≤ x <1.1) and Na y Mn 2 O 4 ), Na 2 M 3 O 7 system, NaMPO 4 system, NaM 2 (PO 4 ) 3 system, Na 2 The MPO 4 F system, and in all formulas, includes (but is not limited to) tunnel-structured Na 0.44 MO 2 , which comprises at least one transition metal. Typical transition metals are Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, Mo (among other things), or combinations thereof, to replace Mn, Fe, or combinations thereof in whole or in part Mn or Fe (for cost and environmental reasons). In embodiments of the present invention, Mn is the preferred transition metal. In some embodiments, the cathode electrodes may be a homogeneous or nearly homogeneous mixture, or may include a plurality of layered active cathode materials within the cathode electrode.

In some embodiments, the initial active cathode material optionally includes NaMnO 2 (burseite structure) doped with one or more metals such as Li or Al.

In some embodiments, the initial active cathode material comprises a lambda-MnO 2 (i.e., cubic oxide manganese) based material, optionally doped with one or more metals such as Li or Al.

In these embodiments, cubic spinel λ-MnO 2 may be formed by first forming a lithium containing manganese oxide such as lithium manganate (eg cubic spinel LiMn 2 O 4 or non-stoichiometric variants thereof). . In embodiments using a cubic spinel λ-MnO 2 active cathode material, most of the Li or all of cubic spinel λ-MnO 2 type material (i.e., 1: 2 having a Mn for O ratio, and / or Mn is another From a cubic spinel LiMn 2 O 4 electrochemically or chemically to form a material which can be replaced by a metal, and / or also contains an alkali metal, and / or where the Mn to O ratio is not exactly 1: 2 Can be extracted. This extraction may occur as part of the initial device charge cycle. In these cases, Li- ions are deintercalated from the cubic spinel LiMn 2 O 4 that was formed during the first charge cycle. Upon discharge, the Na- ions from the electrolyte intercalate in the cubic spinel [lambda] -MnO 2 . As such, the formula for the active cathode material during operation is Na y Li x Mn 2 O 4 (optionally doped with one or more additional metals, preferably Al, as described above), 0 <x <1, 0 <y <1, and x + y ≦ 1.1. Preferably, the quantity x + y changes from about 0 (fully charged) to about 1 (fully discharged) through the charge / discharge cycle. However, one or more values may be used during a full discharge. In addition, any other suitable forming method may be used. Non-stoichiometric Li x Mn 2 0 4 materials having at least 1 Li for every 2 Mn and 4 O atoms can be used as initial materials from which cubic spinel λ-MnO 2 can be formed (1 ≦ x <1.1 for example). Accordingly, the cubic spinel λ-manganate has the formula Al z Li x Mn 2-z 0 4 , before use, wherein 0 ≦ x <1.1, 0 ≦ x < It may have Al z Li x Na y Mn 2 0 4 with 1, 0 ≦ x + y <1.1, and 0 ≦ z <0.1 (and Al may be substituted by another dopant).

In some embodiments, the initial cathode material optionally comprises Na 2 Mn 3 O 7 doped with one or more metals such as Li or Al.

In some embodiments, the initial cathode material optionally comprises Na 2 FePO 4 F doped with one or more metals such as Li or Al.

In some embodiments, the cathode material optionally comprises Na 0.44 Mn0 2 doped with one or more metals such as Li or Al. This active cathode material can be made by mixing Na 2 CO 3 and Mn 2 O 3 with perfectly suitable molecular ratios and calcining, for example, at about 800 ° C. The degree of Na content mixed in this material during firing determines the oxidation state of Mn and how much it bonds locally with 0 2 . This material was demonstrated to be cyclic between 0.33 &lt; x < 0.66 for Na x MnO 2 in a non-aqueous electrolyte.

Optionally, the cathode electrode may comprise one or more active cathode materials (e.g., a minor component such as 1 to 49% of a tetragonal tunnel structure material, such as 2 to 10% by weight), a high surface area conductive diluent (such as conductive grade Carbon blacks such as graphite, acetylene black, non-reactive metals, and / or conductive polymers), binders, plasticizers, and / or fillers in the form of composites including fillers. Representative binders include polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC) -based composites (including PVC-SiO 2 composites), cellulose-based materials, polyvinylidene fluoride (PVDF) When the active cathode material comprises another material), other non-reactive non-corrosive polymer materials, or combinations thereof. The composite cathode may be formed by mixing a portion of one or more desirable active cathode materials with a conductive diluent, and / or a polymeric binder, and pressing the mixture into pellets. In some embodiments, the composite cathode electrode may be formed from a mixture of about 50 to 90 wt% active cathode material and the remainder of the mixture comprises one or more combinations of diluent, binder, plasticizer, and / or filler. For example, in some embodiments, the composite cathode electrode may be formed from about 10 to 15 wt% diluent that is about 80 wt% active cathode material, such as carbon black, and about 5 to 10 wt% binder, such as PTFE .

One or more additional functional materials may optionally be added to the composite cathode to increase the capacity and replace the polymeric binder. These optional materials include, but are not limited to, Zn, Pb, hydrated NaMn0 2 (Burnesite), and hydrated Na 0.44 Mn0 2 (orthogonal tunnel structure). In the case that the composite cathode added hydrated NaMn0 2 (Burnet site) and / or a hydrated Na 0.44 Mn0 2 (orthorhombic tunnel structure), the resultant apparatus has a function of the cathode material compound 2.

The cathode electrode will generally have a thickness in the range of about 40-800 μm.

Anode:

The anode includes any material capable of reversibly storing Na-ions through surface adsorption / desorption (via electrochemical bilayer reactions and / or pseudocapacitive reactions (ie, partial charge transfer surface interactions)). It may have sufficient capacity in the voltage range. Representative materials that meet these requirements include porous activated carbon, graphite, mesoporous carbon, carbon nanotubes, disordered carbon, Ti-oxide (Tiles oxide titania) materials, V-oxide materials, phospho-olivine materials And other suitable mesoporous ceramic materials, and combinations thereof. In preferred embodiments, activated carbon is used as anode material.

Optionally, the anode electrode comprises one or more anode materials, a high surface area conductive diluent (such as conductive grade graphite, carbon blacks such as acetylene black, non-reactive metals, and / or conductive polymers), a binder such as PTFE, Composite anodes comprising PVC-based composites (including PVC-SiO 2 composites), cellulose-based materials, PVDF, other non-reactive non-corrosive polymeric materials, or combinations thereof, plasticizers, and / or fillers It may be in the form. The composite anode may be formed by mixing a portion of one or more preferred anode materials with a conductive diluent, and / or a polymeric binder, and pressing the mixture into pellets. In some embodiments, the composite anode electrode is formed from a mixture of about 50 to 90 wt% anode material and the remainder of the mixture comprises a combination of one or more of diluents, binders, plasticizers, and / or fillers. For example, in some embodiments, the composite cathode electrode may be formed from about 80 wt% activated carbon, about 10 to 15 wt% diluent such as carbon black, and about 5 to 10 wt% binder such as PTFE.

One or more additional functional materials may optionally be added to the composite anode to increase capacity and replace the polymeric binder. These optional materials include, but are not limited to, Zn, Pb, hydrated NaMn0 2 (Burnesite), and hydrated Na 0.44 Mn0 2 (orthogonal tunnel structure).

The anode electrode will generally have a thickness in the range of about 80 to 1600 μm.

Electrolyte:

Electrolytes useful in embodiments of the present invention include salts that are completely soluble in water. For example, the electrolyte S0 4 2-, N0 3 -, ClO 4 -, P0 4 3-, CO 3 2-, Cl -, and / or OH - at least one anion selected from the group consisting of 0.1 M to 10 M solution. Accordingly, Na cation containing salts may include, but are not limited to, Na 2 S0 4 , NaN0 3 , NaCl0 4 , Na 3 P0 4 , Na 2 C0 3 , NaCl, and NaOH, or a combination thereof. ).

In some embodiments, the electrolyte solution may be substantially free of Na. In these cases, the cations in the salts of the anions listed above may be alkali (such as K) or alkaline earth (such as Ca, or Mg) cations other than Na. Accordingly, alkalis other than Na cation containing salts may include (but are not limited to) K 2 S0 4 , KN0 3 , KCl0 4 , K 3 P0 4 , K 2 C0 3 , KCl, and KOH. Alkaline earth cation-containing salts include CaS0 4 , Ca (N0 3 ) 2 , Ca (Cl0 4 ) 2 , CaC0 3 , and Ca (OH) 2 , MgS0 4 , Mg (N0 3 ) 2 , Mg (Cl0 4 ) 2 , MgC0 3 , and Mg (OH) 2. Substantially Na-free electrolyte solutions may be made in any combination of these salts In other embodiments, the electrolyte solution may be combined with a Na cation containing salt. It may contain a solution of the above non-Na cation-containing salt.

The molar concentrations are preferably from about 0.05 M to 3 M at 100 ° C. for Na 2 SO 4 in water depending on the desired performance characteristics of the energy storage device and the degradation / performance limiting mechanism associated with the higher salt concentrations. It is in the range of 0.1 to 1 M. Similar ranges for other salts are desirable.

Blends of different salts (such as a blend of alkali, alkaline earth, lanthanide, one or more of aluminum and zinc salts and a sodium-containing salt) can make the system optimal. Such a blend may provide the electrolyte with sodium cations and one or more cations selected from the group consisting of alkali (such as K), alkaline earth (such as Mg and Ca), lanthanide, aluminum, and zinc cations.

Alternatively, some additional OH to the electrolyte solution to be more alkaline (basic) - with the addition of ionic species, for example by adding NaOH and other OH- containing salt, or other any other OH - concentration complexes affecting by adding (such as H2 S O 4 for the electrolytic solution to be more acidic), the pH of the electrolyte can be changed. The pH of the electrolyte affects the range of the cell's voltage stability window (with respect to the reference electrode), can affect the stability and degradation of the active cathode material, and can inhibit proton (H + ) intercalation, This can play a role in the active cathode material capacity loss and cell deterioration. In some cases, the pH can be increased from 11 to 13, thereby allowing different active cathode materials to be stable (rather than stable at neutral pH 7). In some embodiments, the pH may be in the range of about 3 to 13, such as about 3 and 6 or about 8 to 13.

Optionally, the electrolyte solution contains an additive to alleviate the deterioration of the active cathode material, such as the burnseite material. Representative additives may be, but are not limited to, Na 2 HP0 4 in amounts sufficient to establish concentrations ranging from 0.1 mM to 100 mM.

Separator:

Separators for use in embodiments of the present invention may include cotton sheets, PVC (polyvinyl chloride), PE (polyethylene), glass fibers, or any other suitable material.

Operating features

As described above, in embodiments in which the active cathode material contains alkali-atoms (preferably Na or Li) prior to use, some or all of these atoms are deintercalated during the first cell charge cycle. . Alkali cations from the electrolyte (overwhelmingly Na cations) are re-intercalated during cell discharge. This is different from almost all hybrid capacitor systems that draw intercalate electrodes against activated carbon. In most systems, cations from the electrolyte are absorbed on the anode during the charge cycle. At the same time, counter-anions in the electrolyte intercalate to the active cathode material, thus preserving the charge balance in the electrolyte solution but reducing the ion concentration. During discharge, cations are released from the anode and anions are released from the cathode, thus preserving the charge balance in the electrolyte solution but increasing the ion concentration. This is a different mode of operation from the devices in the embodiments of the present invention.

Yes

Hybrid energy storage devices with prismatic / parallel electrical connections shown in FIG. 1A and physical structures shown in FIGS. 5-7 were assembled. The device comprising non-woven and anode 104 / cathode 106 sets (of 2 each) with expanded graphite sheet current collectors 110a, 110c structures (500 micron thick), as shown in FIG. 3 levels of fiber separator material 108. The cathode contained the λ-MnO 2 phase active material, as described above, and was made from granulated compacts of the active material, carbon black, graphite powder and PTFE. The anode contained activated carbon mixed with carbon black and PTFE. Pressure was used to contact each of the graphite anode and cathode current collectors 110a, 110c to each of the anode and cathode graphite bus bars 122a used as positive and negative bus bars for the device. Polypropylene enclosure 116 was used to accommodate the device, graphite bus bars 122a and 122c were supplied through holes of suitable size in the polypropylene enclosure and then sealed against polypropylene with a silicone adhesive material. It became. The copper wires were then connected by pressurization to external (non-electrolyte) bus bars 124 coming from the enclosure, and the entire external bus bar was covered with potting epoxy.

The device was then taken 15 formation cycles and then tested for energy storage capacity and stability through many cycles. 12 shows these test results. 12 (a) shows the storage capacity versus device potential under charge and discharge conditions over 30 cycles. Cycling was performed at the C / 6 current rating and the device had a capacity of approximately 1.1 Ah. The data shows almost complete overlap of voltage profiles per cycle, which represents a system that is extremely stable and shows no loss in capacity or no internal corrosion. 12 (b) is a plot of cell charge and discharge capacity as a function of cycle. There is no loss in capacity as a function of cycle over at least 60 cycles. Data from other cells indicates that this will be maintained over thousands of cycles. In addition, the column efficiency was found to be 98-100% during these cycles.

This example shows that a very stable aqueous electrolyte hybrid energy storage device is created without the use of any metal in the battery case. The device shows good stability and shows great prospects for long term use in various energy storage applications.

Although the foregoing has mentioned certain preferred embodiments, it will be understood that the invention is not limited thereto. It will be apparent to those skilled in the art that various modifications may be made to the disclosed embodiments and that such modifications are within the scope of the invention. All publications, patent applications, and patents cited herein are hereby incorporated by reference in their entirety.

Claims (29)

  1. In the electrochemical device,
    housing;
    Each electrochemical cell comprises an anode electrode; A cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And a stack of electrochemical cells in the housing;
    A current collector located between neighboring electrochemical cells;
    An anode bus operably connected to the anodes of the electrochemical cells in the stack; And
    A cathode bus operably connected to the cathodes of the electrochemical cells in the stack;
    And the housing, the anode electrode, the cathode electrode, the separator, the anode bus and the cathode bus are nonmetals.
  2. The electrochemical device of claim 1, wherein the current collector comprises exfoliated graphite, carbon fiber paper, or an inert substrate coated with a carbon material.
  3. The electrochemical device of claim 2, wherein the graphite has a density greater than 0.6 g / cm 3 .
  4. The electrochemical device of claim 1, wherein the electrochemical device is a hybrid aqueous electrolyte energy storage device in which the electrolyte is not in contact with a metallic material.
  5. 5. The electrochemical device of claim 4, wherein the cathode comprises an alkali ion intercalate material and the anode is a pseudocapacitive or electrochemical bilayer capacitive material that is electrochemically stable to -1.3 V relative to NHE.
  6. The method of claim 5, wherein the cathode electrode comprises a doped or undoped cubic spinel λ-Mn0 2 -type material or a tetragonal material of NaMn 9 O 18 tunnel structure, the anode electrode comprising activated carbon, The electrolyte comprises sodium ions.
  7. The non-intercalate MnO 2 of claim 1, wherein the cathode electrode is selected from electrolyte manganese dioxide (EMD), alpha or gamma. An electrochemical device comprising a phase.
  8. The electrochemical device of claim 5, wherein the anode electrode comprises one or more of porous activated carbon, mesoporous carbon, carbon nanotubes, pseudocapacitive metal-oxide materials, or a combination thereof.
  9. 5. The dissolved alkali ions of claim 4 which can interact with both the anode and the cathode such that charge can be stored via intercalates at the cathode and by pseudocapacitive non-Faraday surface reactions at the anode. An electrochemical device, which is an aqueous solution containing them.
  10. The electrochemical device of claim 1, wherein the anode bus and the cathode bus comprise a conductive composite based on graphite, carbon fiber, or carbon.
  11. The electrochemical device of claim 1, wherein the housing comprises an electrochemically inert polymer.
  12. The electrochemical device of claim 1, wherein the electrochemical cells in the stack of electrochemical cells are stacked in a prismatic configuration.
  13. 13. The method of claim 12, wherein the cathode current collectors are operably and electrically connected to the cathode bus by cathode side carbon tabs, and the anode current collectors are operably and electrically connected to the anode bus by anode side carbon tabs. Connected to the electrochemical device.
  14. 14. The apparatus of claim 13, wherein the current collectors comprise: a pressure / friction fit; Conductive electrochemically inert cured paint; Or an electrochemical device operatively connected to the anode and cathode buses with a conductive electrochemically inert cured epoxy.
  15. The electrochemical device of claim 1, wherein the housing is hermetically sealed.
  16. The electrochemical device of claim 1, further comprising metal contacts protruding outside the housing and electrically connected to the anode bus and the cathode bus.
  17. 17. The electrochemical device of claim 16, further comprising an airtight seal coating the contacts of the bus bars with respective contacts.
  18. The method of claim 1,
    The anode electrode comprises a plurality of individual anode electrode members separated by anode boundary regions; And
    And the cathode electrode comprises a plurality of individual cathode electrode members separated by cathode boundary regions.
  19. In the method of making an electrochemical device,
    Stacking a first non-metal anode electrode;
    Stacking a first non-metal separator on the anode electrode;
    Stacking a first non-metal cathode on the separator;
    Operatively connecting the first anode electrode to a nonmetal anode bus; And
    And operably connecting the first cathode electrode to a non-metal cathode bus.
  20. 20. The electrochemical device of claim 19, further comprising laminating a nonmetal current collector on the cathode electrode.
  21. 21. The method of claim 20,
    Stacking a second nonmetal cathode on the nonmetal current collector;
    Stacking a second non-metal separator on the second cathode electrode; And
    And depositing a second nonmetal anode electrode on the second nonmetal separator.
  22. In the electrochemical device,
    housing;
    Each electrochemical cell comprises an anode electrode; A cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And a stack of electrochemical cells in the housing;
    A plurality of carbon cathode and anode current collectors, alternately located between neighboring electrochemical cells;
    A plurality of tabs configured to connect to an electrical bus and operably connected to the plurality of carbon cathode and anode current collectors;
    The cathode electrode of the first electrochemical cell is in electrical contact with the first cathode current collector;
    A cathode electrode of a second electrochemical cell is in electrical contact with the first cathode current collector, and the second electrochemical cell is located adjacent to a first side of the first electrochemical cell in the stack;
    An anode electrode of the first electrochemical cell is in electrical contact with a second anode current collector; And
    An anode electrode of a third electrochemical cell is in electrical contact with the second anode current collector, and the third electrochemical cell is located adjacent to a second side of the first electrochemical cell in the stack .
  23. In the electrochemical device,
    housing;
    Granular anode electrodes in which each electrochemical cell is compressed; Compressed granular cathode electrodes; A separator positioned between the anode electrode and the cathode electrode; And a stack of electrochemical cells in the housing;
    A plurality of cathode and anode current collectors, alternately located between neighboring electrochemical cells,
    The cathode electrode of the first electrochemical cell is in electrical contact with the first cathode current collector;
    A cathode electrode of a second electrochemical cell is in electrical contact with the first cathode current collector, and the second electrochemical cell is located adjacent to a first side of the first electrochemical cell in the stack;
    An anode electrode of the first electrochemical cell is in electrical contact with a second anode current collector; And
    An anode electrode of a third electrochemical cell is in electrical contact with the second anode current collector, and the third electrochemical cell is located adjacent to a second side of the first electrochemical cell in the stack .
  24. In the electrochemical device,
    housing;
    Each electrochemical cell comprises an anode electrode; A cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And a plurality of stacks of electrochemical cells arranged side by side in the housing, comprising an electrolyte;
    A current collector located between neighboring electrochemical cells in each of said stacks;
    And the separator of at least one cell comprises a separator sheet extending continuously between at least two of the plurality of stacks.
  25. In the electrochemical device,
    housing;
    Each electrochemical cell comprises an anode electrode; A cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And a stack of electrochemical cells in the housing;
    A graphite sheet located between neighboring electrochemical cells;
    The graphite sheet is a current collector for the neighboring electrochemical cells.
  26. In an electrochemical cell,
    An anode comprising a plurality of individual anode electrode members separated by anode boundary regions;
    A cathode electrode comprising a plurality of individual cathode electrode members separated by cathode boundary regions;
    A separator positioned between the anode electrode and the cathode electrode; And
    An electrolyte;
    The electrolyte is located in the separator and in anode and cathode electrode boundary regions; And
    At least 50% of the anode boundary regions are not aligned with respective cathode boundary regions across the separator.
  27. A method of making an electrochemical device comprising a stack of electrochemical cells,
    Forming stack electrochemical cells; And
    Pouring an electrically insulating polymer around the stack of electrochemical cells to form a solid insulating shell or providing a preformed solid insulating shell around the stack of electrochemical cells.
  28. In the method of making an electrochemical device,
    Stacking an anode electrode comprising a plurality of individual anode electrode members separated by anode boundary regions;
    Stacking a separator on the anode; and
    Stacking a cathode electrode on the separator, the cathode electrode comprising a plurality of individual cathode electrode members separated by cathode boundary regions;
    At least 50% of the anode boundary regions are not aligned with respective cathode boundary regions across the separator, and the plurality of anode electrode members and the plurality of cathode electrode members are arranged in an array of rows and columns.
  29. A secondary hybrid aqueous energy storage device,
    housing;
    Each electrochemical cell comprises an anode electrode; A cathode electrode; A separator positioned between the anode electrode and the cathode electrode; And a stack of electrochemical cells in the housing;
    A graphite sheet located between neighboring electrochemical cells;
    And the anode and cathode electrodes are 0.05 to 1 cm thick.
KR1020137025490A 2011-03-09 2012-03-08 Metal-free aqueous electrolyte energy storage device KR101823873B1 (en)

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US61/450,774 2011-03-09
US13/043,787 US8298701B2 (en) 2011-03-09 2011-03-09 Aqueous electrolyte energy storage device
PCT/US2012/028228 WO2012122353A2 (en) 2011-03-09 2012-03-08 Metal free aqueous electrolyte energy storage device

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AU2012225439A1 (en) 2013-09-19
BR112013023007A2 (en) 2018-02-14
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CA2829224A1 (en) 2012-09-13
CN103597649A (en) 2014-02-19
EP2684245A4 (en) 2014-09-03
CA2829224C (en) 2016-10-04
JP2016219426A (en) 2016-12-22
JP2014512638A (en) 2014-05-22
CN103597649B (en) 2016-05-25
EP2684245A2 (en) 2014-01-15
CN105761941A (en) 2016-07-13
AU2012225439B2 (en) 2016-10-13
AU2016200438B2 (en) 2016-04-28
KR101823873B1 (en) 2018-01-31

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