CN105761941A - Metal Free Aqueous Electrolyte Energy Storage Device - Google Patents

Metal Free Aqueous Electrolyte Energy Storage Device Download PDF

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Publication number
CN105761941A
CN105761941A CN201610179405.5A CN201610179405A CN105761941A CN 105761941 A CN105761941 A CN 105761941A CN 201610179405 A CN201610179405 A CN 201610179405A CN 105761941 A CN105761941 A CN 105761941A
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China
Prior art keywords
electrochemical cell
electrode
anode
cathode
stacking
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CN201610179405.5A
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Chinese (zh)
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CN105761941B (en
Inventor
杰·怀特奎
唐·汉弗莱斯
杨文卓
爱德华·林奇-贝尔
亚历克斯·穆罕默德
埃里克·韦伯
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亚奎尼能源公司
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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 亚奎尼能源公司 filed Critical 亚奎尼能源公司
Priority to CN201280012476.6A priority patent/CN103597649B/en
Publication of CN105761941A publication Critical patent/CN105761941A/en
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Publication of CN105761941B publication Critical patent/CN105761941B/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
    • 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
    • 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
    • H01M4/665Composites
    • 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

The present invention relates to a metal free aqueous electrolyte energy storage device. An electrochemical device includes a housing and a stack of electrochemical cells in the housing. Each electrochemical cell includes an anode electrode, a cathode electrode, a separator located between the anode electrode and the cathode electrode and an electrolyte. The electrochemical device also includes a current collector located between adjacent electrochemical cells, an anode bus operatively connected to the anodes of the electrochemical cells in the stack and a cathode bus operatively connected to the cathodes of the electrochemical cells in the stack. The housing, the anode electrode, the cathode electrode, the separator, the anode bus and the cathode bus are non-metallic.

Description

Metal-free aqueous electrolyte energy storing device

The relevant information of divisional application

This case is divisional application.The application for a patent for invention case that female case of this division is the applying date, and to be on March 8th, 2012, application number be 201280012476.6, denomination of invention is " metal-free aqueous electrolyte energy storing device ".

Related application

Subject application advocates the 61/450th of application on March 9th, 2011, the 13/043rd applied in No. 774 U. S. application cases and on March 9th, 2011, the benefit of priority of No. 787 U. S. application cases, 61/450th, the full content of No. 774 and the 13/043rd, No. 787 application cases is incorporated herein by reference hereby.

Technical field

The present invention relates to containing aqueous secondary battery and mixed tensor storage device, and relate in particular to the electrochemical storage device of the metal parts not contacted with aqueous electrolyte.

Background technology

Small-sized rechargeable energy collection is with generation technology (such as, solar battery array, wind turbine, miniature Stirling engine (sterlingengine) and SOFC) rise, and the needs of medium sized secondary (rechargeable) energy storage capability are powerful equally.Accumulator for these stationary applications is commonly stored the energy (depending on application) between 1 and 50kWh, and is based on plumbic acid (Pb acid) chemical reaction in the past.Assemble deeper cavity lead-acid battery group at distributed power generation place place, and these set of cells known depend on exemplary operation circulation and sustainable use 1 to 10 years.Although these batteries can operate to support that this applies enough well, but exist and use the many problems being associated with it, comprise: use the lead polluted the environment and acid (to estimate often to be only to result at U.S.'s Pb technic acid and discharge more than 100 in environment in a large number, the Pb of 000 ton), when be maintained at middle charged state or daily be recycled to deep discharge grade significant performance degradation, need routine servicing to maintain performance, and implement the recirculation plan of necessity.The replacement needs such as the Pb acid chemical composition that auto industry uses are very strong.Unfortunately, so far, the economy of substituting battery chemistries composition still makes it not have very much captivation.

Although battery technology achieves nearest being made progress, but still without to the low cost of Pb acid chemical composition, clean replacement scheme.It is cheap ($ 200/kWh) significantly compared with other chemical composition that this is particularly since Pb acid accumulator, and current just concentrating on develops the higher-energy system (it is significantly more more expensive than Pb acid accumulator inherently) for transport applications.

Summary of the invention

One embodiment relates to a kind of electrochemical appliance, and it comprises the electrochemical cell stacks in shell and described shell.Each electrochemical cell comprises anode electrode, cathode electrode, dividing plate between described anode electrode and described cathode electrode and electrolyte.Electrochemical appliance also comprises the current collector between adjacent electrochemical cell, be operatively connectable to described stacking in the anode bus of anode of electrochemical cell and be operatively connectable to described stacking in the cathode bus of negative electrode of electrochemical cell.Described shell, described anode electrode, described cathode electrode, described dividing plate, described anode bus and described cathode bus are nonmetallic." nonmetal " in the context of this specification means the conductive material not being made up of simple metal or metal alloy.The example of nonmetallic materials is including (but not limited to) conducting metal oxide or carbon.

Another embodiment relates to a kind of method manufacturing electrochemical appliance.Method comprises: stacking first non-metallic anode electrode;Stacking first nonmetal dividing plate on described anode electrode;And on described dividing plate stacking first non-metallic cathode electrode.Method also comprises: operatively described first anode electrode is connected to non-metallic anode bus;And operatively described first cathode electrode is connected to non-metallic cathode bus.

One embodiment relates to a kind of electrochemical appliance, and it comprises the electrochemical cell stacks in shell and described shell.Each electrochemical cell comprises anode electrode, cathode electrode, dividing plate between described anode electrode and described cathode electrode and electrolyte.Device also comprises: multiple carbon cathodes and anode collector, it is alternately positioned between adjacent electrochemical cell;And multiple tab, it is operatively connectable to the plurality of carbon cathode and anode collector, and the plurality of tab is configured to connect to electric bus.The cathode electrode of the first electrochemical cell electrically contacts the first cathode collector.The cathode electrode of the second electrochemical cell electrically contacts the first cathode collector.Second electrochemical cell be positioned adjacent to stacking in the first side of the first electrochemical cell.The anode electrode electrical contact second plate current collector of described first electrochemical cell.The anode electrode electrical contact second plate current collector of the 3rd electrochemical cell.3rd electrochemical cell be positioned adjacent to stacking in the second side of the first electrochemical cell.

Another embodiment relates to a kind of electrochemical appliance, and it comprises the electrochemical cell stacks in shell and described shell.Each electrochemical cell comprises the granular anode electrode of compacting, the granular cathode electrode of compacting, the dividing plate between described anode electrode and described cathode electrode and electrolyte.Electrochemical appliance also comprises multiple negative electrode and anode collector, and it is alternately positioned between adjacent electrochemical cell.The cathode electrode of the first electrochemical cell electrically contacts the first cathode collector.The cathode electrode of the second electrochemical cell electrically contacts the first cathode collector.Second electrochemical cell be positioned adjacent to stacking in the first side of the first electrochemical cell.The anode electrode electrical contact second plate current collector of the first electrochemical cell, and the anode electrode electrical contact second plate current collector of the 3rd electrochemical cell.3rd electrochemical cell be positioned adjacent to stacking in the second side of the first electrochemical cell.

Another embodiment relates to a kind of electrochemical appliance, and it comprises shell and the multiple electrochemical cell stacks in the housing that are arranged side by side.Each electrochemical cell comprises anode electrode, cathode electrode, dividing plate between described anode electrode and described cathode electrode and electrolyte.Described device also comprise described stacking in each in adjacent electrochemical cell between current collector.The dividing plate of at least one battery include the plurality of stacking in the dividing plate thin slice extended continuously at least between the two.

One embodiment relates to a kind of electrochemical appliance, and it comprises the electrochemical cell stacks in shell and described shell.Each electrochemical cell comprises anode electrode, cathode electrode, dividing plate between described anode electrode and described cathode electrode and electrolyte.Described electrochemical appliance also comprise described stacking in adjacent electrochemical cell between graphite flake.Described graphite flake is the current collector of adjacent electrochemical cell.

Another embodiment relates to a kind of electrochemical cell, and it comprises: have the anode electrode of the multiple discrete anode electrod assemblies separated by anode side boundary region;And there is the cathode electrode of the multiple discrete cathode electrode parts separated by cathode-side boundary region.Electrochemical cell also comprises the dividing plate between anode electrode and cathode electrode and electrolyte.Described electrolyte is arranged in described dividing plate and is arranged in anode electrode borderline region and cathode electrode borderline region.Additionally, at least the 50% of anode side boundary region is not directed at the respective cathode borderline region on dividing plate opposite.

Another embodiment relates to a kind of method that manufacture has the electrochemical appliance of electrochemical cell stacks.Described method comprises: form stacked electrochemical cells;And electric insulating copolymer is cast in around described electrochemical cell stacks and makes described polymer solidify to form solid insulation housing, or around described electrochemical cell stacks offer preformed solid insulation shell.

Another embodiment relates to a kind of method manufacturing electrochemical appliance.Described method comprises: stacking anode electrode, and it includes the multiple discrete anode electrod assemblies separated by anode side boundary region;Stack separator on described anode electrode;And on described dividing plate stacking cathode electrode, described cathode electrode includes the multiple discrete cathode electrode parts separated by cathode-side boundary region.At least the 50% of described anode side boundary region is not directed at the respective cathode borderline region on described dividing plate opposite, and the plurality of anode electrode parts and the plurality of cathode electrode parts are arranged to the array with multirow and multiple row.

Another embodiment relates to secondary and mixes moisture energy storing device.Secondary mixes moisture energy storing device and comprises the electrochemical cell stacks in shell and described shell.Each electrochemical cell comprises anode electrode, cathode electrode and the dividing plate between described anode electrode and described cathode electrode, electrolyte and the graphite flake between adjacent electrochemical cell.The thickness of described anode and cathode electrode is between 0.05cm and 1cm.

Accompanying drawing explanation

Fig. 1 is stacking the schematically illustrating of prism of the electrochemical cell according to embodiment.

Fig. 2 is schematically illustrating of the details of the sandwich-type current collector according to embodiment.

Fig. 3 is the perspective view of the electrochemical appliance stacking according to multiple prisms with electrochemical cell of embodiment.

Fig. 4 is another perspective view of embodiment illustrated in fig. 3.

Fig. 5 is the perspective view of the electrochemical appliance stacking according to the single prism with electrochemical cell of embodiment.

Fig. 6 is the perspective view of the embodiment of Fig. 5, and it removes electrochemical cell for clarity.

Fig. 7 is the schematic side elevational cross-sectional view of the details of the part that embodiment illustrated in fig. 5 is described.

Fig. 8 is the cell potential curve chart to battery capacity of embodiment.

Fig. 9 is the schematically illustrating of electrochemical cell according to an embodiment of the invention.Described electrochemical cell can bipolar or prism stack arrangement come stacking.

Figure 10 is the cross-sectional view of the electrochemical cell according to embodiment, and it has the anode electrode being made up of discrete anode electrod assembly and the cathode electrode being made up of discrete cathode electrode parts.Described electrochemical cell can bipolar or prism stack arrangement come stacking.

Figure 11 is schematically illustrating of the electrochemical appliance of the bipolar stack including electrochemical cell according to an embodiment of the invention.

Figure 12 (a) is the curve chart to institute's cumulative capacity of the cell potential in 30 circulations when charge and discharge.Figure 12 (b) is the curve chart of battery charge and discharge capacity and the efficiency become with circulation.

Detailed description of the invention

Embodiments of the invention relate to electrochemical energy storage system, for instance described below once store system with secondary accumulator battery and mixed tensor.Although it is the preferred embodiments of the present invention that secondary described below mixes moisture energy storage system, but present disclosure additionally applies for any suitable electrochemical energy storage system, such as contain the accumulator of moisture and non-aqueous electrolyte (such as, there is the anode and negative electrode that embed from electrolytical ion, comprise Li ion accumulator etc.), or electrolysis condenser is (also referred to ultra-capacitor and ultracapacitor, such as, it has capacitor or pseudocapacitors anode and cathode electrode, described electrode stores electric charge via cationic reversible non-faraday (nonfaradiac) reaction on the surface of electrode (bilayer) and/or fake capacitance, but not by embedding alkali ion).

The hybrid electrochemical energy storage system of embodiments of the invention comprises the double layer capacitor or pseudocapacitors electrode (such as, anode) that couple with active electrode (such as, negative electrode).In such systems, capacitor or pseudocapacitors electrode store electric charge via the reaction of reversible non-faraday and/or the fake capacitance of the alkaline kation on the surface of electrode (bilayer), and active electrode is in the reversible faraday reaction embedded and in the transition metal oxide of deintercalation alkaline kation, experience is similar to accumulator.

The example of Na based system has described that in the 12/385th, No. 277 U.S. patent application case of application on April 3rd, 2009 and is incorporated herein by reference in full, and described example utilizes spinel structure LiMn2O4Battery terminal, activated carbon electrode for capacitors and moisture Na2SO4Electrolyte.In such a system, negative anode electrode reacts via the reversible non-faraday of the Na ion on the surface of active carbon electrode and stores electric charge.Positive cathode electrode utilizes spinelle λ-MnO2In Na ion embedding/deintercalation reversible faraday reaction.

In alternative system, cathode electrode can include non-embedded (such as, non-alkaline ion embeds) MnO2Phase.The non-embedded phase of example of manganese dioxide comprises α phase and γ phase electrolytic manganese dioxide (EMD).

Fig. 1 illustrates the stacking 100P of prism of the electrochemical cell 102 according to embodiment.In this embodiment, each in the electrochemical cell 102 in the stacking 100P of prism comprises anode electrode 104, cathode electrode 106 and the dividing plate between anode electrode 104 and cathode electrode 106 108.Electrochemical cell 102 also comprises the electrolyte (that is, flowing in dividing plate and/or electrode) between anode electrode 104 and cathode electrode 106.Each in the electrochemical cell 102 of stacking for prism 100P can be arranged in framework 112 (referring to Fig. 9-10).Additionally, alternatively or additionally, it is possible to stacking for prism 100P is enclosed in shell 116 (referring to Fig. 3-6).The additional features of shell 116 is provided in more detail below with respect to the embodiment illustrated in Fig. 3-6.The other embodiments of electrochemical cell 102 is illustrated in Fig. 9 and Figure 10 and discusses in greater detail hereinafter.Multiple carbon cathodes that the stacking 100P of prism is also included between adjacent electrochemical cell 102 positioned alternate and anode collector 110a, 110c.Current collector can include the conductive carbon of any suitable form, for instance expanded graphite, carbon fiber paper or scribble the inert substrate of material with carbon element.Preferably, current collector includes density more than 0.6g/cm3Graphite.

In an embodiment, the stacking 100P of prism comprises multiple conductive junction point (such as, tab) 120, and it is operatively connectable to multiple carbon cathode and anode collector 110a, 110c.Conductive junction point 120 can attach to carbon cathode and the side of anode collector 110a, 110c.Or, as illustrated in figure 2, conductive junction point 120 can be located between two carbon collector 110a or 110c, thus constituting sandwich 110s.Preferably, the stacking 100P of prism also comprises two electric bus 122a, 122c.One electric bus 122a is electrically connected to the anode collector 110a in the stacking 100P of prism, and an electric bus 122c is connected to the cathode collector 110c in the stacking 100P of prism.In an embodiment, it is via conductive junction point 120 from anode and cathode collector 110a, 110c to the electrical connection of electric bus 122a, 122c.In this way, the electrochemical cell 102 in stacking 100P can in parallel electrically connect.

In an embodiment, positive cathode bus 122c makes the cathode electrode 106 of the electrochemical cell 102 in stacking 100P electrically connect with stacking positive electrical output-parallel, and negative anode bus 122a makes the anode electrode 104 of electrochemical cell 102 in stacking 100P electrically connect with the negative electrical output-parallel of stacking 100P.

In the stacking 100P of prism, cathode collector 110c can be located between adjacent electrochemical cell 102.That is, paired electrochemical cell 102 is configured as " face-to-face " and " back-to-back ".As an example, it is considered to the first electrochemical cell 102 is in the stacking 100P of prism at the center of stacking 100P wherein.In first pair of battery 102, first cathode collector 110c is located and makes the cathode electrode 106 of the first electrochemical cell 102 electrically contact the first cathode collector 110c, and the cathode electrode 106 of the second electrochemical cell 102 also electrically contacts the first cathode collector 110c.First (negative electrode) side of first electrochemical cell being positioned adjacent in the stacking 100P of prism of the second electrochemical cell 102.

Second (anode) side of first electrochemical cell 102 being positioned adjacent in the stacking 100P of prism of the 3rd electrochemical cell 102.The anode electrode 104 of the first electrochemical cell 102 electrically contacts first anode current collector 110a, and the anode electrode 104 of the 3rd electrochemical cell 102 also electrically contacts first anode current collector 110a.Stacking can continue in this way.Therefore the stacking 100P of gained prism can comprise that anode electrode 104 alternately is adjacent and cathode electrode 106 is adjacent face-to-face and back-to-back stacked pairs of multiple electrochemical cells 102.

The stacking 100P of prism can be described in the axial direction.For stacking 100P illustrated in fig. 1, it is axially parallel to bus 122a, 122c.Electrochemical cell 102 in stacking 100P is stacking in the axial direction along the axis of stacking 100P.Each in the electrochemical cell 120 of stacking middle odd number or even-numbered has the cathode electrode 106 of the first end of the axis in the face of stacking 100P and the anode electrode 104 of opposite second end of the axis in the face of stacking 100P.In stacking 100P, each in other person in the electrochemical cell 102 of even number or odd-numbered has the cathode electrode 106 of the second end of the axis in the face of stacking 100P and the anode electrode 104 of contrary first end of the axis in the face of stacking 100P.

In an embodiment, the stacking 100P of prism comprises electrochemical cell 102, and wherein anode electrode 104 and/or cathode electrode 106 are made up of granular bead that suppressing.The thickness of anode electrode 104 and cathode electrode 106 can between 0.05cm and 1cm.Or, the thickness of anode electrode 104 and cathode electrode 106 is between 0.05cm and 0.15cm.Borderline region between the granular bead of compacting can provide electrolytical storage, as will be described in further detail below.

In an embodiment, electrochemical cell 102 mixes moisture energy storing device for secondary.In an embodiment, cathode electrode 106 reversibly embeds alkali metal cation in operation.Anode electrode 104 can include the reversible non-faraday reaction of the alkali metal cation on the surface via anode electrode 104 and store the capacitive electrode of electric charge, or the fake capacitance electrode of experience and the Partial charge transitional surface interaction of the alkali metal cation on the surface of anode electrode 104.In an embodiment, anode is fake capacitance or electrochemical double layer capacitative materials, and it is electrochemically stable less than under-1.3V at relative standard hydrogen electeode (NHE).In an embodiment, cathode electrode 106 can include doping or unadulterated cubic spinel λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, and anode electrode 104 can include activated carbon.Or, cathode electrode can include non-embedded MnO2Phase, for instance α or γ phase electrolytic manganese dioxide (EMD).

Fig. 3 and Fig. 4 illustrates another embodiment of the present invention.In this embodiment, that electrochemical appliance 300 comprises electrochemical cell 102 is two eight the stacking 100P taking advantage of four arrays.But, the stacking 100P of any number can be comprised.For example, electrochemical appliance 300 can comprise two the stacking 100P taking advantage of two arrays in, three the stacking 100P taking advantage of three arrays in, 12 the stacking 100P taking advantage of four arrays in three or in five 25 the stacking 100P taking advantage of five arrays.The exact number of stacking 100P can be selected according to the needs of end user or electricity needs.

Electrochemical appliance 300 preferably comprises shell 116.In this embodiment, shell 116 comprises substrate 116b and multiple side member 116a.In an embodiment, anode electrode 104 and the cathode electrode 106 of the electrochemical cell 102 in each in multiple stacking 100P expose to the open air along its edge, but are subject to shell 116 and retrain.Preferably, shell 116 provides the pressure through each stacking 100P, thus the stacking 100P of electrochemical appliance 300 is kept fastening.In alternative embodiments, the anode electrode 104 of the electrochemical cell 102 in each in multiple stacking 100P and cathode electrode 106 are along its edge partially or completely through covering and constraint.For example, this can realize in framework 112 by the anode electrode 104 of each battery 102 and cathode electrode 106 being arranged on, as shown in Figure 9.It is also possible to use the configuration of other shell.For example, shell 116 can comprise substrate 116b and be similar to the single integral side walls parts 116a of bell jar.

In this embodiment, the dividing plate 108 of at least one electrochemical cell 102 and/or anode collector 110a and/or cathode collector 110c at least extending continuously between the two in multiple stacking 100P.Preferably, extend continuously between dividing plate 108, anode collector 110a and the cathode collector 110c all stacking 100P in electrochemical appliance 300.In this way, electrochemical appliance 300 can easily and inexpensively be manufactured.But, another battery 102 in the cathode electrode 106 of each battery 102 in cell stacks 100P and the anode electrode 104 preferably discontinuous another one extended in stacking 100P.In an embodiment, electrolyte storage is contained in the space between the electrode 104,106 of adjacent stacks 100P.

In an embodiment, electrochemical appliance 300 comprises the positive bus of combination type and the first end plate 122c that electrically connect multiple stacking all positive outputs further, and the combination type electrically connecting all negative outputs of multiple stacking 100P bears bus and the second end plate 122a.It addition, substrate 116b can comprise external electrical contact 124, described external electrical contact 124 allows electrochemical appliance 300 is rapidly and easily attached to load.

In an embodiment, electrochemical appliance 300 is above-described hybrid electrochemical device.Preferably in this embodiment, all electrochemical cells 102 of the stacking 100P of electrochemical cell 102 are hybrid electrochemical battery.As, in embodiments discussed above, hybrid electrochemical battery 102 can comprise cathode electrode 106 and anode electrode 104, wherein cathode electrode 106 comprises doping or unadulterated cubic spinel λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, and anode electrode 104 comprises activated carbon, and electrolyte includes the aqueous electrolyte containing sodium ion.Other negative electrode and anode material can be used as discussed below.Device can include secondary accumulator battery in alternative embodiments, for instance Li ion or Na ion accumulator.

Fig. 5 and Fig. 6 illustrates another embodiment of the present invention.In this embodiment, electrochemical appliance 500 as described comprises the stacking 100P of single prism of electrochemical cell 102.Can use more than one stacking.The stacking 100P of single prism of electrochemical cell 102 is arranged in shell 116.Electrochemical appliance 500 comprises anode bus 122a and cathode bus 122c.The each in the anode 104 in electrochemical cell 102 in the stacking 100P of prism is electrically connected to anode bus 122a via anode collector 110a.In this embodiment, anode 104 is connected in parallel.Similarly, each in the negative electrode 106 in the electrochemical cell 102 in the stacking 100P of prism is electrically connected to cathode bus 122c via cathode collector 110c.In this embodiment, negative electrode 106 is connected in parallel.Preferably, anode collector 110a and cathode collector 110c is connected to its respective anode bus 122a and cathode bus 122c by conduction tab 120.Current collector 110a, 110c can be operatively connectable to corresponding tab 120 and/or anode and cathode bus 122a, 122c by the following: pressure/friction fitting, conduction electrochemicaUy inert solidify paint or conduction electrochemicaUy inert cured epoxy resin.Electrochemical appliance 500 also comprises external electrical contact 124 to power from electrochemical appliance 500 to external device (ED) or circuit.In an embodiment, external electrical contact 124 is positioned on the top of anode bus 122a and cathode bus 122c.Or, described contact can be located on bottom or the side of bus.Described contact can be located on the identical or different side of device.

In an embodiment, the usual all component (that is, anode 104, negative electrode 106, dividing plate 108, current collector 110, bus 122, tab 120 and shell 116) with electrolyte contact of electrochemical appliance 500 is made up of nonmetallic materials.In an embodiment, current collector 110, bus 122 and tab 120 can be made up of the carbon of any suitable Conducting forms.Bus and tab can be made up of graphite, carbon fiber or carbon-based conductive complex (such as, the polymeric matrix of carbon fiber-containing or packing material).Shell 116 can be made up of (but not limited to) electrochemicaUy inert and electric insulating copolymer.In this way, electrochemical appliance 500 is corrosion resistant.If bus 122 does not contact electrolyte (that is, tab extends through encapsulant to external bus), then bus can be made of metal.External electrical contact 124 can be made up of metal material.In the embodiment illustrated in the figure 7, bus 122 by gas-tight seal 114 around, between top and the contact 124 of the described gas-tight seal 114 stacking 100P of prism at the top of bus 122, electrochemical cell 102.Sealing member can include polymer or the epoxide resin material of impermeable electrolyte and oxygen, for instance based on the epoxy resin of polymer, glue, quick lime or melting sealed polymer.Bus 122 can be connected to contact 124 by pressure that welding, bolt, clamp and/or encapsulant provide.In this way, external electrical contact 124 can be isolated with electrolyte, thus allowing external electrical contact 124 to be made up of metal material (such as copper).Therefore, only hard contact or cross tie part 124 are prominent from sealing member 114 region of shell 116.

Fig. 8 is the cell potential curve chart to battery capacity of the embodiment of electrochemical appliance 500.In curve chart visible, it may be achieved high battery capacity, for instance for the voltage of 0.5V and below 0.5V more than 1200mAh.

Fig. 9 illustrates the embodiment of electrochemical cell 102.Electrochemical cell 102 comprises anode electrode 104, cathode electrode 106 and the dividing plate between anode electrode 104 and cathode electrode 106 108.Electrochemical cell 102 also comprises the electrolyte between anode electrode 104 and cathode electrode 106.In an embodiment, dividing plate 108 can be porous, and wherein electrolyte is arranged in described hole.Electrolyte can be moisture or non-aqueous.Electrochemical cell 102 also can comprise the graphite flake 110 of the current collector serving as electrochemical cell 102.Preferably, graphite flake 110 is fine and close.In an embodiment, the density of graphite flake 110 is more than 0.6g/cm3.Graphite flake 110 can be made up of (such as) expanded graphite.In an embodiment, graphite flake 110 can comprise one or more layers of foil.Discuss in greater detail for anode electrode 104, cathode electrode 106, dividing plate 108 and electrolytical suitable material below.

Anode electrode 104, cathode electrode 106, dividing plate 108 and graphite flake current collector 110 can be arranged in the framework 112 sealing each Individual cells.Framework 112 is preferably made up of electrically insulating material, for instance electrically insulating plastic material or epoxy resin.Framework 112 can be made up of preforming ring, casting epoxy resin or both combinations.In an embodiment, framework 112 can include independent anode and cathode frame.In an embodiment, graphite flake current collector 110 can be configured to serve as the sealing member 114 of framework 112.That is, graphite flake current collector 110 may extend in the recess in framework 112 to serve as sealing member 114.In this embodiment, sealing member 114 prevents electrolyte from flowing to adjacent electrochemical cell 102 from an electrochemical cell 102.In alternative embodiments, it is possible to provide independent sealing member 114 (such as, packing ring or pad) so that graphite flake current collector does not serve as sealing member.

In an embodiment, electrochemical cell is hybrid electrochemical battery.Namely, cathode electrode 106 reversibly embeds alkali metal cation in operation, and anode electrode 104 includes the reversible non-faraday reaction of alkali metal cation on the surface via (1) anode electrode and stores the fake capacitance electrode that the Partial charge transitional surface of the capacitive electrode of electric charge or (2) experience and the alkali metal cation on the surface of anode electrode interacts.

Figure 11 illustrates the bipolar stack 100B of the electrochemical cell 102 according to another embodiment.Compared with stacking with the conventional electrochemical cell comprising independent anode-side and cathode side current collector, bipolar stack 100B is operated by the single graphite flake current collector 110 between the cathode electrode 106 of an electrochemical cell 102 and the anode electrode 104 of adjacent electrochemical cell 102.Therefore, the current collector that bipolar stack 100B only uses conventional electrochemical cell stacking current collector half is many.

In an embodiment, bipolar stack 100B is enclosed in outer enclosure 116 and possesses conductive header 118 on the top and bottom of bipolar stack 100B.Head 118 preferably includes corrosion-resistant current collector metal, including (but not limited to) aluminum, nickel, titanium and rustless steel.Preferably, pressure is applied to bipolar stack 100B when assembling.What the help offer of described pressure was good is sealed against electrolyte leakage.

In an embodiment, electrochemical cell 102 mixes moisture energy storing device for secondary.In this embodiment, the thickness of anode electrode 104 and cathode electrode 106 can between 0.05cm and 1cm, for instance thickness is between 0.05cm and 0.15cm.

Figure 10 illustrates another embodiment of the present invention.In this embodiment, anode electrode 104 can comprise the discrete anode electrod assembly 104a separated by anode side boundary region 104b.Additionally, cathode electrode 106 can comprise the discrete cathode electrode parts 106a separated by cathode-side boundary region 106b.As described, anode electrode 104 comprises two discrete anode electrod assembly 104a, and cathode electrode 106 comprises three discrete cathode electrode parts 106a.But, this is only for explanation.Anode electrode 104 and cathode electrode 106 can comprise any number discrete anode electrod assembly 104a and discrete cathode electrode parts 106a respectively.It addition, in an embodiment, anode side boundary region 104b and cathode-side boundary region 106b can include filling electrolytical space.

Additionally, Figure 10 only illustrates the cross section in a dimension.Cross-sectional view on orthogonal direction also can illustrate anode electrode 104 and the cathode electrode 106 with discrete anode electrod assembly 104a and discrete cathode electrode parts 106a.That is, anode electrode 104 and cathode electrode 106 can include two dimension checkerboard pattern.In other words, discrete anode electrod assembly 104a and discrete cathode electrode parts 106a may be disposed to the array with multirow and multiple row.The shape of individual other discrete anode electrod assembly 104a and discrete cathode electrode parts 106a can be such as square or rectangle.In an embodiment, the inventors have discovered that: provide the anode electrode 104 with different number discrete anode electrod assembly 104a and discrete cathode electrode parts 106a and cathode electrode 106 to improve the structural intergrity of electrochemical cell 102.In this embodiment, the row and column of anode deviates from the row and column of negative electrode.In an embodiment, at least 50% (such as, 50-100%, comprise 75-95%) of anode side boundary region 104b is not directed at the respective cathode borderline region 106b on dividing plate 108 opposite.Or, anode electrode 104 and cathode electrode 106 can comprise equal number of discrete anode electrod assembly 104a and discrete cathode electrode parts 106a.In alternative embodiments, anode electrode 104 or in cathode electrode 106, any one can include single one-piece sheet, and another electrode includes the checkerboard pattern of discreet component.

In an embodiment, anode electrode parts 104a and cathode electrode parts 106a rolled sheet or pressed pellet by activated carbon and manganese oxide respectively is made.Another embodiment relates to a kind of method of electrochemical appliance manufacturing Figure 10, it comprises the steps of (1) stacking anode electrode 104, anode electrode 104 comprises the multiple discrete anode electrod assembly 104a separated by anode side boundary region 104b, (2) dividing plate 108 is stacked on anode electrode 104, and cathode electrode 106 is stacked on dividing plate 108 by (3), cathode electrode 106 includes the multiple discrete cathode electrode parts 106a separated by cathode-side boundary region 106b.In one aspect, at least the 50% of anode side boundary region 104b is not directed at the respective cathode borderline region 106b on dividing plate 108 opposite.Method also can comprise graphite flake current collector 110 is stacked on the step on cathode electrode 106.Can by forming anode electrode parts 104a and/or cathode electrode parts 106b from rolled sheet cutting part 104a, 106a of male or female material or the bead by pressed-powder anode or cathode material.

Another embodiment of the present invention relates to a kind of method of stacking 100B, 100P manufacturing electrochemical cell 102.Described method can comprise formation stacked electrochemical cells and electric insulating copolymer is cast in the step around stacking 100B, P of electrochemical cell 102.Method also can comprise makes polymer solidify to form solid insulation housing or framework 112.Or, method can be included in the step of the stacking surrounding offer preformed solid insulation shell 112 of electrochemical cell 102.Polymer can be (but not limited to) epoxy resin or acrylic resin.

Method also can comprise top and bottom that the conducting end plates head 118 shown in Figure 11 attaches to stacking 110.Then stacking 110 and solid insulation housing or framework 112 can be placed in hollow circular cylinder housing or outer enclosure 116.Method also comprises and is placed between the adjacent electrochemical cell 102 in stacking 100B, the P of electrochemical cell 102 by graphite flake current collector 110.In an embodiment, each electrochemical cell 102 in stacking 100B, the P of electrochemical cell 102 includes the anode electrode 104 of active anode region and the cathode electrode 106 of active cathode zone.Graphite flake current collector 110 can have more than the area of active anode areas and active cathode areas to serve as sealing member as shown in Figure 9.

Device assembly

Negative electrode

The some materials including transition metal oxide, sulfide, phosphate or fluoride can be used as to carry out the active cathode material of reversible Na ion embedding/deintercalation.The material of the active cathode material being suitable as in embodiments of the invention preferably before as active cathode material containing basic atom, for instance sodium, lithium or both.Active cathode material need not under green state (that is, for energy storing device in before) containing Na and/or Li.But, allow for being incorporated in active cathode material by the embedding during the operation of energy storing device from electrolytical Na cation.Therefore, can be used as the material of the negative electrode in the present invention and include to contain under green state Na, but the material that the reversible embedding/deintercalation of Na ion can be carried out during the charged/discharged of energy storing device circulates and lose without substantial amounts of overpotential.

Contain in the embodiment of basic atom (being preferably Na or Li) before the use at active carbon material, the deintercalation during first time battery charge cycle of some or all in these atoms.Again embed during battery discharge from electrolytical alkaline kation (most for Na cation).These are different from the nearly all mixed capacitor system requiring intercalation electrode opposing activity carbon (intercalationelectrodeoppositeactivatedcarbon).In many number systems, it is adsorbed on anode during charging cycle from electrolytical cation.Meanwhile, the counter anion (such as hydrion) in electrolyte is embedded in active cathode material, therefore keeps charge balance in electrolyte solution but consumes ion concentration.During discharging, discharge cation from anode, and discharge anion from negative electrode, therefore in electrolyte solution, keep charge balance but add ion concentration.This is the operator scheme different from the device in embodiments of the invention, preferably hydrion or other anion is not embedded in active material of cathode in an embodiment of the present invention.

Suitable active cathode material can have below general formula: A during usexMyOz, wherein A is the one or more of mixture in Na or Na and Li, K, Be, Mg and Ca, and wherein x is before the use in the scope of 0 to 1 (comprising 0 and 1) and during use in the scope (comprising 0 and 10) of 0 to 10;M includes any or more than one transition metal, and wherein y is in the scope (comprising 1 and 3) of 1 to 3;Preferably in the scope (comprising 1.5 and 2.5) of 1.5 and 2.5;And O is oxygen, wherein z is in the scope (comprising 2 and 7) of 2 to 7;Preferably in the scope of 3.5 to 4.5 (comprising 3.5 and 4.5).

There is formula AxMyOzSome active cathode materials in, energy storing device charged/discharged circulate during, Na ion reversible ground embedding/deintercalation.Therefore, when device is in use, the amount x in active cathode material formula changes.

There is formula AxMyOzSome active cathode materials in, A include optionally with Li combination Na, K, Be, Mg or Ca at least one or one or more of at least 50 atom %;M includes any or more than one transition metal;O is oxygen;X ranges for 3.5 to 4.5 before the use and ranges for 1 to 10 during use;Y range for 8.5 to 9.5 and z range be 17.5 to 18.5.In these embodiments, A preferably includes Li, K, Be, Mg or Ca of the Na (such as the Na of at least 75 atom %) and 0 to 49 atom % (such as 0 to 25 atom %) of at least 51 atom %;It is one or more that M includes in Mn, Ti, Fe, Co, Ni, Cu, V or Sc;X is about 4 before the use, and ranges for 0 to 10 during use;Y is about 9;And z is about 18.

There is formula AxMyOzSome active cathode materials in, A includes the one or more of mixture in Na and the Li of Na or at least 80 atomic percent, K, Be, Mg and Ca.In these embodiments, x is preferably from about 1 before the use, and ranges for 0 to about 1.5 during use.In some preferred active cathode materials, it is one or more that M includes in Mn, Ti, Fe, Co, Ni, Cu and V, and can adulterate (less than 20 atom %, for instance 0.1 to 10 atom %;Such as 3 to 6 atom %) Al, Mg, Ga, In, one or more in Cu, Zn and Ni.

The suitable activity cathode material of common species is including (but not limited to) layering/iris NaMO2(birnessite (birnassite)), manganate (such as, MO based on cubic spinel2, for instance based on λ-MnO2Material, wherein M is Mn, for instance be Li before the usexM2O4(wherein, 1≤x < 1.1) and be in use NayMn2O4)、Na2M3O7System, NaMPO4System, NaM2(PO4)3System, Na2MPO4The Na of F system and tunnel construction0.44MO2, the M in all of which formula includes at least one transition metal.Typical transition metal can be Mn or Fe (for cost and environment reason), but Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, Mo (especially) or its combination can be used completely or partially to replace Mn, Fe or its combination.In an embodiment of the present invention, Mn is preferred transition metal.In certain embodiments, cathode electrode can include various active cathode material, is layered in homogenizing or close to the form of uniform homogeneous blend or in cathode electrode.

In certain embodiments, initial activity cathode material includes optionally adulterating the NaMnO of one or more metals (such as Li or Al)2(birnessite structure).

In certain embodiments, initial activity cathode material include optionally adulterating one or more metals (such as Li or Al) based on λ-MnO2The material of (that is, cube isomorphy of manganese oxide).

In these embodiments, manganese oxide (such as, LiMn2O4 (such as, the cubic spinel LiMn being initially formed containing lithium can be passed through2O4Or its non-stoichiometric variant)) form cubic spinel λ-MnO2.Utilizing cubic spinel λ-MnO2In the embodiment of active cathode material, it is possible to electrochemical means or chemical mode are from cubic spinel LiMn2O4Extract most or all of Li, to form cubic spinel λ-MnO2Types of material (that is, has the Mn of 1:2 and the material of O ratio, and/or wherein Mn can be replaced by another metal, and/or it is possibly together with alkali metal, and/or wherein Mn is not just 1:2 with O ratio).This extraction can occur as a part for initial installation charging cycle.In such cases, Li ion during the first charging cycle from nascent cubic spinel LiMn2O4Deintercalation.When electric discharge, it is embedded into cubic spinel λ-MnO from electrolytical Na ion2In.Thus, the formula of active cathode material is Na during operationyLixMn2O4(optionally doping one or more additional metal described above, it is preferred to Al), wherein 0 < x < l, 0 < y < l and x+y≤1.1.Preferably, amount x+y is changed to about 1 (completely electric discharge) from about 0 (fully charged) by charge/discharge cycle.But, the value of 1 can be used more than during electric discharge completely.Additionally, other suitable forming method any can be used.Can by non-stoichiometric LixMn2O4Material (every 2 Mn atoms and 4 O atom have more than 1 Li) is used as to may be used to form cubic spinel λ-MnO2Original material (such as, wherein 1≤x < 1.1).Therefore, cubic spinel λ manganate can have formula Al before the usezLixMn2-zO4(wherein 1≤x < 1.1 and 0≤z < 0.1), and in use there is formula AlzLixNayMn2O4(wherein 0≤x < 1.1,0≤y < 1,0≤x+y < 1.1 and 0≤z < 0.1) (and wherein Al can be replaced by another adulterant).

In certain embodiments, initial cathode material includes optionally adulterating the Na of one or more metals (such as Li or Al)2Mn3O7

In certain embodiments, initial cathode material includes optionally adulterating the Na of one or more metals (such as Li or Al)2FePO4F。

In certain embodiments, cathode material includes optionally adulterating the Na of one or more metals (such as Li or Al)0.44MnO2.Can pass through Na2CO3With Mn2O3Be sufficiently mixed to suitable molar ratio and at (such as) about 800 DEG C roasting and make this active cathode material.The degree of the Na content being incorporated in this material during baking determines the state of oxidation of Mn and itself and O2In the mode that local combines.Have turned out for the Na in non-aqueous electrolytexMnO2, this material < circulates between 0.66 0.33 < x.

Optionally, cathode electrode can be the form of composite cathode, comprising: one or more active cathode materials are (such as, 1-49 weight %, such as 2-10 weight % microcomponent, such as iris tunnel construction material), high surface area conductive diluent (such as, conduction level graphite, the carbon black of such as acetylene black, non-reactive metal and/or conducting polymer), binding agent, plasticizer and/or filler.Exemplary adhesives can include politef (PTFE), polrvinyl chloride (PVC) base complex (comprises PVC-SiO2Complex), cellulosic-based material, polyvinylidene fluoride (PVDF), hydration birnessite (when active cathode material includes another material), other non-reacted non-corrosive polymeric material or its combination.By a part for one or more preferred active cathode materials is mixed with Conductive diluents and/or polymeric binder and described mixture can be compressed to bead and forms composite cathode.In certain embodiments, composite cathode electrode can be formed by the mixture of the active cathode material of about 50 to 90 weight %, and the remainder of described mixture includes the one or more of combination in diluent, binding agent, plasticizer and/or filler.For example, in certain embodiments, composite cathode electrode can be formed by the active cathode material of about 80 weight %, the diluent (such as carbon black) of about 10 to 15 weight % and the binding agent (such as PTFE) of about 5 to 10 weight %.

One or more additional functionality materials can be optionally added to composite cathode to increase capacity and to replace polymeric binder.These optional material are including (but not limited to) Zn, Pb, hydration NaMnO2(birnessite) and hydration Na0.44MnO2(iris tunnel structure).By hydration NaMnO2(birnessite) and/or hydration Na0.44MnO2When (iris tunnel structure) adds composite cathode to, gained device has bifunctional material composite cathode.

The thickness that cathode electrode will generally have in about 40 μm to the scope of 800 μm.

Anode:

Anode can include (can reacting (namely via electrochemical double layer reaction and/or fake capacitance via surface adsorption/desorption, Partial charge transitional surface interacts)) and reversibly store any material of Na ion, and there is the abundant capacity in wanted voltage range.The exemplary materials meeting these requirements comprises: porous active carbon, graphite, mesoporous carbon, CNT, disordered carbon, Ti oxide (such as titanium dioxide) material, V oxide material, phosphorus olivine material, other suitable mesoporous ceramic material and its combination.In a preferred embodiment, activated carbon is used as anode material.

Optionally, anode electrode can be the form of composite anode, comprising: one or more anode materials, high surface area conductive diluent (such as, conduction level graphite, the carbon black of such as acetylene black, non-reactive metal and/or conducting polymer), binding agent (such as PTFE), PVC base complex (comprise PVC-SiO2Complex), cellulosic-based material, PVDF, other non-reacted non-corrosive polymeric material or its combination, plasticizer and/or filler.By a part for one or more preferred anodes materials is mixed with Conductive diluents and/or polymeric binder and described mixture can be compressed to bead and forms composite anode.In certain embodiments, composite anode electrode can be formed by the mixture of the anode material of about 50 to 90 weight %, and the remainder of described mixture includes the one or more of combination in diluent, binding agent, plasticizer and/or filler.For example, in certain embodiments, composite anode electrode can be formed by the activated carbon of about 80 weight %, the diluent (such as carbon black) of about 10 to 15 weight % and the binding agent (such as PTFE) of about 5 to 10 weight %.

One or more additional functionality materials can be optionally added to composite anode to increase capacity and to replace polymeric binder.These optional material are including (but not limited to) Zn, Pb, hydration NaMnO2(birnessite) and hydration Na0.44MnO2(iris tunnel structure).

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

Electrolyte:

Electrolyte useful in an embodiment of the present invention includes the salt being dissolved completely in water.For example, electrolyte can include 0.1M to the 10M solution of the choosing freely at least one anion of the group of following thing composition: SO4 2-、NO3 -、ClO4 -、PO4 3-、CO3 2-、Cl-And/or OH-.Therefore, can including (but not limited to) Na containing Na cationic salts2SO4、NaNO3、NaClO4、Na3PO4、Na2CO3, NaCl and NaOH or its combination.

In certain embodiments, electrolyte solution can be substantially free of Na.In these cases, the cation in the salt of those listed above anion can be the alkali metal (such as K) or alkaline-earth metal (such as Ca or the Mg) cation that are different from Na.Therefore, containing be different from the cationic alkali-metal salt of Na can including (but not limited to) K2SO4、KNO3、KClO4、K3PO4、K2CO3, KCl and KOH.The cationic salt of exemplary alkaline including earth metal can comprise CaSO4、Ca(NO3)2、Ca(ClO4)2、CaCO3With Ca (OH)2、MgSO4、Mg(NO3)2、Mg(ClO4)2、MgCO3, and Mg (OH)2.The electrolyte solution being substantially free of Na can be made up of any combination of this class salt.In other embodiments, electrolyte solution can include containing the cationic salt of Na and one or more solution containing the cationic salt of non-Na.

The wanted Performance Characteristics depending on energy storing device and the degradation/performance restriction scheme being associated with higher salt concentrations, for the Na in water at 100 DEG C2SO4, molar concentration scope is preferably in about 0.05M to 3M, for instance about 0.1 arrives 1M.For other salt, similar ranging for is preferred.

The admixture (such as, containing sodium salt and one or more the admixture in alkali metal, alkaline-earth metal, lanthanide, aluminum and zinc salt) of different salt can produce optimization system.This type of admixture can provide one or more cationic electrolyte with sodium cation and the choosing freely group of following thing composition: alkali metal (such as K), alkaline-earth metal (such as Mg and Ca), lanthanide, aluminum and zinc cation.

Optionally, can pass through to add some extra OH-Ionic species is so that electrolyte solution is more alkaline and change electrolytical pH value, for instance by add be different from NaOH containing OH salt, by adding some other OH-Concentration affects compound and (such as, adds H2SO4So that electrolyte solution is more acid).Electrolytical pH value can affect the scope (relative to reference electrode) of the voltage stabilization window of battery, and the stability of active cathode material and degradation also can have impact, and can suppress proton (H+) embed, proton (H+) embed and can work in active cathode material capacitance loss and battery degradation.In some cases, pH value rises to 11 to 13, thus allowing different active cathode material stable (stablizing for 7 times compared in pH neutral).In certain embodiments, pH value can in the scope of about 3 to 13, for instance about between 3 and 6 or about between 8 and 13.

Optionally, electrolyte solution contains the additive of the degradation for alleviating active cathode material (such as, birnessite material).Exemplary additive can be (but not limited to) Na2HPO4, present in an amount at least sufficient to the concentration setting up in the scope of 0.1mM to 100mM.

Dividing plate:

Dividing plate for using in an embodiment of the present invention can include cotton thin slice, PVC (polrvinyl chloride), PE (polyethylene), glass fibre or other suitable material any.

Operating characteristic:

As described above, contain in the embodiment of basic atom (being preferably Na or Li) before the use at active cathode material, the deintercalation during first time battery charge cycle of some or all in these atoms.Again embed during battery discharge from electrolytical alkaline kation (most for Na cation).These are different from the nearly all mixed capacitor system requiring intercalation electrode opposing activity carbon.In many number systems, it is adsorbed on anode during charging cycle from electrolytical cation.Meanwhile, the counter anion in electrolyte is embedded in active cathode material, therefore keeps charge balance in electrolyte solution but consumes ion concentration.During discharging, discharge cation from anode, and discharge anion from negative electrode, therefore in electrolyte solution, keep charge balance but add ion concentration.This is the operator scheme different from the device in embodiments of the invention.

Example

Assemble the mixed tensor storage device that there is the prism shown in Figure 1A/parallel connection electrical connection with the physical arrangement shown in Fig. 5-7.Device contains 106 groups of anode 104/ negative electrode (often group two) of three levels, wherein has graphite flake current collector 110a, 110c structure (500 microns of thickness) and the non-woven fiber separator material 108 of expansion, as shown in Figure 5.Negative electrode is containing, for example λ-MnO mentioned above2Phase active material, and be made up of the compressing granular thing of active material, carbon black, powdered graphite and PTFE.Anode contains the activated carbon mixed with carbon black and PTFE.Respective anode that pressure makes each graphite anode and cathode collector 110a, 110c with the positive and negative busbar serving as described device and negative electrode graphite busbar 122a, 122c is used to contact.Use polypropylene case 116 to carry out accommodation apparatus, and graphite busbar 122a, 122c via the appropriately sized hole feed-in in polypropylene case and are then used by silicone adhesive agent material relative to polypropylene seal.Then make copper cash via pressure to be connected with outside (the not touching electrolytical) busbar 124 coming from case, and use encapsulated epoxy resin to cover whole external bus.

Then make described device form circulation by 15, and in many circulations, then test its energy storage capacity and stability.Figure 12 shows the result of this test.The device current potential that Figure 12 (a) is illustrated in when charge and discharge in 30 circulations is to institute's cumulative capacity.Under C/6 rated current, perform circulation, and described device has the capacity of approximate 1.1Ah.The almost ideal overlap of described data display voltage's distribiuting between circulation, instruction is extreme stable and does not represent capacitance loss or has the system of any internal corrosion.Figure 12 (b) is the curve chart of the battery charge and discharge capacity become with circulation.At at least 60 capacitance loss not become along with circulation in circulating.Data from other battery indicate and can maintain this situation in several thousand circulations.Further, it was found that the coulombic efficiency of these circulations is 98 to 100%.

This example is illustrated in inside accumulator outer housing not use and produces high stability aqueous electrolyte mixed tensor storage device when any metal.Described device represents splendid stability and shows long-term for the long-range future in multiple kinds of energy storage application.

Although foregoing is with reference to certain preferred embodiment, it will be understood that, the present invention is not limited to this.Those skilled in the art will appreciate that, disclosed embodiment can be carried out various amendment, and this type of amendment is wished within the scope of the present invention.All publication set forth herein, patent application case and patent are incorporated by herein by reference.

Claims (49)

1. an electrochemical appliance, comprising:
Shell;
Electrochemical cell in the housing stacking, each electrochemical cell includes:
Anode electrode;
Cathode electrode;
Dividing plate, it is between described anode electrode and described cathode electrode;And
Electrolyte;
Multiple carbon cathodes and anode collector, it is alternately positioned between adjacent electrochemical cell;
More than first tab, it is operatively connectable to the plurality of carbon cathode current collector and more than second tab, and it is operatively connectable to the plurality of carbon anode current collector;
Wherein,
The cathode electrode of the first electrochemical cell electrically contacts the first cathode collector;
The cathode electrode of the second electrochemical cell electrically contacts described first cathode collector, described second electrochemical cell be positioned adjacent to described stacking in the first side of the first electrochemical cell;
The anode electrode electrical contact second plate current collector of described first electrochemical cell;And
The anode electrode of the 3rd electrochemical cell electrically contacts described second plate current collector, described 3rd electrochemical cell be positioned adjacent to described stacking in the second side of described first electrochemical cell.
2. electrochemical appliance according to claim 1, wherein said more than first tab is configured to be connected to each other, and described more than second tab is configured to be connected to each other.
3. electrochemical appliance according to claim 1, wherein said electrochemical appliance is mixing aqueous electrolyte energy storing device.
4. electrochemical appliance according to claim 3, wherein said negative electrode includes alkali ion insert material, and described anode is at fake capacitance electrochemically stable less than under-1.3V for relative NHE or electrochemical double layer capacitative materials.
5. electrochemical appliance according to claim 4, wherein said cathode electrode includes doped or undoped cubic spinel λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, described anode electrode includes activated carbon, titanic oxide material or phosphorus olivine material, and described electrolyte comprises sodium ion, and described current collector includes carbon fiber paper, scribbles the inert substrate of material with carbon element or have density more than 0.6g/cm3Expanded graphite.
6. electrochemical appliance according to claim 5, wherein said electrolyte is containing the aqueous solution of alkali ion dissolved, and described alkali ion can interact with anode and negative electrode and make to store electric charge via the embedding at described cathode electrode place and by the fake capacitance non-faraday surface reaction at described anode electrode place.
7. electrochemical appliance according to claim 1, wherein said shell comprises seal, the polymer shell of electrochemicaUy inert that is hedged off from the outer world, and electrochemical cell stacking in described electrochemical cell come stacking with prismatic configuration.
8. electrochemical appliance according to claim 1, wherein:
Described anode electrode comprises the multiple discrete anode parts separated by anode side boundary region;
Described cathode electrode comprises the multiple discrete cathode assembly separated by cathode-side boundary region;
Described dividing plate extends to above or below described anode side boundary region and described cathode-side boundary region;And
Described electrolyte is arranged in described dividing plate and is arranged in anode electrode borderline region and cathode electrode borderline region.
9. electrochemical appliance according to claim 1, wherein:
The thickness of described anode electrode and cathode electrode is between 0.05cm and 1cm;
Described anode electrode comprises the granular anode electrode of compacting;And
Described cathode electrode comprises the granular cathode electrode of compacting.
10. an electrochemical appliance, comprising:
Shell;
Electrochemical cell in the housing stacking, each electrochemical cell includes:
The granular anode electrode of compacting;
The granular cathode electrode of compacting;
Dividing plate, it is between described anode electrode and described cathode electrode;And
Electrolyte;
Multiple negative electrodes and anode collector, it is alternately positioned between adjacent electrochemical cell;
Wherein,
The cathode electrode of the first electrochemical cell electrically contacts the first cathode collector;
The cathode electrode of the second electrochemical cell electrically contacts described first cathode collector, described second electrochemical cell be positioned adjacent to described stacking in the first side of the first electrochemical cell;
The anode electrode electrical contact second plate current collector of described first electrochemical cell;And
The anode electrode of the 3rd electrochemical cell electrically contacts described second plate current collector, described 3rd electrochemical cell be positioned adjacent to described stacking in the second side of described first electrochemical cell.
11. electrochemical appliance according to claim 10, the thickness of wherein said anode electrode and cathode electrode is between 0.05cm and 1cm, and described current collector comprises carbon collector.
12. electrochemical appliance according to claim 11, wherein said current collector includes carbon fiber paper, scribbles the inert substrate of material with carbon element or have density more than 0.6g/cm3Expanded graphite.
13. electrochemical appliance according to claim 10, wherein said electrochemical appliance is mixing aqueous electrolyte energy storing device.
14. electrochemical appliance according to claim 13, wherein said negative electrode includes alkali ion insert material, and described anode is at fake capacitance electrochemically stable less than under-1.3V for relative NHE or electrochemical double layer capacitative materials.
15. electrochemical appliance according to claim 14, wherein said cathode electrode includes doped or undoped cubic spinel λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, described anode electrode includes activated carbon, titanic oxide material or phosphorus olivine material, and described electrolyte comprises sodium ion.
16. electrochemical appliance according to claim 15, wherein said electrolyte is containing the aqueous solution of alkali ion dissolved, and described alkali ion can interact with anode and negative electrode and make to store electric charge via the embedding at described cathode electrode place and by the fake capacitance non-faraday surface reaction at described anode electrode place.
17. electrochemical appliance according to claim 10, wherein said shell comprises seal, the polymer shell of electrochemicaUy inert that is hedged off from the outer world, and electrochemical cell stacking in described electrochemical cell come stacking with prismatic configuration.
18. electrochemical appliance according to claim 10, wherein:
Described anode electrode comprises the multiple discrete anode parts separated by anode side boundary region;
Described cathode electrode comprises the multiple discrete cathode assembly separated by cathode-side boundary region;
Described dividing plate extends to above or below described anode side boundary region and described cathode-side boundary region;And
Described electrolyte is arranged in described dividing plate and is arranged in anode electrode borderline region and cathode electrode borderline region.
19. an electrochemical appliance, comprising:
Shell;
Multiple electrodes stacking, it is laid out in parallel in the housing, each stacking includes anode electrode, cathode electrode and electrolyte;
Multiple dividing plate thin slices, each dividing plate thin slice in wherein said multiple dividing plate thin slices extends continuously between the plurality of stacking at least two is stacking, so that each dividing plate thin slice is between every a stack of adjacent anode electrode and cathode electrode;And
Multiple current collectors;
Wherein:
Described shell comprises the polymer shell that seal, electrochemicaUy inert that is hedged off from the outer world, and the described electrode in described stacking each comes stacking with prismatic configuration;
Each current collector in the plurality of current collector extends continuously between the plurality of stacking at least two is stacking;
Each dividing plate thin slice extend to adjacent stacking in adjacent anode electrode between anode side boundary region above or below;
Each dividing plate thin slice extend to adjacent stacking in neighbouring cathode electrode between cathode-side boundary region above or below;
Each anode collector in the plurality of current collector each stacking in adjacent anode electrode between extend, and extend to adjacent stacking in adjacent anode electrode between described anode side boundary region above and below;
Each cathode collector in the plurality of current collector each stacking in neighbouring cathode electrode between extend, and extend to adjacent stacking in neighbouring cathode electrode between described cathode-side boundary region above and below.
20. electrochemical appliance according to claim 19, the thickness of wherein said anode electrode and cathode electrode is between 0.05cm and 1cm, and described current collector comprises carbon collector.
21. electrochemical appliance according to claim 20, wherein said current collector includes carbon fiber paper, scribbles the inert substrate of material with carbon element or have density more than 0.6g/cm3Expanded graphite.
22. electrochemical appliance according to claim 19, wherein said electrochemical appliance is mixing aqueous electrolyte energy storing device.
23. electrochemical appliance according to claim 22, wherein said negative electrode includes alkali ion insert material, and described anode is at fake capacitance electrochemically stable less than under-1.3V for relative NHE or electrochemical double layer capacitative materials.
24. electrochemical appliance according to claim 23, wherein said cathode electrode includes doped or undoped cubic spinel λ-MnO2Types of material or Na4Mn9O18Tunnel construction iris material, described anode electrode includes activated carbon, titanic oxide material or phosphorus olivine material, and described electrolyte comprises sodium ion.
25. electrochemical appliance according to claim 24, wherein said electrolyte is containing the aqueous solution of alkali ion dissolved, and described alkali ion can interact with anode and negative electrode and make to store electric charge via the embedding at described cathode electrode place and by the fake capacitance non-faraday surface reaction at described anode electrode place.
26. electrochemical appliance according to claim 19, it comprises more than first tab further, and it is operatively connectable to the plurality of cathode collector and more than second tab, and it is operatively connectable to the plurality of anode collector.
27. electrochemical appliance according to claim 20, wherein:
Described anode electrode comprises the granular anode electrode of compacting;And
Described cathode electrode comprises the granular cathode electrode of compacting.
28. electrochemical appliance according to claim 19, each dividing plate thin slice in wherein said multiple dividing plate thin slice the plurality of stacking first stacking and second stacking between extend continuously so that each dividing plate thin slice is described between a stack of adjacent anode electrode and cathode electrode and between described second stacking adjacent anode electrode and cathode electrode.
29. an electrochemical appliance, comprising:
Shell;
Multiple electrodes stacking, it is laid out in parallel in the housing, each stacking includes anode electrode, cathode electrode and electrolyte;
Multiple dividing plate thin slices, so that each dividing plate thin slice is between every a stack of adjacent anode electrode and cathode electrode;And
Multiple current collectors;
Wherein:
Each dividing plate thin slice extend to adjacent stacking in adjacent anode electrode between anode side boundary region above or below;
Each dividing plate thin slice extend to adjacent stacking in neighbouring cathode electrode between cathode-side boundary region above or below;
Each anode collector in the plurality of current collector each stacking in adjacent anode electrode between extend, and extend to adjacent stacking in adjacent anode electrode between described anode side boundary region above and below;
Each cathode collector in the plurality of current collector each stacking in neighbouring cathode electrode between extend, and extend to adjacent stacking in neighbouring cathode electrode between described cathode-side boundary region above and below.
30. electrochemical appliance according to claim 29, it comprises more than first tab further, and it is operatively connectable to the plurality of cathode collector and more than second tab, and it is operatively connectable to the plurality of anode collector.
31. electrochemical appliance according to claim 30, wherein:
Described anode electrode comprises the granular anode electrode of compacting;And
Described cathode electrode comprises the granular cathode electrode of compacting.
32. electrochemical appliance according to claim 29, at least the 50% of wherein said anode side boundary region is not directed at the respective cathode borderline region crossing over described dividing plate thin slice.
33. an energy storing device, comprising:
Multiple electrochemical cells, each of which is formed by anode electrode, cathode electrode, the baffle unit between described anode electrode and described cathode electrode and the electrolyte between described anode electrode and described cathode electrode, the wherein said anode electrode position that to be placed in direction of principal axis with described cathode electrode generally relative;
First electrochemical cell array, its Part I comprising to be essentially perpendicular to the plurality of electrochemical cell of described axial first planar alignment;
Second electrochemical cell array, it comprises with the Part II of described direction of principal axis and the plurality of electrochemical cell stacking on described first array, and each electrochemical cell of wherein said second array is axially stacked on the electrochemical cell of described first array;
Wherein said first electrochemical cell array and described second electrochemical cell array through arrangement with
Face-to-face, the anode electrode of the electrochemical cell of wherein said first array directly with respect to the corresponding anode of the electrochemical cell of described second array, or
Back-to-back, the cathode electrode of the electrochemical cell of wherein said first array is directly with respect to the corresponding negative electrode of the electrochemical cell of described second array;
Wherein said baffle unit comprises the first dividing plate thin slice between described anode electrode and the cathode electrode of each electrochemical cell being positioned over described first array, and be positioned over described second array each electrochemical cell described anode electrode and cathode electrode between second partition thin slice.
34. energy storing device according to claim 33, wherein said first electrochemical cell array and described second electrochemical cell array are through arrangement face-to-face, it farther includes:
Conductive anode collector plate, it is positioned between described first row and described secondary series, and carries out telecommunication with the described anode electrode of each of the plurality of electrochemical cell of described first array and the described anode electrode with each of the plurality of electrochemical cell of described second array carries out telecommunication;
First conductive cathode collector plate, the described cathode electrode of each of its plurality of electrochemical cell with described first array carries out telecommunication;
Second conductive cathode collector plate, the described cathode electrode of each of its plurality of electrochemical cell with described second array carries out telecommunication;
Anode bus, itself and described anode collector carry out telecommunication;And
Cathode bus, its with described first cathode collector and each of described second cathode collector carry out telecommunication.
35. energy storing device according to claim 34, it comprises further:
One or more the first extra electrochemical cell array and the second electrochemical cell array, it is with arrangement in pairs face-to-face, and is stacked between described first array and described second array at described direction of principal axis;
Extra conductive anode collector plate, each of its anode electrode relative with each of extra the first electrochemical cell array with face-to-face in pairs arrangement and the second electrochemical cell array carries out telecommunication;
First extra conductive cathode collector plate, its described cathode electrode with each of the plurality of electrochemical cell of each the first extra array carries out telecommunication;And
Second extra conductive cathode collector plate, its described cathode electrode with each of the plurality of electrochemical cell of each the second extra array carries out telecommunication.
36. energy storing device according to claim 33, wherein said first electrochemical cell array comprises and has the single file electrochemical cell between 2 to 25 electrochemical cells.
37. energy storing device according to claim 33, wherein said first electrochemical cell array comprises and has the multiple lines and multiple rows electrochemical cell between 4 to 25 electrochemical cells.
38. energy storing device according to claim 33, it comprises shell further, and described shell is formed in it to receive described first electrochemical cell array and described second electrochemical cell array.
39. the energy storing device according to claim 38, wherein said shell comprises substrate wall and multiple side member, and each of wherein said electrochemical cell is surrounded by the side member of described shell.
40. energy storing device according to claim 33, wherein said first electrochemical cell array and described second electrochemical cell array are through back-to-back arrangement, it farther includes:
Conductive cathode collector plate, it is positioned between described first array and described second array, and carries out telecommunication with the described cathode electrode of each of the plurality of electrochemical cell of described first electrochemical cell array and the described cathode electrode with each of the plurality of electrochemical cell of described second electrochemical cell array carries out telecommunication;
First conductive anode collector plate, the described anode electrode of each of its plurality of electrochemical cell with described first array carries out telecommunication;
Second conductive anode collector plate, the described anode electrode of each of its plurality of electrochemical cell with described second array carries out telecommunication;
Cathode bus, itself and described cathode collector carry out telecommunication;And
Anode bus, its with described first anode current collector and each of described second plate current collector carry out telecommunication.
41. energy storing device according to claim 40, it comprises further:
One or more the first extra electrochemical cell array and the second electrochemical cell array, it is with back-to-back paired arrangement, and is stacked between described first array and described second array at described direction of principal axis;
Extra conductive cathode collector plate, each of its cathode electrode relative with each of extra the first electrochemical cell array with back-to-back paired arrangement and the second electrochemical cell array carries out telecommunication;
First extra conductive anode collector plate, its described anode electrode with each of the plurality of electrochemical cell of each the first extra array carries out telecommunication;And
Second extra conductive anode collector plate, its described anode electrode with each of the plurality of electrochemical cell of each the second extra electrochemical cell array carries out telecommunication.
42. energy storing device according to claim 33, wherein at the borderline region of described first array and each electrochemical cell of being provided about in described first plane in the described position of each electrochemical cell of described second array.
43. for the method forming energy storing device, it comprises:
Configure the first conductive current collector plate in the enclosure;
Arrange more than first first electrode with two-dimensional array pattern in described enclosure, wherein by borderline region, other electrode each of each of described more than first the first electrodes with described more than first the first electrodes is separated, and each of wherein said more than first the first electrodes carries out telecommunication with described first conductive current collector;
The first dividing plate thin slice, each of wherein said more than first the first electrodes and described first dividing plate thin slice physical contact is configured on described more than first the first electrodes and in described shell;
Arrange more than first second electrode with two-dimensional array pattern in described enclosure, wherein each of the second electrode more than first with the direction of principal axis top in each of described more than first the first electrodes and axially opposing carry out stacking, and wherein by described borderline region, other electrode each of each of described more than first the second electrodes with described more than first the second electrodes is separated;
Configuring the second conductive current collector sheet on described more than first the second electrodes and in described shell, each of wherein said more than first the second electrodes and described second conductive current collector carry out telecommunication;
Arrange more than second second electrode with two-dimensional array pattern in described enclosure, the each of wherein said more than second the second electrodes with the direction of principal axis top in the one of described more than first the second electrodes and axially opposing carry out stacking, and each of wherein said more than second the second electrodes carries out telecommunication with described second conductive current collector, and further, wherein by described borderline region, other electrode each of each of described more than second the second electrodes with described more than second the second electrodes is separated;
Second partition thin slice, each of wherein said more than second the second electrodes and described second partition thin slice physical contact is configured on described more than second the second electrodes and in described shell;
Arrange more than second first electrode with two-dimensional array pattern in described enclosure, the wherein each of more than second the first electrode and described second partition thin slice physical contact, and with the direction of principal axis top in the one of which of described more than second the second electrodes and axially opposing carry out stacking, and wherein by described borderline region, other electrode each of each of described more than second the first electrodes with described more than second the first electrodes is separated;
Configuring the 3rd conductive current collector plate on described more than second the first electrodes and in described shell, each of wherein said more than second the first electrodes and described 3rd conductive current collector plate carry out telecommunication;
The each of described first conductive current collector plate and described 3rd conductive current collector plate is electrically connected to the first conductive bus, and wherein said first conductive bus and the first electric terminals being arranged in described housing exterior carry out telecommunication;
Described second conductive current collector plate is electrically connected to the second conductive bus, and wherein said second conductive bus and the second electric terminals being arranged in described housing exterior carry out telecommunication;
Electrolyte is provided between the first contrary in pairs electrode and the second electrode.
44. method according to claim 43, its further comprise formed two take advantage of two arrays as described in two-dimensional array pattern.
45. method according to claim 43, the step that described first conductive current collector plate and described 3rd conductive current collector plate are wherein electrically connected to described first conductive bus connects different conduction tabs further contained between each and described first conductive bus of described first conductive current collector plate and described 3rd conductive current collector plate.
46. method according to claim 43, wherein described second conductive current collector plate is electrically connected to the step of described second conductive bus further contained in being connected conduction tab between described second conductive current collector plate and described second conductive bus.
47. method according to claim 43, it comprises each that forms described more than first the first electrodes and described more than second the first electrodes further and as cathode electrode and forms each of described more than first the second electrodes and described more than second the second electrodes as anode electrode.
48. method according to claim 43, it comprises each that forms described more than first the first electrodes and described more than second the first electrodes further and as anode electrode and forms each of described more than first the second electrodes and described more than second the second electrodes as cathode electrode.
49. method according to claim 43, wherein:
Described more than first the second electrode package of arranging are containing with two-dimensional array pattern arrangement described more than first second electrodes identical with described more than first the first electrodes;
Described more than second the second electrode package of arranging are containing with two-dimensional array pattern arrangement described more than second second electrodes identical with described more than first the first electrodes;And
Described more than second the first electrode package of arranging are containing with two-dimensional array pattern arrangement described more than second first electrodes identical with described more than first the first electrodes.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108923042A (en) * 2018-07-24 2018-11-30 南京大学 Sodium-ion battery stratiform manganese-based anode material and preparation method thereof

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8298701B2 (en) 2011-03-09 2012-10-30 Aquion Energy Inc. Aqueous electrolyte energy storage device
US8652672B2 (en) * 2012-03-15 2014-02-18 Aquion Energy, Inc. Large format electrochemical energy storage device housing and module
US8945756B2 (en) * 2012-12-12 2015-02-03 Aquion Energy Inc. Composite anode structure for aqueous electrolyte energy storage and device containing same
WO2014159976A1 (en) 2013-03-14 2014-10-02 Maxwell Technologies, Inc. Collector graphite film and electrode divider ring for an energy storage device
US9905850B2 (en) 2013-07-26 2018-02-27 Lg Chem, Ltd. Polycrystalline lithium manganese oxide particles, preparation method thereof, and cathode active material including the same
EP2918545B1 (en) * 2013-07-26 2016-11-23 LG Chem, Ltd. Polycrystalline lithium manganese oxide particles, method for preparing same, and anode active material containing polycrystalline lithium manganese oxide particles
US9905851B2 (en) 2013-07-26 2018-02-27 Lg Chem, Ltd. Cathode active material and method of preparing the same
US10347947B2 (en) * 2013-11-06 2019-07-09 Nazarbayev University Research and Innovation System Aqueous lithium-ion battery
CN105006528A (en) * 2014-04-17 2015-10-28 中国科学院上海硅酸盐研究所 Green and low-cost water-based sodium-ion battery
DE102014210803A1 (en) * 2014-06-05 2015-12-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Electric energy storage element, method and apparatus for its manufacture
WO2020067606A1 (en) * 2018-09-27 2020-04-02 재단법인 포항산업과학연구원 Sodium secondary battery module

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101310350A (en) * 2005-11-14 2008-11-19 富士重工业株式会社 Lithium ion capacitor
WO2009111744A2 (en) * 2008-03-07 2009-09-11 Mobius Power, Inc. Electrochemical cells with tabs
US20090253025A1 (en) * 2008-04-07 2009-10-08 Carnegie Mellon University Sodium ion based aqueous electrolyte electrochemical secondary energy storage device

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100332A (en) * 1977-02-22 1978-07-11 Energy Development Associates Comb type bipolar electrode elements and battery stacks thereof
US4728588A (en) * 1987-06-01 1988-03-01 The Dow Chemical Company Secondary battery
JPH065467A (en) * 1992-06-24 1994-01-14 Nec Corp Electric double layer capacitor
JPH0794169A (en) * 1993-09-20 1995-04-07 Yuasa Corp Nonaqueous electrolyte battery
JPH07240347A (en) * 1994-02-28 1995-09-12 Fuji Elelctrochem Co Ltd Coin type electrical double layer capacitor and its manufacture
US5476734A (en) * 1994-04-28 1995-12-19 Westinghouse Electric Corporation Current collector with integral tab for high temperature cell
JP3791149B2 (en) * 1997-09-29 2006-06-28 旭硝子株式会社 Electric double layer capacitor and manufacturing method thereof
CN1468455A (en) * 2000-10-06 2004-01-14 纳幕尔杜邦公司 High performance lithium or lithium ion cell
US6699623B1 (en) * 2000-04-26 2004-03-02 E. I. Du Pont De Nemours And Company High performance lithium or lithium ion cell
US8021775B2 (en) * 2001-07-13 2011-09-20 Inventek Corporation Cell structure for electrochemical devices and method of making same
JP2004164911A (en) * 2002-11-11 2004-06-10 Toyota Motor Corp Electrode for storage element, its manufacturing method, and its manufacturing device
US20060176675A1 (en) * 2003-03-14 2006-08-10 Bourns, Inc. Multi-layer polymeric electronic device and method of manufacturing same
JP2007019211A (en) * 2005-07-07 2007-01-25 Mitsubishi Electric Corp Electric double layer capacitor and its manufacturing method
BRPI0621977A2 (en) * 2006-08-31 2011-12-20 Firefly Energy Inc Electrode plate of an energy storage device, and, energy storage device
JP2010521053A (en) * 2007-03-26 2010-06-17 ザ ジレット カンパニー Battery electrode and battery including such electrode
JP5157244B2 (en) * 2007-05-11 2013-03-06 Tdk株式会社 Electrochemical device and manufacturing method thereof
CN101087018A (en) * 2007-06-28 2007-12-12 复旦大学 A water solution Na ion chargeable battery
JP2010232011A (en) * 2009-03-27 2010-10-14 Nissan Motor Co Ltd Secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101310350A (en) * 2005-11-14 2008-11-19 富士重工业株式会社 Lithium ion capacitor
WO2009111744A2 (en) * 2008-03-07 2009-09-11 Mobius Power, Inc. Electrochemical cells with tabs
US20090253025A1 (en) * 2008-04-07 2009-10-08 Carnegie Mellon University Sodium ion based aqueous electrolyte electrochemical secondary energy storage device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108923042A (en) * 2018-07-24 2018-11-30 南京大学 Sodium-ion battery stratiform manganese-based anode material and preparation method thereof

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