CN105761941B - Metal-free aqueous electrolyte energy storage device - Google Patents

Metal-free aqueous electrolyte energy storage device Download PDF

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Publication number
CN105761941B
CN105761941B CN201610179405.5A CN201610179405A CN105761941B CN 105761941 B CN105761941 B CN 105761941B CN 201610179405 A CN201610179405 A CN 201610179405A CN 105761941 B CN105761941 B CN 105761941B
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China
Prior art keywords
cathode
electrochemical cell
anode
electrode
collector
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CN201610179405.5A
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Chinese (zh)
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CN105761941A (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
    • 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
    • H01G11/04Hybrid capacitors
    • H01G11/06Hybrid capacitors with one of the electrodes allowing ions or anions to be reversibly doped thereinto, e.g. lithium-ion capacitors [LICs]
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/10Multiple hybrid or EDL capacitors, e.g. arrays or modules
    • H01G11/12Stacked hybrid or EDL capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/66Current collectors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00Hybrid cells; Manufacture thereof
    • H01M12/005Hybrid cells; Manufacture thereof composed of a half-cell of the capacitor type and of a half-cell of the primary or secondary battery type
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/0257Cases, jackets or wrappings characterised by the material
    • H01M2/0277Insulating material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/06Arrangements for introducing electric connectors into or through cases
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/20Current conducting connections for cells
    • H01M2/22Fixed connections, i.e. not intended for disconnection
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/20Current conducting connections for cells
    • H01M2/22Fixed connections, i.e. not intended for disconnection
    • H01M2/26Electrode connections
    • H01M2/266Interconnections of several platelike electrodes in parallel, e.g. electrode pole straps or bridges
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/665Composites
    • 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 metal-free aqueous electrolyte energy storage devices.The present invention relates to a kind of electrochemical appliances, and it includes the electrochemical cell stacks in shell and the shell.Each electrochemical cell includes anode electrode, cathode electrode, partition board and electrolyte between the anode electrode and the cathode electrode.The cathode bus of the anode bus of the anode of the electrochemical appliance also comprising current-collector, the electrochemical cell being operatively connectable in the stacking between adjacent electrochemical cell and the cathode for the electrochemical cell being operatively connectable in the stacking.The shell, the anode electrode, the cathode electrode, the partition board, the anode bus and the cathode bus are nonmetallic.

Description

Metal-free aqueous electrolyte energy storage device

The relevant information of divisional application

This case is divisional application.The female case of the division be the applying date be on March 8th, 2012, application No. is 201280012476.6, the invention patent application case of entitled " metal-free aqueous electrolyte energy storage device ".

Related application

Present application advocates No. 61/450,774 US application case and March 9 in 2011 filed in 9 days March in 2011 The benefit of priority of 13/043rd, No. 787 US application case filed in day, the 61/450th, No. 774 and the 13/043rd, No. 787 The full content of application case 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 not with aqueous electrolyte The electrochemical storage device of the metal parts of contact.

Background technology

Small-sized rechargeable energy acquisition is with generation technology (for example, solar battery array, wind turbine, this miniature spy Woods engine (sterling engine) and solid oxide fuel cell) rising, and to it is medium sized it is secondary (can be again Charging) energy storage capability needs it is equally powerful.Accumulator for these stationary applications is commonly stored between 1 and 50kWh Energy (depend on application), and be based on plumbic acid (Pb acid) chemical reaction in the past.Deep follow is assembled at distributed power generation place Ring lead-acid battery group, and these known battery packs depending on exemplary operation recycle and it is sustainable use 1 to 10 years.Although these are electric Pond can operate well enough to support this application, but exist and use associated many problems with it, including:It is a large amount of to use meeting The lead and acid for polluting environment (are estimated often to be only and result in discharging more than 100,000 tons into environment in U.S.'s Pb technic acids Pb), be maintained at intermediate charged state or it is daily be recycled to deep discharge grade in the case of significant performance degradation, needs Routine servicing is to maintain performance, and implements necessary recycling plan.Replace the Pb acid chemical group as used in auto industry At needs it is very strong.Unfortunately, so far, the economy of alternative battery chemistries composition still makes it not inhale very much Gravitation.

Although battery technology achieve it is nearest made progress, still without to the inexpensive, dry of Pb acid chemical compositions Net alternative solution.This is particularly since Pb acid accumulators significantly cheap ($ compared with other chemical compositions 200/kWh), it and current just concentrate on exploitation (it is inherently more aobvious than Pb acid accumulator for the higher-energy systems of transport applications It writes more expensive).

Invention content

One embodiment is related to a kind of electrochemical appliance, and it includes the electrochemical cell stacks in shell and the shell.Often One electrochemical cell include anode electrode, cathode electrode, the partition board between the anode electrode and the cathode electrode, with And electrolyte.Electrochemical appliance includes also current-collector between adjacent electrochemical cell, is operatively connectable to the heap The anode bus of the anode of electrochemical cell in folded and the moon for the electrochemical cell being operatively connectable in the stacking The cathode bus of pole.The shell, the anode electrode, the cathode electrode, the partition board, the anode bus and described the moon Pole bus is nonmetallic." nonmetallic " in the context of this specification means not leading made of simple metal or metal alloy Electric material.The example of nonmetallic materials is including (but not limited to) conductive metal oxide or carbon.

Another embodiment is related to a kind of method of manufacture electrochemical appliance.Method includes:Stack the first non-metallic anode electricity Pole;The first nonmetallic partition board is stacked on the anode electrode;And the first non-metallic cathode electrode is stacked on the partition board. Method also includes:The first anode electrode is operatively connected to non-metallic anode bus;And it operatively will be described First cathode electrode is connected to non-metallic cathode bus.

One embodiment is related to a kind of electrochemical appliance, and it includes the electrochemical cell stacks in shell and the shell.Often One electrochemical cell include anode electrode, cathode electrode, the partition board between the anode electrode and the cathode electrode, with And electrolyte.Device also includes:Multiple carbon cathodes and anode collector, are alternately positioned between adjacent electrochemical cell;With And multiple tabs, it is operatively connectable to the multiple carbon cathode and anode collector, the multiple tab is configured to connect It is connected to electric bus.The cathode electrode of first electrochemical cell is in electrical contact the first cathode collector.The moon of second electrochemical cell Pole electrode is in electrical contact the first cathode collector.The first electrochemical cell of second electrochemical cell being positioned adjacent in stacking First side.The anode electrode of first electrochemical cell is in electrical contact second plate current-collector.The anode of third electrochemical cell Electrode is in electrical contact second plate current-collector.Third electrochemical cell be positioned adjacent to stack in the first electrochemical cell the Two sides.

Another embodiment is related to a kind of electrochemical appliance, and it includes the electrochemical cell stacks in shell and the shell. Each electrochemical cell includes the granular anode electrode of compacting, the granular cathode electrode of compacting, positioned at the anode electrode and institute State the partition board and electrolyte between cathode electrode.Electrochemical appliance is also comprising multiple cathodes and anode collector, alternately Between adjacent electrochemical cell.The cathode electrode of first electrochemical cell is in electrical contact the first cathode collector.Second electrification The cathode electrode for learning battery is in electrical contact the first cathode collector.The first electricity of second electrochemical cell being positioned adjacent in stacking First side of chemical cell.The anode electrode of first electrochemical cell is in electrical contact second plate current-collector, and third electrochemistry electricity The anode electrode in pond is in electrical contact second plate current-collector.The first electrochemistry of third electrochemical cell being positioned adjacent in stacking The second side of battery.

Another embodiment is related to a kind of electrochemical appliance, and it includes shells and the multiple electricity being arranged side by side in the housing Chemical cell stacks.Each electrochemical cell includes anode electrode, cathode electrode, is located at the anode electrode and cathode electricity Partition board between pole and electrolyte.Described device also includes the adjacent electrochemical electricity being located in each of described stacking Current-collector between pond.The partition board of at least one battery is included in being at least extended continuously between the two in the multiple stacking Partition board thin slice.

One embodiment is related to a kind of electrochemical appliance, and it includes the electrochemical cell stacks in shell and the shell.Often One electrochemical cell include anode electrode, cathode electrode, the partition board between the anode electrode and the cathode electrode, with And electrolyte.The electrochemical appliance also includes the graphite flake between the adjacent electrochemical cell being located in the stacking.Institute State the current-collector that graphite flake is adjacent electrochemical cell.

Another embodiment is related to a kind of electrochemical cell, it includes:It is multiple discrete with being separated by anode borderline region The anode electrode of anode electrode component;And the cathode with the multiple discrete cathode electrode components separated by cathode borderline region Electrode.Electrochemical cell also includes the partition board and electrolyte between anode electrode and cathode electrode.The electrolyte position In the partition board and in anode electrode borderline region and cathode electrode borderline region.In addition, anode borderline region At least 50% is not aligned with the respective cathode borderline region on partition board opposite.

Another embodiment is related to a kind of method of electrochemical appliance of the manufacture with electrochemical cell stacks.The method packet Contain:Form stacked electrochemical cells;And electric insulating copolymer is cast in around the electrochemical cell stacks and is made described Polymer solidification is to form solid insulation shell, or preformed solid insulation shell is provided around the electrochemical cell stacks Body.

Another embodiment is related to a kind of method of manufacture electrochemical appliance.The method includes:Stack anode electrode, packet Include the multiple discrete anode electrod assemblies separated by anode borderline region;The stack separator on the anode electrode;And institute It states and stacks cathode electrode on partition board, the cathode electrode includes the multiple discrete cathode electrode portions separated by cathode borderline region Part.At least the 50% of the anode borderline region is not aligned with the respective cathode borderline region on the partition board opposite, and described Multiple anode electrode components and the multiple cathode electrode component are arranged to the array with rows and columns.

Another embodiment is related to the secondary aqueous energy storage device of mixing.The secondary aqueous energy storage device of mixing includes outer Electrochemical cell stacks in shell and the shell.Each electrochemical cell is comprising anode electrode, cathode electrode and is located at institute It is thin to state partition board between anode electrode and the cathode electrode, electrolyte and graphite between adjacent electrochemical cell Piece.The thickness of the anode and cathode electrode is between 0.05cm and 1cm.

Description of the drawings

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

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

Fig. 3 is the perspective view for the electrochemical appliance that multiple prisms according to the embodiment with electrochemical cell stack.

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

Fig. 5 is the perspective view for the electrochemical appliance that the single prism according to the embodiment with electrochemical cell stacks.

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

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

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

Fig. 9 is schematically illustrating for electrochemical cell according to an embodiment of the invention.The electrochemical cell can be double Pole or prism stack arrangement stack.

Figure 10 is the cross-sectional view of electrochemical cell according to the embodiment, with what is be made of discrete anode electrod assembly Anode electrode and the cathode electrode being made of discrete cathode electrode component.The electrochemical cell can bipolar or prism stacking match It sets to stack.

Figure 11 is the signal of the electrochemical appliance of the bipolar stack according to an embodiment of the invention including electrochemical cell Property explanation.

Figure 12 (a) is curve graph of cell potential under the conditions of charge and discharge in 30 cycles to institute's cumulative capacity. Figure 12 (b) is the curve graph of the battery charge and discharge capacity and efficiency that become with cycle.

Specific implementation mode

The embodiment of the present invention be related to electrochemical energy storage system, such as primary and secondary accumulator described below with And mixed tensor storage system.Although the secondary aqueous energy storage system of mixing described below is the preferred implementation of the present invention Example, but the present disclosure additionally applies for any suitable electrochemical energy storage systems, such as contain aqueous and non-aqueous electrolyte Accumulator (for example, anode and cathode with the embedded ion from electrolyte, including Li ion accumulators etc.), or electrolysis electricity Container (also referred to ultra-capacitor and ultracapacitor, for example, it is with capacitor or pseudocapacitors anode and cathode electrode, institute Electrode is stated via reversible non-faraday (nonfaradiac) reaction of the cation on the surface of electrode (bilayer) and/or counterfeit electricity Hold and store charge, rather than pass through embedded alkali ion).

The hybrid electrochemical energy storage system of the embodiment of the present invention includes to be coupled with active electrode (for example, cathode) Double layer capacitor or pseudocapacitors electrode (for example, anode).In such systems, capacitor or pseudocapacitors electrode are via electrode The reversible non-faraday of alkaline kation on the surface of (bilayer) react and/or fake capacitance and store charge, and active electrode Reversible faraday's reaction of the experience similar to accumulator in embedded and deintercalation alkaline kation transition metal oxide.

The example of Na based systems is described in No. 12/385,277 U.S. patent application case filed in 3 days April in 2009 In and full text be incorporated herein by reference, the example utilize spinel structure LiMn2O4Battery terminal, activated carbon Electrode for capacitors and aqueous Na2SO4Electrolyte.In such a system, bear anode electrode via the Na on the surface of active carbon electrode from The reversible non-faraday of son reacts and stores charge.Positive cathode electrode utilizes spinelle λ-MnO2In Na ions insertion/deintercalation Reversible faraday's reaction.

In alternative system, cathode electrode may include non-embedded (for example, non-alkaline ion is embedded in) MnO2Phase.Manganese dioxide The non-embedded phase of example include α phases and γ phases electrolytic manganese dioxide (EMD).

Fig. 1 illustrates that the prism of electrochemical cell 102 according to the embodiment stacks 100P.In this embodiment, prism stacks Each of electrochemical cell 102 in 100P is comprising anode electrode 104, cathode electrode 106 and is located at anode electrode 104 Partition board 108 between cathode electrode 106.Electrochemical cell 102 also include be located at anode electrode 104 and cathode electrode 106 it Between electrolyte (that is, flowing into partition board and/or electrode).Prism can be stacked each in the electrochemical cell 102 of 100P Person is mounted in frame 112 (referring to Fig. 9-10).In addition, alternatively or additionally, prism can also be stacked to 100P closings In shell 116 (referring to Fig. 3-6).The additional of shell 116 is provided in more detail below with respect to the embodiment illustrated in Fig. 3-6 Feature.The other embodiments of electrochemical cell 102 are illustrated in Fig. 9 and Figure 10 and are hereinafter relatively discussed in detail.Prism stacks 100P is also included in the multiple carbon cathodes and anode collector 110a, 110c of positioned alternate between adjacent electrochemical cell 102.Collection Electric appliance may include the conductive carbon of any suitable form, such as expanded graphite, carbon fiber paper or the inert substrate for being coated with carbon material.It is excellent Selection of land, current-collector include that density is more than 0.6g/cm3Graphite.

In embodiment, it includes multiple conductive junction points (for example, tab) 120 that prism, which stacks 100P, is operatively connected To multiple carbon cathodes and anode collector 110a, 110c.Conductive junction point 120 can attach to carbon cathode and anode collector 110a, The side of 110c.Alternatively, as illustrated in figure 2, conductive junction point 120 can be located between two carbon collectors 110a or 110c, from And constitute sandwich 110s.Preferably, it includes two electric bus 122a, 122c that prism, which stacks 100P also,.One electrical total Line 122a is electrically connected to the anode collector 110a in prism stacking 100P, and an electric bus 122c is connected to prism stacking Cathode collector 110c in 100P.In embodiment, from anode and cathode current-collector 110a, 110c to electric bus 122a, The electrical connection of 122c is via conductive junction point 120.By this method, stack 100P in electrochemical cell 102 can parallel connection be electrically connected It connects.

In embodiment, positive cathode bus 122c makes the cathode electrode 106 and heap of the electrochemical cell 102 in stacking 100P Folded positive electrical output-parallel electrical connection, and negative anode bus 122a makes the anode electricity of the electrochemical cell 102 in stacking 100P Pole 104 is electrically connected with the negative electrical output-parallel for stacking 100P.

In prism stacks 100P, cathode collector 110c can be between adjacent electrochemical cell 102.That is, pairs of Electrochemical cell 102 is configured as " face-to-face " and " back-to-back ".As example, the first electrochemical cell 102 wherein is considered Prism in the center for stacking 100P stacks 100P.In first pair of battery 102, the first cathode collector 110c it is located and So that the cathode electrode 106 of the first electrochemical cell 102 is in electrical contact the first cathode collector 110c, and the second electrochemical cell 102 cathode electrode 106 is also in electrical contact the first cathode collector 110c.Second electrochemical cell 102 is positioned adjacent to prism Stack first (cathode) side of the first electrochemical cell in 100P.

Be positioned adjacent to the first electrochemical cell 102 that prism stacks in 100P second of third electrochemical cell 102 (anode) side.The anode electrode 104 of first electrochemical cell 102 is in electrical contact first anode current-collector 110a, and third electrochemistry The anode electrode 104 of battery 102 is also in electrical contact first anode current-collector 110a.Stacking can continue by this method.Gained prism heap Therefore folded 100P may include that alternate anode electrode 104 is adjacent and the adjacent face-to-face and back-to-back pairs of heap of cathode electrode 106 Folded multiple electrochemical cells 102.

Prism can be described in the axial direction stacks 100P.For stacking 100P illustrated in fig. 1, it is axially parallel to bus 122a、 122c.The electrochemical cell 102 stacked in 100P stacks in the axial direction along the axis for stacking 100P.Odd number in stacking Or each of electrochemical cell 120 of even-numbered has the cathode electrode of the first end of the axis in face of stacking 100P 106 and in face of stack 100P axis opposite second end anode electrode 104.Stack the electricity of even number or odd-numbered in 100P Each of other persons in chemical cell 102 have 106 He of cathode electrode of the second end of the axis in face of stacking 100P In face of the anode electrode 104 of the opposite first end for the axis for stacking 100P.

In embodiment, it includes electrochemical cell 102, wherein anode electrode 104 and/or cathode electrode that prism, which stacks 100P, The 106 granular bead by suppressing is made.The thickness of anode electrode 104 and cathode electrode 106 can be between 0.05cm and 1cm.Or The thickness of person, anode electrode 104 and cathode electrode 106 is between 0.05cm and 0.15cm.Side between the granular bead of compacting Battery limit (BL) domain can provide the storage of electrolyte, such as will be described in further detail below.

In embodiment, electrochemical cell 102 is the secondary aqueous energy storage device of mixing.In embodiment, cathode electricity Pole 106 is reversibly embedded in alkali metal cation in operation.Anode electrode 104 may include on the surface via anode electrode 104 Alkali metal cation the reaction of reversible non-faraday and store the capacitive electrode of charge, or experience and anode electrode 104 The fake capacitance electrode of the Partial charge transitional surface interaction of alkali metal cation on surface.In embodiment, anode For fake capacitance or electrochemical double layer capacitative materials, in the case where relative standard's hydrogen electrode (NHE) is less than -1.3V, electrochemistry is steady It is fixed.In embodiment, cathode electrode 106 may include doping or undoped cubic spinel λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, and anode electrode 104 may include activated carbon.Alternatively, cathode electrode may include it is non-embedded MnO2Phase, such as α or γ phases electrolytic manganese dioxide (EMD).

Illustrate another embodiment of the present invention in Fig. 3 and Fig. 4.In this embodiment, electrochemical appliance 300 includes electrochemistry Eight stacking 100P for multiplying four arrays in two of battery 102.However, may include that any number stacks 100P.For example, electric Chemical devices 300 may include three stacking 100P for stacking 100P in multiply two arrays two, multiplying three arrays in one, multiply in three 25 stacking 100P that 12 of four arrays stack 100P or multiply five arrays in five.It can be according to the needs or electric power of end user Demand and select stack 100P exact number.

Electrochemical appliance 300 preferably comprises shell 116.In this embodiment, shell 116 includes substrate 116b and multiple sides Wall components 116a.In embodiment, multiple 104 Hes of anode electrode for stacking the electrochemical cell 102 in each of 100P Cathode electrode 106 exposes to the open air along its edge, but is constrained by shell 116.Preferably, shell 116 is provided across each stacking The pressure of 100P, to which the stacking 100P of electrochemical appliance 300 is kept fastening.In alternative embodiments, multiple stacking 100P Each of in electrochemical cell 102 anode electrode 104 and cathode electrode 106 along its edge and partially or completely Ground is through covering and constraining.For example, this can be by the way that the anode electrode 104 of each battery 102 and cathode electrode 106 to be mounted on It is realized in frame 112, as shown in Figure 9.Other shells also can be used to configure.For example, shell 116 may include substrate 116b and single integral side walls component 116a similar to bell jar.

In this embodiment, the partition board 108 of at least one electrochemical cell 102 and/or anode collector 110a and/or the moon Pole current-collector 110c at least continuously extending between the two in multiple stacking 100P.Preferably, partition board 108, anode current collection Device 110a and cathode collector 110c continuously extends between all stacking 100P in electrochemical appliance 300.By this method, Electrochemical appliance 300 can easily and inexpensively be manufactured.However, the cathode electrode of each battery 102 in cell stacks 100P 106 and anode electrode 104 preferably discontinuously extend to another battery 102 stacked in the other of 100P.In embodiment In, electrolyte storage is contained in the space between the electrode 104,106 of adjacent stacks 100P.

In embodiment, electrochemical appliance 300 further includes the combined type for all positive outputs for being electrically connected multiple stackings Positive bus and first end plate 122c, and the combined type of the multiple all negative outputs for stacking 100P of electrical connection bear bus and second end Plate 122a.In addition, substrate 116b may include that external electrical contact 124, the external electrical contact 124 allow electrochemical appliance 300 are rapidly and easily attached to load.

In embodiment, electrochemical appliance 300 is above-described hybrid electrochemical device.Preferably in this embodiment In, all electrochemical cells 102 of the stacking 100P of electrochemical cell 102 are hybrid electrochemical battery.Such as discussed above In embodiment, hybrid electrochemical battery 102 may include that cathode electrode 106 and anode electrode 104, wherein cathode electrode 106 include Doping or undoped cubic spinel λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, and anode electricity Pole 104 includes activated carbon, and electrolyte includes the aqueous electrolyte containing sodium ion.Can use as discussed below other cathodes and Anode material.Device may include secondary accumulator battery, such as Li ions or Na ion accumulators in alternative embodiments.

Illustrate another embodiment of the present invention in Fig. 5 and Fig. 6.In this embodiment, electrochemical appliance 500 as described Including the single prism of electrochemical cell 102 stacks 100P.More than one stacking can be used.Electrochemical cell 102 it is single Prism stacks 100P and is located in shell 116.Electrochemical appliance 500 includes anode bus 122a and cathode bus 122c.Prism heap Each of the anode 104 in electrochemical cell 102 in folded 100P is electrically connected to anode via anode collector 110a Bus 122a.In this embodiment, anode 104 is connected in parallel.Similarly, prism stacks in the electrochemical cell 102 in 100P Each of cathode 106 be electrically connected to cathode bus 122c via cathode collector 110c.In this embodiment, cathode 106 are connected in parallel.Preferably, anode collector 110a and cathode collector 110c are connected to its phase by conductive tab 120 Answer anode bus 122a and cathode bus 122c.Current-collector 110a, 110c can be operatively connectable to phase by the following terms The tab 120 and/or anode and cathode bus 122a, 122c answered:Pressure/friction fitting, conductive electrochemicaUy inert solidified oil The electrochemicaUy inert cured epoxy resin of paint or conduction.Electrochemical appliance 500 also includes external electrical contact 124 with from electrification Device 500 is learned to power to external device (ED) or circuit.In embodiment, external electrical contact 124 is located at anode bus 122a and the moon On the top of pole bus 122c.Alternatively, the contact can be located in the bottom or side of bus.The contact can be located at device On identical or different side.

In embodiment, all components that the usual and electrolyte of electrochemical appliance 500 contacts are (that is, anode 104, cathode 106, partition board 108, current-collector 110, bus 122, tab 120 and shell 116) it is made of nonmetallic materials.In embodiment, collect Electric appliance 110, bus 122 and tab 120 can be made of the carbon of any suitable Conducting forms.Bus and tab can be by graphite, carbon Fiber or carbon-based conductive compound (for example, polymer substrate of carbon fiber-containing or packing material) are made.Shell 116 can by (but It is not limited to) electrochemicaUy inert and electric insulating copolymer be made.By this method, electrochemical appliance 500 is corrosion resistant.If total Line 122 does not contact electrolyte (that is, tab extends through sealing material to external bus), then bus can be made of metal.Outside Portion's electric terminal 124 can be made of metal material.In the embodiment being illustrated in Figure 7, bus 122 is enclosed by gas-tight seal 114 It is located at the top of bus 122 around, the gas-tight seal 114, the prism of electrochemical cell 102 stacks top and the contact of 100P Between 124.Sealing element may include the polymer or epoxide resin material of impermeable electrolyte and oxygen, such as the ring based on polymer Oxygen resin, glue, quick lime or melting sealed polymer.Bus 122 can be carried by welding, bolt, clamp and/or sealing material The pressure of confession and be connected to contact 124.By this method, external electrical contact 124 can be isolated with electrolyte, to allow outside Electric terminal 124 is made of metal material (such as copper).Therefore, the only sealing element of hard contact or interconnection piece 124 from shell 116 114 regions protrude.

Fig. 8 is curve graph of the cell potential to battery capacity of the embodiment of electrochemical appliance 500.As can in curve graph See the battery capacity, it can be achieved that high, such as 1200mAh is more than for 0.5V and 0.5V voltages below.

Fig. 9 illustrates the embodiment of electrochemical cell 102.Electrochemical cell 102 includes anode electrode 104, cathode electrode 106 and the partition board 108 between anode electrode 104 and cathode electrode 106.Electrochemical cell 102 also includes to be located at anode electricity Electrolyte between pole 104 and cathode electrode 106.In embodiment, partition board 108 can be porous, and wherein electrolyte is located at institute It states in hole.Electrolyte can be aqueous or non-aqueous.Electrochemical cell 102 also may include the collection for serving as electrochemical cell 102 The graphite flake 110 of electric appliance.Preferably, graphite flake 110 is fine and close.In embodiment, the density of graphite flake 110 is more than 0.6g/cm3.Graphite flake 110 can be made of (for example) expanded graphite.In embodiment, graphite flake 110 may include one or More than one layers of foil.The conjunction for anode electrode 104, cathode electrode 106, partition board 108 and electrolyte is relatively discussed in detail below Suitable material.

It is each anode electrode 104, cathode electrode 106, partition board 108 and graphite flake current-collector 110 can be mounted on sealing In the frame 112 of Individual cells.Frame 112 is preferably formed of an electrically insulating material, such as electrically insulating plastic material or epoxy resin.Frame 112 can be made of the combination of preforming ring, casting epoxy resin or both.In embodiment, frame 112 may include individually Anode and cathode frame.In embodiment, graphite flake current-collector 110 can be configured to serve as the sealing element 114 of frame 112. That is, to serve as sealing element 114 in the recess that graphite flake current-collector 110 may extend into frame 112.In this embodiment, close Sealing 114 prevents electrolyte from flowing to adjacent electrochemical cell 102 from an electrochemical cell 102.In alternative embodiments, may be used There is provided individual sealing element 114 (for example, washer or gasket) so that graphite flake current-collector does not serve as sealing element.

In embodiment, electrochemical cell is hybrid electrochemical battery.That is, cathode electrode 106 is reversibly embedding in operation Enter alkali metal cation, and anode electrode 104 includes the reversible non-of the alkali metal cation on surface via (1) anode electrode Faraday's reaction and store the capacitive electrode of charge or the portion of (2) experience and the alkali metal cation on the surface of anode electrode Divide the fake capacitance electrode of charge transfer surface interaction.

Figure 11 illustrates the bipolar stack 100B of electrochemical cell 102 according to another embodiment.With include individual anode Side is compared with the conventional electrochemical cell of cathode side current collector stacking, and bipolar stack 100B is by being located at an electrochemical cell Single graphite flake current-collector 110 between 102 cathode electrode 106 and the anode electrode 104 of adjacent electrochemical cell 102 Operation.Therefore, the current-collector more than the current-collector half that conventional electrochemical cell stacks is used only in bipolar stack 100B.

In embodiment, bipolar stack 100B is enclosed in outer enclosure 116 and at the top and bottom of bipolar stack 100B Has conductive header 118 in portion.Head 118 preferably includes corrosion-resistant current-collector metal, including (but not limited to) aluminium, nickel, titanium and Stainless steel.Preferably, it pressure is applied to bipolar stack 100B in assembling.Pressure help provide good sealing to prevent Only electrolyte leakage.

In embodiment, electrochemical cell 102 is the secondary aqueous energy storage device of mixing.In this embodiment, anode The thickness of electrode 104 and cathode electrode 106 can between 0.05cm and 1cm, such as thickness between 0.05cm and 0.15cm it Between.

Figure 10 illustrates another embodiment of the present invention.In this embodiment, anode electrode 104 may include by anode frontier district The discrete anode electrod assembly 104a that domain 104b separates.In addition, cathode electrode 106 may include by cathode borderline region 106b points Every discrete cathode electrode component 106a.As described, anode electrode 104 includes two discrete anode electrod assembly 104a, and Cathode electrode 106 includes three discrete cathode electrode component 106a.However, this is only for illustrating.Anode electrode 104 and cathode Electrode 106 can separately include any number discrete anode electrod assembly 104a and discrete cathode electrode component 106a.In addition, In embodiment, anode borderline region 104b and cathode borderline region 106b may include the gap for filling electrolyte.

In addition, Figure 10 only illustrates the cross section in a dimension.Cross-sectional view on orthogonal direction also it is explainable have from Dissipate the anode electrode 104 and cathode electrode 106 of anode electrode component 104a and discrete cathode electrode component 106a.That is, anode is electric Pole 104 and cathode electrode 106 may include two-dimentional checkerboard pattern.In other words, discrete anode electrod assembly 104a and discrete the moon Pole electrod assembly 106a may be disposed to the array with rows and columns.A other discrete anode electrod assembly 104a and discrete The shape of cathode electrode component 106a may be, for example, square or rectangle.In embodiment, inventor has found:There is provided has not With the anode electrode 104 and cathode electrode 106 of number discrete anode electrod assembly 104a and discrete cathode electrode component 106a Improve the structural intergrity of electrochemical cell 102.In this embodiment, the row and column of anode deviates from the row and column of cathode. In embodiment, at least 50% (for example, 50-100%, including 75-95%) of anode borderline region 104b not in partition board 108 The respective cathode borderline region 106b alignments on opposite.Alternatively, anode electrode 104 and cathode electrode 106 may include it is equal number of Discrete anode electrod assembly 104a and discrete cathode electrode component 106a.In alternative embodiments, anode electrode 104 or cathode electricity Any one in pole 106 may include single one-piece sheet, and another electrode includes the checkerboard pattern of discreet component.

In embodiment, anode electrode component 104a and cathode electrode component 106a rolling by activated carbon and manganese oxide respectively Thin slice processed or pressed pellet are made.Another embodiment is related to a kind of method of the electrochemical appliance of manufacture Figure 10, and it includes following Step:(1) anode electrode 104 is stacked, anode electrode 104 includes the multiple discrete anodes electricity separated by anode borderline region 104b Partition board 108 is stacked on anode electrode 104 by pole component 104a, (2), and cathode electrode 106 is stacked on partition board 108 by (3) On, cathode electrode 106 includes the multiple discrete cathode electrode component 106a separated by cathode borderline region 106b.A side Face, at least the 50% of anode borderline region 104b is not aligned with the respective cathode borderline region 106b on 108 opposite of partition board.Method Also may include step graphite flake current-collector 110 being stacked on cathode electrode 106.It can be by from anode or cathode material Rolled sheet cutting part 104a, 106a forms anode electrode component 104a by the bead of pressed-powder anode or cathode material And/or cathode electrode component 106b.

Another embodiment of the present invention is related to a kind of method of stacking 100B, 100P of manufacture electrochemical cell 102.It is described Method may include being formed stacked electrochemical cells and by electric insulating copolymer be cast in electrochemical cell 102 stacking 100B, The step of around P.Method also may include making polymer solidification to form solid insulation shell or frame 112.Alternatively, method can wrap The step of preformed solid insulation shell 112 are provided is contained in around the stacking of electrochemical cell 102.Polymer can be (but unlimited In) epoxy resin or acrylic resin.

Method also may include attaching to conducting end plates head 118 shown in Figure 11 into the top and bottom for stacking 110.It connects Can will stack 110 and solid insulation shell or frame 112 be placed in hollow cylinder shell or outer enclosure 116.Method It also include the adjacent electrochemical cell 102 being placed on graphite flake current-collector 110 in the stacking 100B, P of electrochemical cell 102 Between.In embodiment, each electrochemical cell 102 in the stacking 100B, P of electrochemical cell 102 includes active sun The anode electrode 104 in polar region domain and the cathode electrode 106 of active cathode zone.Graphite flake current-collector 110 can have big In the area of active anode areas and active cathode areas to serve as sealing element as shown in Figure 9.

Device assembly

Cathode

If can be used as the dry substance including transition metal oxide, sulfide, phosphate or fluoride, can carry out can The active cathode material of inverse Na ions insertion/deintercalation.It is suitable as the material of the active cathode material in the embodiment of the present invention Material preferably contains basic atom, such as sodium, lithium or both before as active cathode material.Active cathode material need not be (that is, before in for energy storage device) contains Na and/or Li under green state.However, the Na sun from electrolyte from Son allows for being embedded in and being incorporated into active cathode material during the operation in energy storage device.Therefore, it can use The material for making the cathode in the present invention include need not contain Na under green state, but can energy storage device electric discharge/ The material for carrying out reversible insertion/deintercalation of Na ions during charging cycle and being lost without a large amount of overpotential.

In the embodiment that active carbon material contains basic atom (preferably Na or Li) before the use, in these atoms Some or all deintercalations during first time battery charge cycle.(overwhelming majority is Na to alkaline kation from electrolyte Cation) it is embedded in again during battery discharge.This with require embedded electrode opposing activity carbon (intercalation Electrode opposite activated carbon) nearly all mixed capacitor system it is different.In most systems In, the cation from electrolyte is adsorbed on during charging cycle on anode.Meanwhile counter anion (the example in electrolyte Such as hydrogen ion) it is embedded into active cathode material, therefore charge balance but consumption ion concentration are kept in electrolyte solution. During electric discharge, from anode discharge cation, and from cathode discharge anion, therefore in electrolyte solution keep charge balance but Increase ion concentration.This is the operation mode different from the device in the embodiment of the present invention, in an embodiment of the present invention Hydrogen ion or other anion are not embedded into active material of cathode preferably.

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

With general formula AxMyOzSome active cathode materials in, energy storage device charged/discharged recycle the phase Between, the embedded/deintercalation in Na ion reversibles ground.Therefore, when device is in use, the amount x in active cathode material formula changes.

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

With general formula AxMyOzSome active cathode materials in, A include the Na or at least Na of 80 atomic percents with One of Li, K, Be, Mg and Ca or one or more of mixture.In these embodiments, x is preferably from about 1 before the use, And during use ranging from 0 to about 1.5.In some preferred active cathode materials, M include Mn, Ti, Fe, Co, Ni, Cu and One of V or one or more of, and can adulterate and (be less than 20 atom %, such as 0.1 to 10 atom %;Such as 3 to 6 atom %) One of Al, Mg, Ga, In, Cu, Zn and Ni or one or more of.

The suitable activity cathode material of common species is including (but not limited to) layering/iris NaMO2(birnessite (birnassite)), the manganate based on cubic spinel is (for example, MO2, such as based on λ-MnO2Material, wherein M be Mn, Such as before the use be LixM2O4(wherein, 1≤x<1.1) and it is Na in useyMn2O4)、Na2M3O7System, NaMPO4System System, NaM2(PO4)3System, Na2MPO4The Na of F systems and tunnel construction0.44MO2, wherein the M in all formulas includes at least one Kind transition metal.Typical transition metal can be Mn or Fe (for cost and environment reason), but can be used Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, Mo (especially) or combinations thereof are completely or partially to replace Mn, Fe or combinations thereof.In the implementation of the present invention In example, Mn is preferred transition metal.In some embodiments, cathode electrode may include various active cathode material, in homogeneous or It is layered close to the form of homogeneous mixture or in cathode electrode.

In some embodiments, initial activity cathode material include optionally adulterate one or more kinds of metals (such as Li or Al) NaMnO2(birnessite structure).

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

It in these embodiments, can be by being initially formed the manganese oxide containing lithium (for example, LiMn2O4 is (for example, cubic spinel LiMn2O4Or its non-stoichiometric variant)) form cubic spinel λ-MnO2.Utilizing cubic spinel λ-MnO2Activity It, can electrochemically or chemical mode is from cubic spinel LiMn in the embodiment of cathode material2O4It extracts most or all of Li, to form cubic spinel λ-MnO2Types of material is (that is, have 1:2 Mn and the material of O ratio, and/or wherein Mn can be by Another metal replaces and/or it also contains alkali metal, and/or wherein Mn is just not 1 with O ratio:2).This extraction can be made A part for initial installation charging cycle occurs.In such cases, Li ions during the first charging cycle from nascent Cubic spinel LiMn2O4Deintercalation.In electric discharge, the Na ions from electrolyte are embedded into cubic spinel λ-MnO2In. Thus, the formula of active cathode material is Na during operationyLixMn2O4(optionally doping is described above a kind of or a kind of The above additional metal, preferably Al), wherein 0<x<l、0<y<L and x+y≤1.1.Preferably, amount x+y is followed by charge/discharge Ring (fully charged) change to about 1 and (discharges completely) from about 0.However, can be used during complete electric discharge be more than 1 value.In addition, Any other suitable forming method can be used.It can be by non-stoichiometric LixMn2O4Material (every 2 Mn atoms and 4 O originals Son has 1 or more Li) it is used as may be used to form cubic spinel λ-MnO2Original material (for example, wherein 1≤x<1.1). Therefore, cubic spinel λ manganates can have formula Al before the usezLixMn2-zO4(wherein 1≤x<1.1 and 0≤z<0.1), And there is formula Al in usezLixNayMn2O4(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 dopant).

In some embodiments, initial cathode material include optionally adulterate one or more kinds of metals (such as Li or Al Na)2Mn3O7

In some embodiments, initial cathode material include optionally adulterate one or more kinds of metals (such as Li or Al Na)2FePO4F。

In some embodiments, cathode material includes optionally adulterating one or more kinds of metals (such as Li or Al) Na0.44MnO2.It can be by by Na2CO3With Mn2O3Be sufficiently mixed to appropriate molar ratio and roasted at (for example) about 800 DEG C and This active cathode material is made.The degree for the Na contents being incorporated into during baking in this material determine Mn the state of oxidation and Itself and O2In the mode locally combined.It is proved for the Na in non-aqueous electrolytexMnO2, this material is 0.33<x<0.66 it Between recycle.

Optionally, cathode electrode can be in the form of composite cathode comprising:One or more active cathode materials (for example, the microcomponent of 1-49 weight %, such as 2-10 weight %, such as iris tunnel construction material), high surface area are led Electric diluent (for example, conductive grade graphite, the carbon black of such as acetylene black, non-reactive metal and/or conducting polymer), bonding Agent, plasticizer and/or filler.Exemplary adhesives may include that polytetrafluoroethylene (PTFE) (PTFE), polyvinyl chloride (PVC) base are compound Object (includes PVC-SiO2Compound), cellulosic-based material, polyvinylidene fluoride (PVDF), hydration birnessite is (when active cloudy When pole material includes another material), other non-reacted non-corrosive polymer materials or combinations thereof.It can be by will be a kind of or a kind of A part for the above preferably active cathode material mixes with Conductive diluents and/or polymeric binder and suppresses the mixture Composite cathode is formed for bead.In some embodiments, composite cathode electrode can be by the activated cathode of about 50 to 90 weight % The mixture of material is formed, and the remainder of the mixture includes in diluent, adhesive, plasticizer and/or filler One or more of combination.For example, in some embodiments, composite cathode electrode can be by the activity of about 80 weight % Adhesive (such as PTFE) shape of cathode material, the diluent (such as carbon black) of about 10 to 15 weight % and about 5 to 10 weight % At.

One or more kinds of additional functionality materials can be optionally added to composite cathode to increase capacity and replace poly- Close adhesive.These optional materials are including (but not limited to) Zn, Pb, hydration NaMnO2(birnessite) and hydration Na0.44MnO2 (iris tunnel structure).NaMnO will be hydrated2(birnessite) and/or hydration Na0.44MnO2(iris tunnel structure) adds In the case of being added to composite cathode, gained device has bifunctional material composite cathode.

Cathode electrode will be generally with thickness in the range of about 40 μm to 800 μm.

Anode:

Anode may include (to react via electrochemical double layer reaction and/or fake capacitance via adsorption/desorption (that is, Partial charge transitional surface interact)) and any materials of Na ions is reversibly stored, and in wanted voltage model Enclose interior abundant capacity.The exemplary materials for meeting these requirements include:Porous active carbon, graphite, mesoporous carbon, carbon nanotube, Disordered carbon, Ti oxides (such as titanium dioxide) material, V oxide materials, phosphorus olivine material, other suitable mesoporous ceramics Material and a combination thereof.In a preferred embodiment, activated carbon is used as anode material.

Optionally, anode electrode can be in the form of composite anode comprising:One or more kinds of anode materials, high table Area Conductive diluents (for example, conductive grade graphite, the carbon black of such as acetylene black, non-reactive metal and/or conducting polymer), Adhesive (such as PTFE), PVC base complexes (include PVC-SiO2Compound), cellulosic-based material, PVDF, other non-reactions Non-corrosive polymer material of property or combinations thereof, plasticizer and/or filler.It can be by by one or more kinds of preferred anodes materials A part for material mixes with Conductive diluents and/or polymeric binder and the mixture is compressed to bead and forms compound sun Pole.In some embodiments, composite anode electrode can be formed by the mixture of the anode material of about 50 to 90 weight %, described mixed The remainder for closing object includes one of diluent, adhesive, plasticizer and/or filler or one or more of combination.It lifts For example, in some embodiments, composite anode electrode can be by the dilution of the activated carbon, about 10 to 15 weight % of about 80 weight % The formation of the adhesive (such as PTFE) of agent (such as carbon black) and about 5 to 10 weight %.

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

Anode electrode will be generally with thickness in the range of about 80 μm to 1600 μm.

Electrolyte:

Useful electrolyte includes the salt being completely dissolved in water in an embodiment of the present invention.For example, electrolyte It may include 0.1M to the 10M solution of at least one anion selected from the group being made of following object:SO4 2-、NO3 -、 ClO4 -、 PO4 3-、CO3 2-、Cl-And/or OH-.Therefore, cationic salts containing Na may include (but not limited to) Na2SO4、 NaNO3、NaClO4、 Na3PO4、Na2CO3, NaCl and NaOH or combinations thereof.

In some embodiments, electrolyte solution can be substantially free of Na.In these cases, those listed above the moon from Cation in the salt of son can be alkali metal (such as K) or alkaline-earth metal (such as Ca or Mg) cation different from Na.Therefore, Salt containing the alkali metal different from Na cations may include (but not limited to) K2SO4、KNO3、KClO4、 K3PO4、K2CO3, KCl and KOH.The salt of exemplary alkaline including earth metal cation may include CaSO4、Ca(NO3)2、 Ca(ClO4)2、CaCO3With Ca (OH)2、 MgSO4、Mg(NO3)2、Mg(ClO4)2、MgCO3And Mg (OH)2.The electrolyte solution for being substantially free of Na can appointing by this class salt What combination is made.In other embodiments, it is non-to may include that the salt of the cation containing Na contains with one or more for electrolyte solution The solution of the salt of Na cations.

Depending on the wanted performance characteristics of energy storage device and degradation associated with higher salt concentrations/performance limitation Mechanism, for the Na in the water at 100 DEG C2SO4, molar concentration range arrives 1M preferably in about 0.05M to 3M, for example, about 0.1.It is right In other salt, similar is ranging from preferred.

The admixture of different salt is (for example, containing one kind in sodium salt and alkali metal, alkaline-earth metal, lanthanide, aluminum and zinc salt Or more than one admixture) optimization system can be generated.Such admixture can provide with sodium cation and selected from by with Under each object composition group one or more cation electrolyte:Alkali metal (such as K), alkaline-earth metal (such as Mg and Ca), lanthanide, aluminum and zinc cation.

It optionally, can be by adding some additional OH-Ionic species is so that electrolyte solution is more alkaline and changes electrolysis The pH value of matter, such as by addition different from the salt containing OH of NaOH, by adding some other OH-Concentration influences compound (example Such as, H is added2SO4So that electrolyte solution is more acid).The pH value of electrolyte can influence the range of the voltage stabilization window of battery (relative to reference electrode), and can also have an impact to the stability and degradation of active cathode material, and can inhibit proton (H+) embedding Enter, proton (H+) insertion can work in terms of active cathode material capacitance loss and battery degradation.In some cases, pH value 11 to 13 are risen to, to allow different active cathode materials to stablize (compared in 7 times stabilizations of pH neutral).At some In embodiment, pH value can be in the range of about 3 to 13, such as between about 3 and 6 or between about 8 and 13.

Optionally, electrolyte solution contains the degradation for being useful for mitigating active cathode material (for example, birnessite material) Additive.Exemplary additive can be (but not limited to) Na2HPO4, present in an amount at least sufficient to dense in the range of establishing 0.1mM to 100mM Degree.

Partition board:

Partition board for using in an embodiment of the present invention may include cotton thin slice, PVC (polyvinyl chloride), PE (poly- second Alkene), glass fibre or any other suitable material.

Operating characteristic:

As described above, contain the embodiment of basic atom (preferably Na or Li) before the use in active cathode material In, the deintercalation during first time battery charge cycle of some or all of these atoms.Alkaline kation from electrolyte (overwhelming majority is Na cations) is embedded in again during battery discharge.This and require the almost institute of embedded electrode opposing activity carbon There is mixed capacitor system different.In most systems, the cation from electrolyte is adsorbed on anode during charging cycle On.Meanwhile the counter anion in electrolyte is embedded into active cathode material, therefore keep charge flat in electrolyte solution Weighing apparatus but consumption ion concentration.During electric discharge, cation is discharged from anode, and anion is discharged from cathode, therefore in electrolyte Charge balance is kept in solution but increases ion concentration.This is the operation mould different from the device in the embodiment of the present invention Formula.

Example

Assemble the mixed tensor with prism shown in Fig. 1/parallel connection electrical connection and physical arrangement shown in Fig. 5-7 Storage device.Device contains 106 groups of 104/ cathode of anode (every group two) there are three level, wherein the graphite flake with expansion Current-collector 110a, 110c structure (500 microns of thickness) and non-woven fiber separator material 108, as shown in Figure 5.Cathode contains as above λ-MnO described in text2Phase active material, and be made of the compressing granular object of active material, carbon black, powdered graphite and PTFE.Sun Contain the activated carbon mixed with carbon black and PTFE in pole.Using pressure make each graphite anode and cathode collector 110a, 110c with Serve as respective anode and cathode graphite busbar 122a, 122c contact of the positive and negative busbar of described device.Use polypropylene Case 116 carrys out accommodation apparatus, and by graphite busbar 122a, 122c via the appropriately sized hole feed-in in polypropylene case and Then use silicone adhesive agent material relative to polypropylene seal.Then make copper wire via pressure and come from the outside of case (no Touch electrolyte) busbar 124 connects, and entire external bus is covered using encapsulated epoxy resin.

Then so that described device is passed through 15 and form cycle, and then test in many cycles its energy storage capacity and Stability.Figure 12 shows the result of this test.Figure 12 (a) is illustrated in the device current potential in 30 cycles under the conditions of charge and discharge To institute's cumulative capacity.Cycle is executed under C/6 rated current, and described device has the capacity of approximation 1.1Ah.The data exhibition Show the almost ideal overlapping of the voltage's distribiuting between cycle, indicate extreme stable and does not show capacitance loss or have in any The system of portion's corrosion.Figure 12 (b) is the curve graph of the battery charge and discharge capacity become with cycle.In being recycled at least 60 The capacitance loss not become with cycle.Data instruction from other batteries can maintain this feelings in thousands of cycles Condition.Further, it was found that the coulombic efficiency of these cycles is 98 to 100%.

This example, which is illustrated in inside accumulator outer cover, highly stable contains water power without using being generated in the case of any metal Solve matter mixed tensor storage device.Described device shows splendid stability and displaying is for a long time in multiple kinds of energy storage application Long-range future.

Although the above refers to certain preferred embodiment, it will be understood that, the present invention is not limited thereto.The skill of fields Art personnel will be understood that, can be carry out various modifications to disclosed embodiment, and such modification is wished within the scope of the present invention.This All publication, patent application case and the patent that text is stated are incorporated by herein by reference.

Claims (16)

1. a kind of electrochemical appliance comprising:
Shell;
The stacking of electrochemical cell in the housing, each electrochemical cell include:
Anode electrode;
Cathode electrode;
Partition board, between the anode electrode and the cathode electrode;And
Electrolyte;
Multiple carbon cathodes and anode collector, are alternately positioned between adjacent electrochemical cell;
A tab more than first is operatively connectable to the multiple carbon cathode current-collector and more than second a tabs, operation It is connected to the multiple carbon anode current-collector to property;
Wherein,
The cathode electrode of first electrochemical cell is in electrical contact the first cathode collector;
The cathode electrode of second electrochemical cell is in electrical contact first cathode collector, the position of second electrochemical cell Adjacent to the first side of the first electrochemical cell in the stacking;
The anode electrode of first electrochemical cell is in electrical contact second plate current-collector;
The anode electrode of third electrochemical cell is in electrical contact the second plate current-collector, the position of the third electrochemical cell Adjacent to the second side of first electrochemical cell in the stacking;
The anode electrode includes the discrete anode component separated by anode borderline region;
The cathode electrode includes the discrete cathode assembly separated by cathode borderline region;
The partition board extends to above or below the anode borderline region and the cathode borderline region;And
The electrolyte is located in the partition board and in anode electrode borderline region and cathode electrode borderline region.
2. electrochemical appliance according to claim 1, wherein a tab is configured to be connected to each other more than described first, and A tab is configured to be connected to each other more than described second.
3. electrochemical appliance according to claim 1 is deposited wherein the electrochemical appliance is mixing aqueous electrolyte energy Storage device.
4. electrochemical appliance according to claim 3, wherein the cathode includes alkali ion insert material, and the sun The extremely fake capacitance or electrochemical double layer capacitative materials electrochemically stable in the case where opposite NHE is less than -1.3V.
5. electrochemical appliance according to claim 4, wherein the cathode electrode includes doped or undoped cube of point Spar λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, the anode electrode include activated carbon, titanium dioxide Material or phosphorus olivine material, the electrolyte includes sodium ion, and the current-collector includes carbon fiber paper, is coated with carbon material Inert substrate is more than 0.6g/cm with density3Expanded graphite.
6. electrochemical appliance according to claim 5, wherein the electrolyte is the water-soluble of the alkali ion containing dissolving Liquid, the alkali ion can with the interaction of both anode and cathodes and make can via the insertion at the cathode electrode with And the fake capacitance non-faraday surface at the anode electrode reacts by stores charge.
7. electrochemical appliance according to claim 1, wherein the shell include be isolated from the outside world sealing, electrochemistry it is lazy The polymer shell of property, and the electrochemical cell in the stacking of electrochemical cell is stacked with prismatic configuration.
8. electrochemical appliance according to claim 1, wherein:
The thickness of the anode electrode and cathode electrode is between 0.05cm and 1cm;
The anode electrode includes the granular anode electrode of compacting;And
The cathode electrode includes the granular cathode electrode of compacting.
9. a kind of electrochemical appliance comprising:
Shell;
The stacking of electrochemical cell in the housing, each electrochemical cell include:
The granular anode electrode of compacting;
The granular cathode electrode of compacting;
Partition board, between the anode electrode and the cathode electrode;And
Electrolyte;
Multiple cathodes and anode collector, are alternately positioned between adjacent electrochemical cell;
Wherein,
The cathode electrode of first electrochemical cell is in electrical contact the first cathode collector;
The cathode electrode of second electrochemical cell is in electrical contact first cathode collector, the position of second electrochemical cell Adjacent to the first side of the first electrochemical cell in the stacking;
The anode electrode of first electrochemical cell is in electrical contact second plate current-collector;
The anode electrode of third electrochemical cell is in electrical contact the second plate current-collector, the position of the third electrochemical cell Adjacent to the second side of first electrochemical cell in the stacking;
The anode electrode includes the discrete anode component separated by anode borderline region;
The cathode electrode includes the discrete cathode assembly separated by cathode borderline region;
The partition board extends to above or below the anode borderline region and the cathode borderline region;And
The electrolyte is located in the partition board and in anode electrode borderline region and cathode electrode borderline region.
10. electrochemical appliance according to claim 9, wherein the thickness of the anode electrode and cathode electrode is in 0.05cm Between 1cm, and the current-collector includes carbon collector.
11. electrochemical appliance according to claim 10, wherein the current-collector includes carbon fiber paper, is coated with carbon material Inert substrate is more than 0.6g/cm with density3Expanded graphite.
12. electrochemical appliance according to claim 9 is deposited wherein the electrochemical appliance is mixing aqueous electrolyte energy Storage device.
13. electrochemical appliance according to claim 12, wherein the cathode includes alkali ion insert material, and it is described Anode is in opposite NHE less than fake capacitance or electrochemical double layer capacitative materials electrochemically stable under -1.3V.
14. electrochemical appliance according to claim 13, wherein the cathode electrode includes doped or undoped cube Spinelle λ-MnO2Types of material or NaMn9O18Tunnel construction iris material, the anode electrode include activated carbon, titanium dioxide Titanium material or phosphorus olivine material, and the electrolyte includes sodium ion.
15. electrochemical appliance according to claim 14, wherein the electrolyte is the water of the alkali ion containing dissolving Solution, the alkali ion can with the interaction of both anode and cathodes and make can be via the insertion at the cathode electrode And the fake capacitance non-faraday surface at the anode electrode reacts by stores charge.
16. electrochemical appliance according to claim 9, wherein the shell includes be isolated from the outside world sealing, electrochemistry Inert polymer shell, and the electrochemical cell in the stacking of electrochemical cell is stacked with prismatic configuration.
CN201610179405.5A 2011-03-09 2012-03-08 Metal-free aqueous electrolyte energy storage device CN105761941B (en)

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