CN104246942B - Advanced electrolyte system and its purposes in energy accumulating device - Google Patents

Advanced electrolyte system and its purposes in energy accumulating device Download PDF

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Publication number
CN104246942B
CN104246942B CN201380022019.XA CN201380022019A CN104246942B CN 104246942 B CN104246942 B CN 104246942B CN 201380022019 A CN201380022019 A CN 201380022019A CN 104246942 B CN104246942 B CN 104246942B
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supercapacitor
shell
electrolyte
degrees celsius
electrode
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CN104246942A (en
Inventor
里卡尔多·西尼奥雷利
约翰·J·库利
克里斯托弗·约翰·西巴尔德·迪恩
詹姆斯·爱泼斯坦
帕德马纳班·萨斯桑·库蒂皮莱
法布里齐奥·马丁尼
林赛·A·威廉默斯
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Kuai Mao System House
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Kuai Mao System House
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Priority claimed from PCT/US2012/045994 external-priority patent/WO2013009720A2/en
Priority claimed from US13/553,716 external-priority patent/US20130026978A1/en
Application filed by Kuai Mao System House filed Critical Kuai Mao System House
Priority to CN201910288116.2A priority Critical patent/CN110233063B/en
Publication of CN104246942A publication Critical patent/CN104246942A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
    • H01G11/18—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors against thermal overloads, e.g. heating, cooling or ventilating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/80—Gaskets; Sealings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)
  • Hybrid Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The present invention provides a kind of supercapacitors, it includes immersing in advanced electrolyte system and being arranged in the intracorporal energy storage unit of gas-tight seal shell, the unit is electrically coupled to positive contact and cathode contact part, wherein exporting electric energy within the temperature range of Cheng Yue -40 degrees Celsius to about 210 degrees Celsius of the ultracapacitor configurations.The present invention also provides its manufacture and purposes.

Description

Advanced electrolyte system and its purposes in energy accumulating device
Cross reference to related applications
Entitled " electrolyte (the Electrolytes for supercapacitor submitted this application claims on 2 24th, 2012 For Ultracapacitors) " U.S. Provisional Patent Application the 61/602,713rd, on July 9th, 2012 submit it is entitled The international application PCT/ of " high temperature energy storage device (High Temperature Energy Storage Device) " No. US2012/045994, entitled " power supply (the Power Supply for for downhole instrument that submits on July 19th, 2012 Downhole Instruments) " U.S.Application Serial the 13/553,716th and submit on November 9th, 2012 entitled The U.S. Provisional Patent Application of " electrolyte (Electrolytes for Ultracapacitors) for supercapacitor " The equity of No. 61/724,775 priority.Each of these disclosures are incorporated herein by reference herein.
Background technique
1. technical field
Disclosed herein the present invention relates to energy storage units, more particularly in these energy storage units Advanced electrolyte system, and for providing the relevant technologies for the double layer capacitor that can be operated at high temperature.
2. description of Related Art
Energy storage unit is prevalent in our society.Although most people simply recognizes energy storage unit To be " battery ", but other kinds of unit should be also included within the scope of this.For example, recently, supercapacitor because Its advantageous characteristic and be concerned.In short, the energy storage unit of many types is known and in use now.
Double layer capacitor, also referred to as " supercapacitor (supercapacitor, supercondenser, Ultracapacitor) ", " pseudocapacitors " or " electrochemical capacitor in double electrode layer " are that one kind is shown better than conventional capacitor The capacitor that significantly improves of performance.One this parameter is energy density.In general, the energy density ratio of supercapacitor High about thousands of times of the order of magnitude of the energy density of high capacity electrolytic capacitor.
Capacitor be in any electronic device with one of the critical component in electronic system.Conventional func includes power supply electricity Pressure smoothing provides support, and filtering to energy source.Multiple industries exist to the demand ring for implementing electronic device and capacitor Border.
Consider for example with needing electrical components (for example, more than 80 degrees Celsius at a temperature of) continuous work at high temperature The industry of some applications, such as oil drilling, space flight, aviation, military project and automobile industry.This heat exposure is together with various factors The performance deterioration of energy storage system at elevated temperatures is caused, and leads to the premature deterioration of energy storage unit.It is durable Property and safety are key requests in typical AEROSPACE APPLICATION and national defense applications.Such as engine, turbofan and control It is arranged with sensing electronic device and is applied those of near rocket engine shell.Automobile application such as small gear-box or insertion Formula alternating current generator/starter also requires durability and long-life at elevated temperatures.
Electronic component in industrial environment must be still physically firm while meeting performance requirement.For For the designer and the producer of supercapacitor, one of adjoint challenge is to obtain to go on well at high temperature and reliably Electrolyte and can be gone on well under both high temperature and low temperature and reliable electrolyte.Regrettably, some electrolyte Desired characteristic cannot show at relatively high temperatures or cannot continue at relatively high temperatures, and even real at high temperature Those of existing durability electrolyte cannot reliably work at low temperature.Thus, what is desired is that being run under conditions of demand The good electrolyte for supercapacitor.Preferably, electrolyte provides stable conductance in the temperature of entire wide scope Rate and low internal resistance and stabilization and high capacitor, and stable and low leakage current.
Summary of the invention
In one embodiment, a kind of supercapacitor is disclosed.The supercapacitor includes in gas-tight seal shell Energy storage unit and advanced electrolyte system (AES), the unit be electrically coupled to positive contact and cathode contact part, In within the temperature range of Cheng Yue -40 degrees Celsius to about 210 degrees Celsius of the ultracapacitor configurations at a temperature of operate.
In another embodiment, a kind of method for manufacturing supercapacitor is provided.This method includes following step It is rapid: will to include the energy storage unit setting of energy storage medium in shell；It is filled with advanced electrolyte system (AES) The shell, so that supercapacitor operates within the temperature range of being fabricated at about -40 degrees Celsius to about 210 degrees Celsius.
In yet another embodiment, a kind of side using high temperature rechargeable energy accumulating device (HTRESD) is provided Method.This method comprises the following steps: obtaining the HTRESD including advanced electrolyte system (AES)；With by handing over HTRESD HTRESD is recycled at least twice for being charged and discharged, while maintaining the voltage at the both ends HTRESD, so that HTRESD is shown 0.01W/ rises to the initial spike power density of 150kW/ liter, so that HTRESD is being about -40 degrees Celsius to about 210 degrees Celsius It is operated under the environment temperature of temperature in temperature range.
In yet another embodiment, a kind of method using supercapacitor is provided.This method comprises the following steps: Supercapacitor as described herein is obtained, wherein the supercapacitor is shown in about 100 degrees Celsius and about 150 degrees Celsius Between essentially constant temperature under (mA/ cubes li of volume leakage current below about 10mA/ cubic centimetres when keeping Rice)；And supercapacitor is recycled by being alternately charged and discharged to the supercapacitor at least twice, while remaining super The voltage at grade capacitor both ends, so that the supercapacitor is between about -40 degrees Celsius to about 210 degrees Celsius It is increased when being kept under essentially constant temperature using the ESR shown after at least 1 hour below about 1000%.
In another embodiment, a kind of side to user's offer high temperature rechargeable energy accumulating device is provided Method.This method comprises the following steps: selection includes the high temperature rechargeable energy accumulating device of advanced electrolyte system (AES) (HTRESD), the high temperature rechargeable energy accumulating device is being exposed to about -40 degrees Celsius to about 210 degrees Celsius of temperature model Shown when enclosing interior environment temperature 0.01W/ rise and 100kW/ rise between initial spike power density and at least 1 hour resistance to The long phase；And the storage device is delivered, so that providing the HTRESD to user.
In yet another embodiment, a kind of side to user's offer high temperature rechargeable energy accumulating device is provided Method.This method comprises the following steps: obtaining any supercapacitor, the supercapacitor as described herein and shows to protect It is below about 10mA/ cubes li when holding under the essentially constant temperature between about -40 degrees Celsius and about 210 degrees Celsius The volume leakage current (mA/ cubic centimetres) of rice；And the storage device is delivered, so that providing the HTRESD to user.
In yet another embodiment, a kind of advanced electrolyte system (AES) is disclosed.The AES includes containing at least It is a kind of cation and at least one anion ion liquid and show lower than 1000ppm halogen ion content and be lower than The water content of 100ppm.
In yet another embodiment, a kind of advanced electrolyte system (AES) is disclosed.The AES includes containing at least The ionic liquid of a kind of cation and at least one anion and at least one solvent and show halogen lower than 1000ppm Ion concentration and water content lower than 1000ppm.
Detailed description of the invention
By following specific embodiment combination attached drawings, aforementioned and other feature and advantage of the invention be it will be evident that The attached drawing should not be considered as restrictive:
Fig. 1 shows the various aspects of exemplary supercapacitor；
Fig. 2 is to describe the block diagram for growing into multiple carbon nanotubes (CNT) on substrate；
Fig. 3 is to describe to deposit to current-collector on the CNT of Fig. 3 to provide the block diagram of electrode member；
Fig. 4 be describe addition transfer band to Fig. 3 electrode member block diagram；
Fig. 5 is the block diagram of the electrode member during describing transfer process；
Fig. 6 is the block diagram for describing the electrode member after transfer；
Fig. 7 is the block diagram for describing the exemplary electrode manufactured by multiple electrodes element；
Fig. 8 depict may include in exemplary supercapacitor cation primary structure embodiment；
Fig. 9 and Figure 10, which is each provided, utilizes the exemplary supercapacitor of original electrolyte and purified electrolyte Compare data；
Figure 11 depicts the embodiment of the shell of exemplary supercapacitor；
Figure 12 shows the embodiment of the storage element of exemplary supercapacitor；
Figure 13 depicts the obstructing instrument on the inside for the main body that shell is arranged in；
Figure 14 A and Figure 14 B (collectively referred to herein as Figure 14) depict the various aspects of the lid of shell；
Figure 15 depicts the sub-assembly according to the supercapacitor instructed herein；
Figure 16 A and Figure 16 B (collectively referred to herein as Figure 16) be respectively describe supercapacitor do not have barrier The figure of embodiment and the performance of the similar embodiment including barrier；
Figure 17 depicts the barrier being arranged in around storage element as wrap member；
Figure 18 A, Figure 18 B and Figure 18 C (collectively referred to herein as Figure 18) depict the reality of the lid of the material including point multilayer Apply scheme；
Figure 19 be include glass to metal seal part (glass-to-metal seal) electrode assembly cross-sectional view；
Figure 20 is mounted in the cross-sectional view of the electrode assembly of Figure 19 in the lid of Figure 18 B；
Figure 21 depicts the arrangement of energy storage unit in sub-assembly；
Figure 22 A, Figure 22 B and Figure 22 C (collectively referred to herein as Figure 22) depict the implementation of the energy storage unit of assembling Scheme；
Figure 23 depicts combination of the polymer insulator into supercapacitor；
Figure 24 A, Figure 24 B and Figure 24 C (collectively referred to herein as Figure 24) depict the another of the lid for energy storage device The various aspects of the template of a embodiment；
Figure 25 be include hemispherical material electrode assembly perspective view；
Figure 26 be include the Figure 25 being mounted in the template of Figure 24 electrode assembly lid perspective view；
Figure 27 is the cross-sectional view of the lid of Figure 26；
Figure 28 depicts the coupling of the terminal of electrode assembly and storage element；
Figure 29 is the transparent isometric view for the energy storage unit being arranged in circular cylindrical shell body；
Figure 30 is the side view of storage element, shows multiple layers an of embodiment；
Figure 31 is rolled up the isometric view of the storage element of (rolled up) comprising for arranging the ginseng of more leads Examine label；
Figure 32 is isometric view of the storage element of Figure 31 after expansion；
Figure 33 depict include more leads the storage element rolled；
Figure 34 is depicted to be imparted to and be folded with the Z- for the lead (that is, terminal) of storage element coupling being aligned；
Figure 35 to Figure 38 is the figure of the performance of depicted example supercapacitor；And
Figure 39 to Figure 43 is the figure of performance of the depicted example supercapacitor under 210 degrees Celsius.
Figure 44 A and Figure 44 B are to describe to have novel electrolytes entity: 1- butyl -1- methyl piperidine respectivelyBis- (fluoroforms Base sulfonyl) imines performance of the supercapacitor at 150 degrees Celsius and 1.5V capacitance curve and ESR curve.
Figure 45 A and Figure 45 B are to describe to have three hexyl myristyl of novel electrolytes entity respectivelyBis- (trifluoromethyl sulphurs Acyl group) imines performance of the supercapacitor at 150 degrees Celsius and 1.5V capacitance curve and ESR curve.
Figure 46 A and Figure 46 B are to describe to have novel electrolytes entity butyl trimethylammonium bis- (trifluoromethyl sulfonyl) respectively The capacitance curve and ESR curve of performance of the supercapacitor of imines under 150 degrees Celsius and 1.5V.
Figure 47 A and Figure 47 B are to describe the ionic liquid having in the electrolyte combination for being used in preparation enhancing respectively The capacitance curve and ESR curve of performance of the supercapacitor of ionic liquid under 125 degrees Celsius and 1.5V.
Figure 48 A and Figure 48 B are to describe to have 37.5% organic solvent-ionic liquid (as in Figure 47) v/v respectively Performance of the supercapacitor at 125 degrees Celsius and 1.5V capacitance curve and ESR curve.
Figure 49 is to describe the supercapacitor with 37.5% organic solvent-ionic liquid (as in Figure 47) v/v The ESR curve of performance under -40 degrees Celsius and 1.5V.
Specific embodiment
Various variables are described in this application, including but not limited to composition (for example, electrode material, electrolyte etc.), item Part (for example, temperature, the freedom degree of various impurity at various levels) and performance characteristics are (for example, relative to initial capacitance Posterior circulation capacitor, low-leakage current etc.).It should be understood that any combination of the aleatory variable in these variables can limit the present invention Embodiment.For example, embodiment of the present invention is specific electrode materials, has particular dielectric, in specific range of temperatures Lower and the combination with the impurity for being less than specific quantity, the operation with posterior circulation capacitor and particular value leakage current is (as much as possible Specific combination may not stated including these variables but emphatically).It can also be specific among variable listed herein Ground selects other combinations of product, composition, condition and/or method to limit other embodiments, these are to those skilled in the art Member is apparent.
It defined below will describe to include advanced electrolyte system and its use with reference to what is be explained below for convenience The present invention on way.Unless otherwise indicated, following term used herein is defined as follows:
I. it defines
In the element for introducing the invention or an embodiment thereof, when not having numeral-classifier compound modification before noun, it is intended to include Singular and plural form.Similarly, it when use adjective " another " modified elements, is intended to include singular and answers Number form formula.The terms "include", "comprise" and " having " mean to include the other element in addition to listed element.
Term " alkenyl " and " alkynyl " are generally acknowledged in the art, and refer to and the length of following alkyl and may take For species like but the unsaturated aliphatic group containing at least one double or triple bonds respectively.
Term " alkyl " is generally acknowledged in the art, and may include the aliphatic group of saturation, including straight chain alkane The alkyl that base, branched alkyl, naphthenic base (alicyclic) group, alkyl-substituted naphthenic base and naphthenic base replace.In certain realities It applies in scheme, linear or branched alkyl group is in its skeleton with about 20 or less carbon atom (for example, the C of straight chain1-C20, branch The C of chain1-C20).Equally, naphthenic base has about 3 to about 10 carbon atoms in its ring structure, or has about in ring structure 5,6 or 7 carbon.The example of alkyl includes but is not limited to methyl, ethyl, propyl, butyl, amyl, hexyl, ethylhexyl, cyclopropyl Base, cyclobutyl, cyclopenta, cyclohexyl etc..
Term " cladding " used herein, " cladding " etc., which refer to, is bonded together different metal.Cladding often pass through by Two kinds of metals are squeezed out by mold and under high pressure suppress piece or roll together to realize.Other methods can be used, Such as laser melting coating.The result is that the piece for the material being made up of multiple layers, plurality of material layer is bonded together such that material can be with It works together as monolithic (for example, being formed as homogeneous material monolithic).
As convention, it is believed that " pollutant " will negatively affect supercapacitor if can be defined as and be introduced into Any unexpected material of 10 performance.It shall yet further be noted that herein in general, pollutant can be assessed with concentration, Such as part/million part (ppm).Concentration can use by weight, by volume, based on example weight or to determine suitable appoint Meaning other modes meter.
Term " cyano " is endowed its common meaning in the art, and refers to group CN.Term " sulfate group (sulfate) " it is endowed its common meaning in the art, and refers to group SO2.Term " sulfonic group " be endowed its Common meaning in this field, and refer to group SO3X, wherein X can be electronics to, hydrogen, alkyl or cycloalkyl.Term " carbonyl Base " is well known in the art, and refers to group C=O.
In general, term " electrode " refers in the device that can be coupled to circuit and often for nonmetallic another material Expect the electric conductor of contact.In general, term " electrode " used herein is related to current-collector 2 and can be with the another of current-collector 2 Outer component (such as energy storage medium 1) is to provide desired functionality (for example, the energy storage to match with current-collector 2 Medium 1 provides energy storage and energy transmission).
" energy density " be peak value device voltage square multiplied by device capacitor half divided by the device matter Amount or volume.
As discussed herein, " airtight " refers to its property (that is, leak rate) with " atm- cubic centimetres/second " for unit The sealing of definition, " atm- cubic centimetres/second " mean environment atmospheric pressure and at a temperature of 1 cubic centimetre of gas (example per second Such as, He).It is indicating for unit that this, which was equivalent to " He- cubic centimetres/second of standard ",.Additionally it is believed that 1atm- cubic centimetres/second etc. In 1.01325 Hao Ba-liter/second.
Term " miscellaneous thiazolinyl " and " miscellaneous alkynyl " are well known in the art, and refer to one of them or more atom It is the alkenyl and alkynyl as described herein of hetero atom (for example, oxygen, nitrogen, sulphur etc.).
It is hetero atom that term " miscellaneous alkyl ", which is well known in the art, and refers to one of them or more atom, The alkyl as described herein of (for example, oxygen, nitrogen, sulphur etc.).For example, alkoxy (for example,-OR) is miscellaneous alkyl.
As convention, term " internal resistance " and " effective series resistance " and " ESR " known in the field are used for announcer The term of the resistance of part uses interchangeably herein.
As convention, the introduced electricity of the capacitor that term " leakage current " measures after generally referring to during given time Stream.The measurement is maintained at substantially stationary potential difference (end voltage) Shi Jinhang in capacitor terminal.It is typical when assessing leakage current Period be 72 (72) hours, but the different periods also can be used.It should be noted that the electric leakage of prior art capacitor Stream is generally simultaneously increased with the increase of the internal surface area of shell with the volume of energy storage medium and increasing for surface area.Generally For, it is believed that raised leakage current indicates the reaction rate gradually risen in supercapacitor 10.The performance requirement one of leakage current As defined by environmental condition universal in specific application.For example, for volume is the supercapacitor 10 of 20mL, leakage current Practical limitation can be brought down below 200mA.
" service life " of capacitor is generally also defined by specific application and is typically expressed as a certain raising percentage of leakage current Than or another parameter (such as capacitor or internal resistance) deterioration (being conclusive when appropriate or for given application).For example, one In a embodiment, in automobile application the service life of capacitor can be defined as leakage current be increased to that it is initial (service life, " BOL ") value 200% time.In another embodiment, the service life of capacitor can define in oil and natural gas application To there is the time of any phenomenon in following phenomenon: capacitor drops to the 50% of its beginning of life；Internal resistance is increased to its beginning of life 200%；Leakage current is increased to the 200% of its beginning of life.It, " durability " of term device used herein and " can as convention By property " relate generally to service life of described device as defined above.
" operating temperature range " of device relate generally to wherein maintain certain level performance temperature range and It is determined generally directed to given application.For example, in one embodiment, the operating temperature range in oil and natural gas field can To be defined as temperature range, the resistance of device is lower than resistance of the described device under 30 degrees Celsius in the temperature range About 1000%, and capacitor is greater than about 10% of the capacitor under 30 degrees Celsius.
In some cases, operating temperature range specification provides the lower limit of effective temperature and lifetime specification provides effectively The upper limit of temperature.
" peak power density " be peak value device voltage square a quarter divided by the device effective series electrical Hinder the quality or volume divided by described device.
As cited herein, " the volume leakage current " of supercapacitor 10 generally refers to leakage current divided by supercapacitor 10 volume, and can for example be indicated as unit of mA/ cubic centimetres.Similarly, " volumetric capacitance " of supercapacitor 10 The capacitor of supercapacitor 10 is generally referred to divided by the volume of supercapacitor 10, and can be for example single with F/ cubic centimetres Position indicates.In addition, " the volume ESR " of supercapacitor 10 generally refers to the ESR of supercapacitor 10 multiplied by supercapacitor 10 Volume, and can for example be indicated as unit of ohm cubic centimetre.
As convention, it is considered that, " can with " be interpreted as optional as used herein, the term；" comprising " is interpreted as not Exclude other options (that is, step, material, component, component etc.)；" answering " does not imply that requirement, and is only accidental preferred or root According to the preferred of situation.Other similar term is similarly used in a manner of generally conventional.
As discussed herein, it is believed that term such as " adjustment ", " configuration ", " construction " etc. are related to disclosed herein The application of what technology and other similar technology (as currently known or developing later), to provide expected results.
II. capacitor of the invention
Disclosed herein is to provide to have the capacitor for improving performance over a wide temperature range for user.Example Such as, the capacitor including advanced electrolyte system described herein of the invention can be about down to -40 degrees Celsius It is operated under to up to about 210 degrees Celsius of temperature ranges.
In general, capacitor of the invention includes being suitable for providing high reliability, wide behaviour compared with prior-art devices Make the combined energy storage medium of temperature range, high power density and high-energy density.Capacitor includes being configured to assure that The component operated in the temperature range, and the electrolyte including being only selected from advanced electrolyte system described herein 6.The combination of construction, energy storage medium and advanced electrolyte system provides steady capacitor (robust of the invention Capacitors), which is capable of providing the property under extreme conditions with the enhancing better than existing capacitor simultaneously And the operation with better performance and durability.
Therefore, the present invention provides a kind of supercapacitor, which includes: the intracorporal energy of gas-tight seal shell Storage element and advanced electrolyte system (AES), the unit are electrically coupled to positive contact and cathode contact part, wherein super Capacitor is configured to operate at the temperature (" operation temperature ") in following temperature range: about -40 degrees Celsius to about 210 Celsius Degree；About -35 degrees Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 205 degrees Celsius；About -30 degrees Celsius to about 210 Celsius Degree；About -40 degrees Celsius to about 200 degrees Celsius about；About -25 degrees Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 195 Celsius Degree；About -20 degrees Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 190 degrees centigrade；About -15 degrees Celsius to about 210 Celsius Degree；About -40 degrees Celsius to about 185 degrees Celsius about；About -10 degrees Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 180 Celsius Degree；About -5 degrees Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 175 degrees Celsius；About 0 degree Celsius to about 210 degrees Celsius； About -40 degrees Celsius to about 170 degrees Celsius；About 5 degrees Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 165 degrees Celsius；About 10 Degree Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 160 degrees Celsius；About 15 degrees Celsius to about 210 degrees Celsius；About -40 take the photograph Family name's degree is to about 155 degrees Celsius；About 20 degrees Celsius to about 210 degrees Celsius；About -40 degrees Celsius to about 150 degrees Celsius.
In one particular embodiment, AES includes novel electrolytes entity (NEE), for example, wherein NEE is suitable for It is used in high temperature ultracapacitor.In certain embodiments, 80 degrees Celsius to about 210 of ultracapacitor configurations Cheng Yue it is Celsius It is operated at a temperature of in the temperature range (for example, about 80 degrees Celsius to about 150 degrees Celsius temperature range) of degree.
In one particular embodiment, AES includes highly purified electrolyte, for example, wherein highly purified electrolysis Matter is suitable for using in high temperature ultracapacitor.In certain embodiments, 80 degrees Celsius of ultracapacitor configurations Cheng Yue It is operated at a temperature of within the temperature range of to about 210 degrees Celsius.
In one particular embodiment, AES includes the electrolyte combination of enhancing, for example, the electrolyte group wherein enhanced Properly used together in both high temperature ultracapacitor and low temperature supercapacitor.In certain embodiments, super capacitor Device is configured to operate at a temperature of within the temperature range of about -40 degrees Celsius to about 150 degrees Celsius.
In this way, and as described above, the advantages of being better than the existing electrolyte of known energy accumulating device selected from changing as follows One or more of into: all-in resistance reduces；The long-time stability of resistance improve, total capacitance increases, capacitor it is steady in a long-term Property improve, energy density increases, voltage stability improves, vapour pressure reduces, the temperature range performance of single capacitor is wider, single The durability temperature of a capacitor improves, ease of manufacture improves and cost-effectiveness is improved.
In certain embodiments of supercapacitor, energy storage unit includes positive electrode and negative electrode.
In certain embodiments of supercapacitor, at least one of electrode includes containing carbon energy storage medium, example Such as, wherein including carbon nanotube containing carbon energy storage medium.In specific embodiments, may include containing carbon energy storage medium At least one of active carbon, carbon fiber, staple fibre, graphene, aeroge, carbon cloth and carbon nanotube.
In certain embodiments of supercapacitor, each electrode includes current-collector.
In certain embodiments of supercapacitor, AES is purified to reduce impurity content.In certain of supercapacitor In a little embodiments, the content of halogen ion is below about 1000 parts/million parts in electrolyte, for example, it is below about 500 parts/million parts, For example, being below about 100 parts/million parts, for example, being below about 50 parts/million parts.In specific embodiments, the halogen in electrolyte Ion is selected from one of halogen ion selected from chloride ion, bromide ion, fluorine ion and iodide ion or more.In specific reality It applies in scheme, the total concentration of impurity is below about 1000 parts/million parts in electrolyte.In certain embodiments, impurity is selected from bromine One of ethane, chloroethanes, 1- bromobutane, 1-chlorobutane, 1- methylimidazole, ethyl acetate and methylene chloride or more.
In certain embodiments of supercapacitor, the total concentration of metallics is below about 1000 parts/hundred in electrolyte Ten thousand parts.In specific embodiments, metallics from Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb and Zn selected from selecting One or more of metals.In another particular embodiment, metallics be selected from from Cd, Co, Cr, Cu, Fe, K, Li, Mo, One or more of alloys of the metal selected in Na, Ni, Pb and Zn.In another specific embodiment, metallics choosing Since one or more of oxides of the metal selected in Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb and Zn.
In certain embodiments of supercapacitor, total water content is below about 500 parts/million parts in electrolyte, example Such as, it is below about 100 parts/million parts, for example, being below about 50 parts/million parts, for example, being below about 20 parts/million parts.
In certain embodiments of supercapacitor, shell includes being provided at its inner portion on the signal portion on surface Barrier.In specific embodiments, barrier includes polytetrafluoroethylene (PTFE) (PTFE), perfluoroalkoxy resin (PFA), fluorination second At least one of allyl alkene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE).In specific embodiments, it obstructs Object includes ceramic material.Barrier can also include showing corrosion resistance, desired dielectric property and low electrochemical reaction The material of property.In the specific embodiment of barrier, barrier includes multiple material layers.
In certain embodiments of supercapacitor, shell includes multilayer material, for example, wherein multilayer material includes packet The first material being layed on the second material.In specific embodiments, multilayer material includes at least one of steel, tantalum and aluminium.
In certain embodiments of supercapacitor, shell includes at least one hemispherical seal.
In certain embodiments of supercapacitor, shell includes at least one glass to metal seal part, for example, its The pin of middle glass to metal seal part provides one of contact.In specific embodiments, glass to metal seal part include by The feedthrough component that is constituted selected from one of following material: iron-nickel-cobalt alloy, dilval, tantalum, molybdenum, niobium, tungsten and certain forms Stainless steel and titanium.In another specific embodiment, glass to metal seal part includes by least one material selected from the following The ontology of composition: nickel, molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminium, carbon and tungsten and its alloy.
In certain embodiments of supercapacitor, energy storage unit includes isolator to provide positive electrode and negative electricity Electric isolution between pole, for example, wherein isolator include selected from polyamide, polytetrafluoroethylene (PTFE) (PTFE), polyether-ether-ketone (PEEK), Aluminium oxide (Al2O3), glass fibre, the material in fiberglass reinforced plastics or any combination thereof.In specific embodiments, Isolator is substantially free of moisture.In another particular embodiment, isolator includes substantially hydrophobic.
In certain embodiments of supercapacitor, gas-tight seal shows following leak rate: being not greater than about 5.0 ×10-6Atm- cubic centimetres/second；For example, being not greater than about 5.0 × 10-7Atm- cubic centimetres/second；For example, no more than about 5.0 × 10-8Atm- cubic centimetres/second；For example, being not greater than about 5.0 × 10-9Atm- cubic centimetres/second；For example, being not greater than about 5.0 × 10 -10Atm- cubic centimetres/second.
In certain embodiments of supercapacitor, at least one contact is configured to match another supercapacitor Another contact.
In certain embodiments of supercapacitor, storage unit includes the wrap member being arranged on its outside, example Such as, wherein the wrap member includes one of PTFE and polyimides.
In certain embodiments of supercapacitor, volume leakage current is in temperature range for below about 10 amperes/liter.
In certain embodiments of supercapacitor, volume leakage current is in particular voltage range for below about 10 peaces Training/liter, the particular voltage range is between about 0 volt to about 4 volts, for example, between about 0 volt to about 3 volts, for example, Between about 0 volt to about 2 volts, for example, between about 0 volt to about 1 volt.In certain embodiments of supercapacitor, The intracorporal moisture level of shell is below about 1000 parts/million parts (ppm), for example, being below about 500 parts/million parts (ppm), for example, low In about 350 parts/million parts (ppm).
In certain embodiments of supercapacitor, the moisture content in the electrode of supercapacitor is below about 1000ppm, for example, being below about 500ppm, for example, being below about 350 parts/million parts (ppm).
In certain embodiments of supercapacitor, the moisture content in the isolator of supercapacitor is below about 1000ppm, for example, being below about 500ppm, for example, being below about 160 parts/million parts (ppm).
In certain embodiments of supercapacitor, for selected from one of electrode, electrolyte and component of isolator, chlorine Ion concentration is below about 300ppm.
In certain embodiments of supercapacitor, the volume leakage current (mA/ cubic centimetres) of supercapacitor is being protected Below about 10mA/ cubic centimetres when holding essentially constant temperature, for example, in specific embodiments, keeping substantially invariable It is below about 1mA/ cubic centimetres when temperature.
In certain embodiments of supercapacitor, the volume leakage current of supercapacitor is keeping substantially invariable temperature Greater than about 0.0001mA/ cubic centimetres when spending.
In certain embodiments of supercapacitor, the volumetric capacitance of supercapacitor is at about 6F/ cubic centimetres and about Between 1mF/ cubic centimetres；Between about 10F/ cubic centimetres and about 5F/ cubic centimetres；Or about 50F/ cubic centimetres and about 8F/ Between cubic centimetre.
In certain embodiments of supercapacitor, the volume ESR of supercapacitor is in about 20 milliohm cubic centimetres Between 200 milliohm cubic centimetres, between about 150 milliohm cubic centimetres and 2 ohm of cubic centimetres, about 1.5 ohm Between cubic centimetre and 200 ohm of cubic centimetres or between about 150 ohm of cubic centimetres and 2000 ohm of cubic centimetres.
In certain embodiments of supercapacitor, supercapacitor is keeping substantially invariable voltage and operation temperature When show below about 90% capacitor decline.In specific embodiments, supercapacitor is in substantially invariable voltage and behaviour Kept at a temperature of work at least 1 hour (for example, at least 10 hours；For example, at least 50 hours；For example, at least 100 hours；For example, At least 200 hours；For example, at least 300 hours；For example, at least 400 hours；For example, at least 500 hours；For example, at least 1000 hours) when show below about 90% capacitor decline.
In certain embodiments of supercapacitor, supercapacitor is protected under substantially invariable voltage and operation temperature It shows the ESR below about 1000% when holding at least 1 hour to increase, for example, at least 10 hours；For example, at least 50 hours；Example Such as, at least 100 hours；For example, at least 200 hours；For example, at least 300 hours；For example, at least 400 hours；For example, at least 500 hours；For example, at least 1000 hours.
For example, as shown in Figure 1, showing the exemplary implementation scheme of capacitor.In this case, capacitor is " super Grade capacitor 10 ".Exemplary supercapacitor 10 is double layer capacitor (EDLC).Supercapacitor 10 may be embodied as several The different shape factor (that is, showing certain appearance).The example of the form factor of potentially useful include cylindrical unit, colyliform or The stacked body of annular unit, flat prism elements or the flat prism elements including boxed unit, and be adapted to accommodate it is special The flat prism elements of geometry (such as curved space).The cylindrical shape factor can combine cylindric system or with It is most useful when the installation of the cylindrical shape factor or system with cylindrical cavity.Colyliform or annular unit form factor can be It is most useful when in conjunction with ring system or with the installation of the tubular shape factor or the system with ring cavity.Flat prism elements shape The shape factor can be most useful when combining rectangular system or with rectangular form factor installation or the system with rectangular enclosure.
Although herein generally with the shape of " glue volume " application (that is, storage unit 12 is configured to cylindrical housings 7) It is open, but the storage unit 23 rolled can take the shape of any desired.For example, relative to storage unit 12 is rolled, it can To carry out the folding of storage unit 12 to provide the storage unit rolled 23.Other types of sub-assembly can be used.As one A example, storage unit 12 can be flat unit, referred to as Coin shape, pouch-type or prismatic unit.Therefore, it rolls and only rolls up One selection of the sub-assembly of the storage unit 23 of system.Therefore, although herein with regard to the aspect of " storage unit 23 rolled " It discusses, but this and non-limiting.It is considered that term " storage unit 23 rolled " is generally included to be well suitable for shell The storage unit 12 of any appropriate form encapsulation or packaging of the given design of body 7.
The supercapacitor 10 of various shapes can be linked together.Known technology can be used and for example weld contact Together, by using at least one mechanical connector, by arranging that contact being electrical contact with each other etc. is described a variety of to connect Shape.Multiple supercapacitors 10 can be electrically connected at least one of in the form of in parallel and serial.
For purposes of the present invention, the volume of supercapacitor 10 can be about 0.05 milliliter to 7.5 liters.
The particularly useful environment of a variety of supercapacitors 10 may be present.For example, in automotive vehicles applications, may be implemented 105 and take the photograph The environment temperature of family name's degree (wherein the actual life of capacitor is about 1 year to 20 years).In some down-hole applications such as geothermal drilling In, can achieve 300 degrees Celsius or higher environment temperature, (wherein the actual life of capacitor is about 1 hour to 10000 small When).
The component of supercapacitor of the invention will be successively discussed now.
A.Advanced electrolyte system of the invention
Advanced electrolyte system of the invention provides the electrolyte composition of supercapacitor of the invention, and in Fig. 1 In be marked as " electrolyte 6 ".Electrolyte 6 fills the void space between electrode 3 and the neutralization of isolator 5.In general, this The advanced electrolyte system of invention includes unique electrolyte, the electrolyte of purifying enhancing or combinations thereof, wherein electrolyte 6 It is to be dissociated into the substance of charged ion (for example, positively charged cation and negatively charged anion) (such as by one or more Kind salt or ionic liquid are constituted) and may include solvent.In advanced electrolyte system of the invention, it is based on certain performances Enhancing with durability characteristics selects such electrolyte composition, and electrolyte composition can be molten with one or more Agent is combined, it is described one or more solvents dissolution above-mentioned substances with generate with novel and useful electrochemical stability with The composition of performance.
Advanced electrolyte system of the invention is provided for supercapacitor of the invention and is filled better than existing energy storage Set (for example, comprising herein without the energy accumulating device of disclosed electrolyte, or the energy comprising the insufficient electrolyte of purity Measure storage device) uniqueness and distinctness advantage.These advantages include the improvement in both performance and durability, such as follows One or more of: all-in resistance reduces；The long-time stability of resistance improve (for example, material is at a given temperature at any time The raised reduction of resistance)；Total capacitance increases；The long-time stability of capacitor improve (for example, capacitor is at a given temperature at any time The reduction that capacitor reduces)；Energy density increases (for example, by providing higher voltage and/or by generating higher capacitor)； Voltage stability improves, and vapour pressure reduces, and the temperature range performance of single capacitor is wider (for example, between two temperature There is no the significant decrease of capacitor and/or the significant raising of ESR when conversion, for example, not having when the conversion from about+30 DEG C to about -40 DEG C There is the capacitor reduction greater than 90% and/or the ESR greater than 1000% to increase), the durability temperature of single capacitor improves (example Such as, at a given temperature after a given time lower than 50% capacitor reduce and/or it is low after a given time at a given temperature ESR in 100% is increased, and/or is lower than the leakage current of 10A/L after a given time at a given temperature, for example, being lower than 40% Capacitor reduce and/or ESR lower than 75% is increased, and/or the leakage current lower than 5A/L；For example, the capacitor lower than 30% drops Low and/or ESR lower than 50% is increased, and/or the leakage current lower than 1A/L), ease of manufacture improves (for example, by having Reduced vapour pressure, to obtain better yield and/or the more effective way with electrolyte filling capacitor)；And at This benefit improves (for example, by filling void space with the relatively inexpensive material of the cost compared with other materials).In order to clearly rise See, performance characteristics are related to following property: these properties are related to practicability of the device under given purpose, the practical sexual compatibility to Material under the similar given purpose used compares；Durability is related to and maintains over time the energy of above-mentioned property simultaneously The related property of power.The above performance and the example of durability should be used to be considered herein as " in performance or durability On significant changes " content provide stage brace.
For the sake of clarity, and in general, being included in energy storage of the invention as used in this article it fills Referring to for " electrolyte 6 " in setting refers to advanced electrolyte system of the invention.
The property of AES or electrolyte 6 can be improved result chosen from the followings: capacitor increase, equivalent series resistance (ESR) reduction, high thermal stability, lower glass transition temperatures (Tg), improved viscosity, specific rheopexy (rhoepectic) or touching Change nature (such as property depending on temperature) and high conductance and good electrical property is showed in wide temperature range.Example Such as, electrolyte 6 can have a high fluidity, or on the contrary, substantially solid, so that ensuring the isolation of electrode 3.
Advanced electrolyte system of the invention include: it is described herein be used in it is new in high temperature ultracapacitor Type electrolyte；For the highly purified electrolyte in high temperature ultracapacitor；And be suitable for from -40 degrees Celsius to The electrolyte combination of the enhancing used at a temperature of 210 degrees Celsius, performance or durability are not remarkably decreased at all temperatures.
Although the disclosure presented herein should be paid close attention to advanced electrolyte system described herein Applied to supercapacitor, but these advanced electrolyte systems can be applied to any energy accumulating device.
I. novel electrolytes entity (NEE)
In one embodiment, advanced electrolyte system (AES) of the invention is included in high temperature ultracapacitor The certain novel electrolytes used.In this respect, it has been found that maintenance purity and low moisture are related to the performance of energy storage 10 Grade；Also, using the electrolyte comprising hydrophobic material and it has been found that show higher purity and lower moisture The electrolyte of content help to obtain improved performance.Temperature model of these electrolyte at about 80 degrees Celsius to about 210 degrees Celsius Good performance characteristics are shown in enclosing, for example, at about 80 degrees Celsius to about 200 degrees Celsius；For example, about 80 degrees Celsius to about 190 degrees Celsius；For example, about 80 degrees Celsius to about 180 degrees Celsius；For example, about 80 degrees Celsius to about 170 degrees Celsius；For example, about 80 Degree Celsius to about 160 degrees Celsius；For example, about 80 degrees Celsius to about 150 degrees Celsius, for example, about 85 degrees Celsius to about 145 are Celsius Degree；For example, about 90 degrees Celsius to about 140 degrees Celsius；For example, about 95 degrees Celsius to about 135 degrees Celsius；For example, about 100 degrees Celsius To about 130 degrees Celsius；For example, about 105 degrees Celsius to about 125 degrees Celsius；For example, about 110 degrees Celsius to about 120 degrees Celsius.
Therefore, can be used as advanced electrolyte system (AES) novel electrolytes entity include comprising cation (for example, Cation shown in fig. 8 and described herein) and anion substance or such substance combination.In some implementations In scheme, it includes heteroaryl that above-mentioned substance, which includes cationic nitrogenous, oxygen-bearing cation, phosphorous cation and/or sulfur-bearing cation, Cation and heterocycle cation.In one group of embodiment, advanced electrolyte system (AES) includes comprising selected from ammonium, miaow Azoles、Azoles、, piperidines, pyrazine, pyrazoles, pyridazine, pyridine, pyrimidine, sulfonium, thiazole, triazole, guanidine, isoquinolin, benzotriazoleAnd purpurine types of cationic cation substance, it is above-mentioned cation in Any cation can be replaced with substituent group as described herein.In one embodiment, for advanced electrolysis of the invention The novel electrolytes entity of plastidome (AES) includes cation shown in fig. 8, and is selected from tetrafluoroborate, bis- (trifluoromethyls Sulphonyl) imines, four cyano borate and trifluoromethanesulfonic acid root anion any combination, it is shown in fig. 8 cation choosing From, piperidinesAnd ammonium, wherein each branched group Rx(for example, R1、R2、R3...Rx) alkyl, miscellaneous alkyl, alkene can be selected from Base, miscellaneous thiazolinyl, alkynyl, miscellaneous alkynyl, halogen, amino, nitro, cyano, hydroxyl, sulfate group, sulfonic group and carbonyl, wherein arbitrarily One is optionally substituted, and wherein at least two RxIt is not H (that is, the selection of R group and orientation is made to generate institute in Fig. 8 The cationic substance shown).
For example, giving the combination of above-mentioned cation and anion, in specific embodiments, AES can be selected from three hexyls MyristylBis- (trifluoromethyl sulfonyl) imines, 1- butyl -1- methyl piperidineBis- (trifluoromethyl sulfonyl) imines and The group of bis- (trifluoromethyl sulfonyl) imines of butyl trimethylammonium.In Figure 44 A and Figure 44 B, Figure 45 A and Figure 45 B and Figure 46 A and figure The performance enhanced in temperature range for supporting to be proved such as the capacitor and ESR measurement result that change over time is provided in 46B The data of characteristic, measurement result show high temperature practicability and long durability.
In certain embodiments, AES is three hexyl myristylsBis- (trifluoromethyl sulfonyl) imines.
In certain embodiments, AES is 1- butyl -1- methyl piperidineBis- (trifluoromethyl sulfonyl) imines.
In certain embodiments, AES is bis- (trifluoromethyl sulfonyl) imines of butyl trimethylammonium.
In another embodiment, the novel electrolytes of advanced electrolyte system (AES) for use in the present invention are real Body includes cation shown in fig. 8, and is selected from tetrafluoroborate, bis- (trifluoromethyl sulfonyl) imines, four cyano borate With any combination of the anion of trifluoromethanesulfonic acid root, cation shown in fig. 8 is selected from imidazolesAnd pyrrolidines, wherein Each branched group Rx(for example, R1、R2、R3...Rx) can selected from alkyl, miscellaneous alkyl, alkenyl, miscellaneous thiazolinyl, alkynyl, miscellaneous alkynyl, The group of halogen, amino, nitro, cyano, hydroxyl, sulfate group, sulphonic acid ester and carbonyl, wherein any one is optionally substituted, And wherein at least two RxIt is not H (that is, the selection of R group and orientation is made to generate cationic substance shown in fig. 8).? It is not two R of H in one specific embodimentxIt is alkyl.In addition, the cation form reveal high thermal stability and High conductance and show the good chemical property in wide temperature range.
For example, the combination of given above cation and anion, in specific embodiments, AES can be selected from 1- butyl- 3- methylimidazoleTetrafluoroborate；1- butyl -3- methylimidazoleBis- (trifluoromethyl sulfonyl) imines, 1- ethyl -3- first Base imidazolesTetrafluoroborate；1- ethyl-3-methylimidazoleFour cyano borate；1- hexyl -3- methylimidazoleFour cyano Borate；1- butyl -1- crassitudeBis- (trifluoromethyl sulfonyl) imines；1- butyl -1- crassitudeThree (pentafluoroethyl group) three fluorophosphate；1- butyl -1- crassitudeFour cyano borate and 1- butyl -3- methylimidazole Fluoroform sulphonate.
In one embodiment, AES is 1- butyl -3- methylimidazoleTetrafluoroborate.
In one embodiment, AES is 1- butyl -3- methylimidazoleBis- (trifluoromethyl sulfonyl) imines.
In one embodiment, AES is 1- ethyl-3-methylimidazoleTetrafluoroborate.
In one embodiment, AES is 1- ethyl-3-methylimidazoleFour cyano borate.
In one embodiment, AES is 1- hexyl -3- methylimidazoleFour cyano borate.
In one embodiment, AES is 1- butyl -1- crassitudeBis- (trifluoromethyl sulfonyl) imines.
In one embodiment, AES is 1- butyl -1- crassitudeThree (pentafluoroethyl group) three fluorophosphates.
In one embodiment, AES is 1- butyl -1- crassitudeFour cyano borate.
In one embodiment, AES is 1- butyl -3- methylimidazoleFluoroform sulphonate.
It is not two R of H in another specific embodimentxFirst is that alkyl, for example, methyl, and the other is with The alkyl that alkoxy replaces.Further, it is found that having the N of formula (1) in the molecule, the cation of O- acetal skeleton structure has High conductivity, and be included in these cations and there is pyrrolidines skeleton and N, the ammonium cation of O- acetal groups is having Electric conductivity and solubility in solvent is especially high, and supports relatively high voltage.In this way, in one embodiment, first Into electrolyte system include following formula salt:
Wherein R1And R2Can be identical or different, and be alkyl, and X- is anion.In some embodiments, R1 It is straight chained alkyl or branched alkyl with 1 to 4 carbon atom, R2It is methyl or ethyl, and X-It is the yin of cyano-containing borate Ion 11.In specific embodiments, X-Including [B (CN)]4And R2It is one of methyl and ethyl.In another particular implementation In scheme, R1And R2It is methyl.In addition, in one embodiment, being suitble to the cyano of advanced electrolyte system of the invention Acid anion 11, X-Including [B (CN) 4]-Or [BFn(CN)4-n]-, wherein n=0,1,2 or 3.
Novel electrolytes entity comprising formula (1) of the invention and quaternary ammonium cation and cyano as shown in formula (I) The example of the cation for the AES that acid anion is constituted is selected from N- methyl-N-methoxy crassitude(N- methoxy methyl Base-N- crassitude), N- ethyl-N- methoxymethylpyrrolidine, N- methoxy-N- n-propyl pyrrolidines、 N- methoxy-N- isopropylpyrrolidine, N- normal-butyl-N- methoxymethylpyrrolidine, N- isobutyl group-N- methoxyl group Crassitude, N- fert-Butyl-N-methoxy crassitude, N- ethoxyl methyl-N- crassitude, N- second Base-N- ethoxyl methyl pyrrolidines(N- ethoxyl methyl-N- ethyl pyrrolidine), N- ethoxyl methyl-N- n-propyl pyrrole Cough up alkane, N- ethoxyl methyl-N- isopropylpyrrolidine, N- normal-butyl-N- ethoxyl methyl pyrrolidines, N- isobutyl group- N- ethoxyl methyl pyrrolidinesWith N- tert-butyl-n-ethoxyl methyl pyrrolidines.Other examples include N- methyl-N- first Oxygroup crassitude(N- methoxy-N- crassitude), N- ethyl-N- methoxymethylpyrrolidineWith N- ethoxyl methyl-N- crassitude。
The other example of the cation of the formula (1) combined with other anion can be selected from N- methyl-N-methoxy first Base pyrrolidinesFour cyano borate (N- methoxy-N- crassitudeFour cyano borate), N- ethyl-N- first Oxygroup crassitudeFour cyano borate, N- ethoxyl methyl-N- crassitudeFour cyano borate, N- methyl- N- methoxymethylpyrrolidineDouble trifyl imines, (N- methoxy-N- crassitudeDouble fluoroforms Sulphonyl imine), N- ethyl-N- methoxymethylpyrrolidineDouble trifyl imines, N- ethoxyl methyl-N- methyl PyrrolidinesDouble trifyl imines, N- methyl-N-methoxy crassitudeFluoroform sulphonate (N- methoxyl group Methyl-N-methyl fluoroform sulphonate).
In the case where being used as electrolyte, the blending of quaternary ammonium salt with suitable organic solvent can be used.It is available molten Agent include cyclic carbonate, linear carbonate, phosphate, cyclic ether, chain ether, lactone compound, chain ester, nitrile compound, Amide compound and sulphones.The example of this kind of compound is listed below, but used solvent is not limited to these chemical combination Object.
The example of cyclic carbonate is ethylene carbonate, propylene carbonate, butylene carbonate etc., wherein preferred carbonic acid is sub- Propyl ester.
The example of linear carbonate is dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate etc., wherein preferred carbonic acid two Methyl esters and methyl ethyl carbonate.
The example of phosphate is trimethyl phosphate, triethyl phosphate, ethyl dimethyl ester, di(2-ethylhexyl)phosphate ethyl methyl esters etc.. The example of cyclic ether is tetrahydrofuran, 2- methyltetrahydrofuran etc..The example of chain ether is glycol dimethyl ether etc..Lactone compound The example of object is gamma-butyrolacton etc..The example of chain ester is methyl propionate, methyl acetate, ethyl acetate, methyl formate etc..Nitrile The example of compound is acetonitrile etc..The example of amide compound is dimethylformamide etc..The example of sulphones be sulfolane, Methyl sulfolane etc..In some embodiments, what is be especially desired to is cyclic carbonate, linear carbonate, nitrile compound and sulfone Compound.
These solvents can be used alone, and at least two solvents can also be used in the form of blend.It is preferred that organic molten The example of agent composition is: the mixture of cyclic carbonate and linear carbonate, such as ethylene carbonate and dimethyl carbonate The mixture of the mixture of mixture, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, polypropylene carbonate The mixture and propylene carbonate and carbonic acid diethyl of the mixture of ester and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate The mixture of ester；The mixture of the mixture of linear carbonate such as dimethyl carbonate and methyl ethyl carbonate；And sulfolane Close the mixture of the mixture such as sulfolane and methyl sulfolane of object.Even more preferably ethylene carbonate and methyl ethyl carbonate The mixture of mixture, the mixture of propylene carbonate and methyl ethyl carbonate and dimethyl carbonate and methyl ethyl carbonate.
In some embodiments, in the case where quaternary ammonium salt of the invention is used as electrolyte, electrolyte concentration is at least 0.1M is at least 0.5M in some cases and can be at least 1M.If concentration is lower than 0.1M, it will lead to low conduction Rate generates the electrochemical appliance that performance weakens.In the case where electrolyte is liquid salt at room temperature, upper concentration is that separation is dense Degree.In the unseparated situation of solution, limting concentration 100%.In the case that salt is solid at room temperature, limting concentration is Concentration when solution is by salt loading.
In certain embodiments, advanced electrolyte system (AES) can be incorporated be mixed in addition to it is disclosed herein that Electrolyte except a little electrolyte, so long as combination do not significantly affect the advantages of realized using advanced electrolyte system , for example, change performance or durability characteristics are more than 10%.It may adapt to the example of the AES electrolyte blended be alkali Metal salt, quaternary ammonium salt, seasonSalt etc..When blending with AES herein disclosed, these electrolyte be can be used alone, or At least two in these electrolyte of person can be used in combination.Workable alkali metal salt includes lithium salts, sodium salt and sylvite.This lithium The example of salt is lithium hexafluoro phosphate, lithium fluoroborate, lithium perchlorate, trifluoromethanesulfonic acid lithium, sulfimide lithium, methylsulfonyl lithium etc., so And this is not limiting.The example of workable sodium salt is sodium hexafluoro phosphate, sodium fluoborate, sodium perchlorate, trifluoromethanesulfonic acid Sodium, sulfimide sodium, methylsulfonyl sodium etc..The example of workable sylvite is Potassium Hexafluorophosphate, potassium fluoborate, potassium hyperchlorate, three Fluorine methanesulfonic acid potassium, sulfimide potassium, methylsulfonyl potassium etc., however these are not limiting.
The above-described workable quaternary ammonium salt that can be applied in combination (uses advanced electrolyte that is, not significantly affecting The advantages of system is realized) it include tetraalkylammonium salt, imidazolesSalt, pyrazolesSalt, pyridineSalt, triazoleSalt, pyridazine Salt etc., this is not limiting.The example of workable tetraalkylammonium salt is etamon four cyano borate, tetramethylammonium four cyano Borate, tetrapropylammonium four cyano borate, tetrabutylammonium four cyano borate, triethyl group first ammonium four cyano borate, trimethyl second Ammonium four cyano borate, dimethyl diethyl ammonium four cyano borate, trimethyl the third ammonium four cyano borate, four cyanogen of trimethyl fourth ammonium Ylboronic acid salt, dimethyl ethyl the third ammonium four cyano borate, Methylethyl propyl fourth ammonium four cyano borate, N, N- dimethyl pyrazole Cough up alkaneFour cyano borate, N- ethyl-N-methyl pyrrolidinesFour cyano borate, N- Methyl-N-propyl pyrrolidinesFour Cyano borate, N- ethyl-N- propyl pyrrole alkaneFour cyano borate, N, N- lupetidineFour cyano borate, N- Methyl-N ethyl piperidinesFour cyano borate, N- Methyl-N-propyl piperidinesFour cyano borate, N- ethyl-N- propyl PiperidinesFour cyano borate, N, N- thebaineFour cyano borate, N- methyl-N ethyl morpholineFour cyano boron Hydrochlorate, N- Methyl-N-propyl morpholineFour cyano borate, N- ethyl-N- propylmorpholinFour cyano borate etc., however These examples are simultaneously unrestricted.
It is above-described that (that is, not significantly affecting the advantages of realized using advanced electrolyte system) can be applied in combination ImidazolesThe example of salt includes 1,3- methylimidazoleFour cyano borate, 1- ethyl-3-methylimidazoleFour cyano boron Hydrochlorate, 1,3- diethyl imidazoliumFour cyano borate, 1,2- dimethyl -3- ethyl imidazol(e)Four cyano borate and 1,2- Dimethyl -3- propyl imidazoleFour cyano borate, but it is not limited to these.PyrazolesThe example of salt is 1,2- dimethyl pyrazoleFour cyano borate, 1- methyl -2- ethylpyrazolFour cyano borate, 1- propyl -2- methylpyrazoleFour cyano boric acid Salt and 1- methyl -2- butyl pyrazolesFour cyano borate, but it is not limited to these.PyridineThe example of salt is N- picolineFour cyano borate, N- ethylpyridineFour cyano borate, N- propyIpyridineFour cyano borate and N- butyl-pyridiniumFour cyano borate, but it is not limited to these.TriazoleThe example of salt is 1- methyl-triazoleFour cyano borate, 1- ethyl TriazoleFour cyano borate, 1- propyl triazoleFour cyano borate and 1- triazbutilFour cyano borate, but it is unlimited In these.PyridazineThe example of salt is 1- methyl pyridazineFour cyano borate, 1- ethyl pyridazineFour cyano borate, 1- Propyl pyridazineFour cyano borate and 1- butyl pyridazineFour cyano borate, but it is not limited to these.SeasonThe example of salt is TetraethylFour cyano borate, tetramethylFour cyano borate, tetrapropylFour cyano borate, the tetrabutylFour Cyano borate, triethyl methylFour cyano borate, trimethylethylFour cyano borate, dimethyl diethyl Four cyano borate, thmethylpropylFour cyano borate, trimethyl butylFour cyano borate, dimethyl ethyl third BaseFour cyano borate, Methylethyl butylFour cyano borate, but it is not limited to these.
In certain embodiments, the selected novel electrolytes for advanced electrolyte system can also be with herein It is purified.Technology well known in the art can be used in such purifying or technology presented herein executes.The purifying can be with It is further improved the characteristic of novel electrolytes entity described herein.
Ii. highly purified electrolyte
In one embodiment, advanced electrolyte system of the invention is included in used in high temperature ultracapacitor Certain highly purified electrolyte.In certain embodiments, the highly purified electrolyte for constituting AES of the invention is to pass through The those described below electrolyte and those as described above novel electrolytes of purification process purifying described herein.This Purification process provided in text generates the impurity level for being capable of providing advanced electrolyte system, the advanced electrolysis plastid The performance used in high temperature application (for example, high temperature ultracapacitor) with enhancing is tied up to, for example, at about 80 degrees Celsius to about Within the temperature range of 210 degrees Celsius, for example, about 80 degrees Celsius to about 200 degrees Celsius；For example, about 80 degrees Celsius to about 190 Celsius Degree；For example, about 80 degrees Celsius to about 180 degrees Celsius；For example, about 80 degrees Celsius to about 170 degrees Celsius；For example, about 80 degrees Celsius To about 160 degrees Celsius；For example, about 80 degrees Celsius to about 150 degrees Celsius；For example, about 85 degrees Celsius to about 145 degrees Celsius；For example, About 90 degrees Celsius to about 140 degrees Celsius；For example, about 95 degrees Celsius to about 135 degrees Celsius；For example, about 100 degrees Celsius to about 130 Degree Celsius；For example, about 105 degrees Celsius to about 125 degrees Celsius；For example, about 110 degrees Celsius to about 120 degrees Celsius.
The improved property for obtaining supercapacitor 10 causes demand more better than existing obtainable electrolyte system Electrolyte system.For example, it has been found that increase operating temperature range can by substantially reduced from certain forms of known electrolyte/ Impurity is removed to realize.Impurity of specific interest include water, halogen ion (chloride ion, bromide ion, fluorine ion and iodide ion), Unhindered amina (ammonia), sulfate radical and metal cation (Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb,Sr,Ti,Zn).Purify in this way through highly purified electrolyte product provide it is unexpected be much better than it is not purified The electrolyte of electrolyte, and therefore, belong to advanced electrolyte system of the invention.
In specific embodiments, the present invention provides the purified cations 9 and yin that may be used as AES of the invention The mixture of ion 11 and solvent in some cases, the AES of aforementioned present invention include being below about 5000 parts/million parts (ppm) chloride ion；Fluorine ion below about 1000ppm；And/or the water below about 1000ppm is (for example, be below about 2000ppm Chloride ion；Fluorine ion below about 200ppm；And/or the water below about 200ppm, for example, below about 1000ppm chlorine from Son；Fluorine ion below about 100ppm；And/or the water below about 100ppm is lower than for example, being below about the chloride ion of 500ppm The fluorine ion of about 50ppm；And/or the water below about 50ppm, for example, being below about 780 parts/million parts of chloride ion；Below about 11 Part/million parts of fluorine ion；With the water for being below about 20 parts/million parts.)
In general, removing the impurity in the electrolyte being purified using purification process described herein.For example, In some embodiments, the total concentration of halogen ion (chloride ion, bromide ion, fluorine ion and iodide ion) be can reduce to being below about 1000ppm.Metallics is (for example, in Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb, Zn, including its alloy and oxide It is at least one) total concentration can reduce to below about 1000ppm.In addition, coming from solvent and precursor used in synthesis process Impurity can reduce to below about 1000ppm, and may include such as bromoethane, chloroethanes, 1- bromobutane, 1- neoprene Alkane, 1- methylimidazole, ethyl acetate, methylene chloride etc..
In some embodiments, using the ion-selective electrode and card of the electrolyte 6 for being applied to supercapacitor 10 Your Fischer (Karl Fischer) titration measures the impurity content of supercapacitor 10.In certain embodiments, It was found that be the halogen ion (Cl- and F-) below about 200ppm according to the total halide content for the supercapacitor 10 instructed herein, Water content is below about 100ppm.
Can be used various technologies such as Atomic Absorption Spectrometer (AAS), inductivity coupled plasma mass spectrometry (ICPMS) or Simplify solubilising and electrochemical sensing trace heavy metal oxide particle to measure impurity.AAS be for using by it is gaseous from The spectroscopic analysis methods of chemical element are qualitatively and quantitatively measured by the absorption of the light radiation (light) of atom.The technology is for true The concentration of element-specific (analyte) in fixed sample to be analyzed.AAS can be used for measuring in solution or directly in solid sample In be more than 70 kinds of different elements.ICPMS is a kind of mass spectrography, High sensitivity and can measure metal and several non-gold What is belonged to is lower than 1012The range of the concentration of/mono- (part per trillion).The technology is to be based on to be used as generating ion (ionization) The inductively coupled plasma body of method be combined together with the mass spectrum as the method for separating and detecting ion.ICPMS can also Enough isotope forms for monitoring selected ion.
Other technology can be used and carry out analysing impurity.Impurity in some pairs of analysing solid samples in these technologies is special It is not advantageous.It is miscellaneous come the halide for measuring trace level in electrolyte 6 (for example, ionic liquid) that ion chromatography (IC) can be used Matter.One advantage of ion chromatography is can to measure relevant halide with monochromatic spectrum analysis.Using comprising 20mM NaOH and The Dionex AS9-HC column of the eluant, eluent of 10% (v/v) acetonitrile is to can be used for setting for halide of the quantification from ionic liquid A standby example.Another technology is X-ray fluorescence spectra.
X-ray fluorescence (XRF) instrument can be used to measure the content of halogen in solid sample.It in the art, will be wait divide Analysis sample is placed in specimen cup, then specimen cup is placed on the X-ray of specific wavelength in the analyzer irradiated.In sample Any halogen atom absorbs a part of X-ray, then reflects the radiation of the characteristic wavelength as given halogen.Then in the instrument Detector the amount of radiation returned from halogen atom is quantified, and measure radiation intensity.By the surface for understanding exposure Product, can determine the concentration of halogen in sample.Other technology for evaluating the impurity in solid sample is pyrolytic technique.
The absorption of impurity can effectively to measure by using pyrolysis and microcoulombmeter (microcoulometer).Microcoulomb Human relations meter can test the chloride content of almost any type of material.As an example, by a small amount of sample (less than 10 milligrams) It injects or is put into quartz combustion tube, the temperature in quartz combustion tube is from about 600 degrees Celsius to about 1000 degree Celsius.Make pure oxygen By quartz ampoule, and any chlorine-containing component of completely burned.Gained combustion product is purged into titration unit, wherein chloride ion is cut It stays in electrolyte solution.Electrolyte solution includes silver ion, and silver ion is immediately with any chloride binding and as insoluble Silver chlorate (drop out) is detached from from solution.The silver electrode electricity titrated in unit replaces used up silver ion, until silver The concentration of ion returns to the concentration before titration starts.The amount of the required electric current of the desired amount of silver, instrument energy are generated by tracking Enough there are how much chlorine in measurement initial sample.The total amount of existing chlorine provides chlorine actually in the sample divided by the weight of sample Concentration.The other technologies for evaluating impurity can be used.
For example, can be by infrared spectrum technology come the surface characteristics and water content in detecting electrode 3.About 1130cm-1、1560cm-1、3250cm-1And 2300cm-1Four prominent absorption bands at place correspond respectively to ν C=O, ν C=in aryl C, ν O-H and ν C-N.By measurement intensity and peak position, the surface impurity in electrode 3 can be quantitatively determined.
Another kind is for determining that the technology of electrolyte 6 and the impurity in supercapacitor 10 is Raman spectrum.The spectrum skill Art depends on monochromatic inelastic scattering or Raman scattering, and described monochromatic light is usually from visible light, near infrared light or close The laser of ultraviolet light range.Molecular vibration, phonon or other excitations in laser and system interact, and lead to laser photon Energy changes up and down.Therefore, which can be used for characterizing atom and molecule in supercapacitor 10.Using Raman spectrum Many versions, and susceptible of proof its content that can be used for characterizing supercapacitor 10.
Iii. the electrolyte combination enhanced
In one embodiment, advanced electrolyte system of the invention includes being suitble to use under following temperature range Certain enhancings electrolyte combination, and be not remarkably decreased in performance or durability, the temperature range is -40 degrees Celsius To 210 degrees Celsius；For example, -40 degrees Celsius to 150 degrees Celsius；For example, -30 degrees Celsius to 150 degrees Celsius；For example, -30 is Celsius Degree is to 140 degrees Celsius；For example, -20 degrees Celsius to 140 degrees Celsius；For example, -20 degrees Celsius to 130 degrees Celsius；For example, -10 take the photograph Family name's degree is to 130 degrees Celsius；For example, -10 degrees Celsius to 120 degrees Celsius；For example, 0 degree Celsius to 120 degrees Celsius；For example, 0 is Celsius Degree is to 110 degrees Celsius, for example, 0 degree Celsius to 100 degrees Celsius；For example, 0 degree Celsius to 90 degrees Celsius；For example, 0 degree Celsius to 80 Degree Celsius；For example, 0 degree Celsius to 70 degrees Celsius.
In general, the durability of higher degree can be with the voltage of higher degree at a lower temperature at a given temperature Stability is consistent.Therefore, the exploitation of the high temperature durability AES of the electrolyte combination using enhancing is normally resulted in while is developed High voltage but lower temperature AES so that electrolyte combinations of these described herein enhancings can also be in higher electricity Pressure uses, and therefore has higher energy density, but lower temperature.
In one embodiment, the present invention provides be suitble to make in energy storage unit (for example, supercapacitor) The electrolyte combination of enhancing, the electrolyte combination of the enhancing include novel electrolytes mixture, and the novel electrolytes are mixed It closes object to be selected from: being mixed with the ionic liquid of the second ionic liquid, is mixed with the ionic liquid of organic solvent and is mixed with second The ionic liquid of ionic liquid and organic solvent.
Wherein, every kind of ionic liquid is selected from the salt of any combination of following cation and anion, wherein cation choosing From: 1- butyl -3- methylimidazole, 1- ethyl-3-methylimidazole, 1- hexyl -3- methylimidazole, 1- butyl -1- methyl Piperidines, butyl trimethylammonium, 1- butyl -1- crassitude, three hexyl myristylsWith 1- butyl -3- methylimidazole；And anion is selected from: tetrafluoroborate, bis- (trifluoromethyl sulfonyl) imines, four cyano borate and trifluoromethanesulfonic acid Root；And
Wherein, organic solvent is selected from straight chain sulfone (for example, ethylisopropyl sulfone, ethyl isobutyl sulfone, ethyl methyl sulfone, methyl isopropyl Sulfone, isopropyl isobutyl sulfone, isopropyl Zhong Ding sulfone, butyl isobutyl sulfone and dimethyl sulfone), linear carbonate (for example, ethylene carbonate, Propylene carbonate and dimethyl carbonate) and acetonitrile.
For example, the combination of given above cation and anion, every kind of ionic liquid can be selected from: 1- butyl -3- methyl ImidazolesTetrafluoroborate, 1- butyl -3- methylimidazoleBis- (trifluoromethyl sulfonyl) imines, 1- ethyl-3-methylimidazoleTetrafluoroborate, 1- ethyl-3-methylimidazoleFour cyano borate, 1- hexyl -3- methylimidazoleFour cyano boric acid Salt, 1- butyl -1- crassitudeBis- (trifluoromethyl sulfonyl) imines, 1- butyl -1- crassitudeThree (five fluorine Ethyl) three fluorophosphates, 1- butyl -1- crassitudeFour cyano borate, three hexyl myristylsBis- (fluoroforms Base sulfonyl) imines, 1- butyl -1- methyl piperidineBis- (trifluoromethyl sulfonyl) imines, the bis- (trifluoromethyls of butyl trimethylammonium Sulfonyl) imines and 1- butyl -3- methylimidazoleFluoroform sulphonate.
In certain embodiments, ionic liquid is 1- butyl -3- methylimidazoleTetrafluoroborate.
In certain embodiments, ionic liquid is 1- butyl -3- methylimidazoleBis- (trifluoromethyl sulfonyl) imines.
In certain embodiments, ionic liquid is 1- ethyl-3-methylimidazoleTetrafluoroborate.
In certain embodiments, ionic liquid is 1- ethyl-3-methylimidazoleFour cyano borate.
In certain embodiments, ionic liquid is 1- hexyl -3- methylimidazoleFour cyano borate.
In certain embodiments, ionic liquid is 1- butyl -1- crassitudeBis- (trifluoromethyl sulfonyls) is sub- Amine.
In one embodiment, ionic liquid is 1- butyl -1- crassitudeThree (pentafluoroethyl group) three fluorophosphoric acid Salt.
In certain embodiments, ionic liquid is 1- butyl -1- crassitudeFour cyano borate.
In certain embodiments, ionic liquid is three hexyl myristylsBis- (trifluoromethyl sulfonyl) imines.
In certain embodiments, ionic liquid is 1- butyl -1- methyl piperidineBis- (trifluoromethyl sulfonyl) imines.
In certain embodiments, ionic liquid is bis- (trifluoromethyl sulfonyl) imines of butyl trimethylammonium.
In certain embodiments, ionic liquid is 1- butyl -3- methylimidazoleFluoroform sulphonate.
In certain embodiments, organic solvent is selected from ethylisopropyl sulfone, ethyl isobutyl sulfone, ethyl methyl sulfone, methyl isopropyl Sulfone, isopropyl isobutyl sulfone, isopropyl Zhong Ding sulfone, butyl isobutyl sulfone or dimethyl sulfone, straight chain sulfone.
In certain embodiments, organic solvent is selected from poly (propylene carbonate), propylene carbonate, dimethyl carbonate, carbonic acid Ethyl.
In certain embodiments, organic solvent is acetonitrile.
In certain embodiments, the electrolyte composition of enhancing is the ionic liquid with organic solvent, wherein organic Solvent is calculated as 55% to 90% by the volume of composition, for example, 37.5%.
In certain embodiments, the electrolyte composition of enhancing is the ionic liquid with the second ionic liquid, wherein A kind of ionic liquid is calculated as 5% to 90% by the volume of composition, for example, 60%.
The electrolyte combination of enhancing of the invention for single capacitor provide broader temperature range performance (such as when Between two temperature convert when there is no the significant decrease of capacitor and/or the significant raising of ESR, for example, when from about+30 DEG C conversion to 90% capacitor is not greater than at about -40 DEG C to be reduced and/or ESR greater than 1000% is increased) and single capacitor temperature Durability improves (for example, the capacitor lower than 50% reduces and/or exists at a given temperature after a given time at a given temperature ESR after given time lower than 100% is increased, and/or is lower than the leakage current of 10A/L after a given time at a given temperature； For example, the capacitor lower than 40% reduces and/or the ESR lower than 75% is increased, and/or the leakage current lower than 5A/L；For example, being lower than 30% capacitor reduces and/or the ESR lower than 50% is increased, and/or the leakage current lower than 1A/L).Figure 47 A and Figure 47 B, figure 48A and Figure 48 B and Figure 49 respectively illustrate the ionic liquid from above-mentioned ionic liquid under 125 degrees Celsius, 37.5% The behavior that organic solvent-ionic liquid (identical) v/v is under 125 degrees Celsius and identical composition is under -40 degrees Celsius.
In the case where being not wishing to be bound by theory, combinations of the above provides the solidification for influencing advanced electrolyte system Point enhancing eutectic characteristic so that supercapacitor can down to -40 degrees Celsius at a temperature of in performance and durability mark Operation in quasi-.
As above for described in novel electrolytes of the invention, in certain embodiments, advanced electrolyte system (AES) Electrolyte can be blended with, so long as combination do not significantly affect the advantages of realized using advanced electrolyte system.
In certain embodiments, the electrolyte of the selected enhancing for advanced electrolyte system herein can also be with It is purified.Technology well known in the art can be used in such purifying or technology presented herein executes.
B.Electrode
EDLC includes that electrode 3 (wherein, can be known as negative electrode 3 and positive electrode 3, just at this by least a pair of electrodes 3 The purpose quoted in text).When being assembled into supercapacitor 10, electric double layer is presented in each electrode 3 at electrolyte interface.? In some embodiments, including multiple electrodes 3 (for example, in some embodiments, including at least two pairs of electrodes 3).However, being The purpose discussed, only shows a pair of electrodes 3.Herein as convention, at least one of electrode 3 is stored up using carbon-based energy Medium 1 (as further discussed herein) is deposited to provide energy stores.But the purpose in order to be discussed herein, it generally assumes that Each of electrode includes carbon-based energy storage media 1.
I current-collector
Each of electrode 3 includes respective current-collector 2 (also referred to as " charge collector ").In some embodiment party In case, electrode 3 is separated by isolator 5.In general, isolator 5 is thin for separating negative electrode 3 and positive electrode 3 Structural material (usually piece).Isolator 5 can also be used to separate multipair electrode 3.Note that in some embodiments, electricity It can not include carbon-based energy storage media 1 on one or both of pole 3.That is, in some embodiments, corresponding electricity Pole 3 can be only made of current-collector 2.Material for providing current-collector 2 can be it is roughened, by anodized etc. To increase its surface area.In these embodiments, individual current-collector 2 can serve as electrode 3.However, for this reason, Term as used herein " electrode 3 " refers generally to the combination of energy storage medium 1 and current-collector 2 (but at least aforementioned original Cause, this is simultaneously unrestricted).
Ii. energy storage medium
In exemplary supercapacitor 10, energy storage medium 1 is formed by carbon nanotube.Energy storage medium 1 can be with Including other carbonaceous materials, including such as active carbon, carbon fiber, staple fibre, graphene, aeroge, carbon cloth and a variety of shapes The carbon nanotube of formula.Activated carbon electrodes can be manufactured for example, by following steps: to obtained by the carbonization of carbon compound Carbon material executes first and is activated to produce carbon-based material；By adding adhesive to form body to manufacture to the carbon-based material； Be carbonized the formation body；And activated carbon electrodes are manufactured eventually by the second activation processing is executed to the formation body of the carbonization.Carbon Fiber electrode can be manufactured for example by using the paper or cloth of the carbon fiber with high surface area are preforming.
In a kind of illustrative methods for manufacturing carbon nanotube, for producing aligned carbon nanotube aggregation The equipment of (aligned carbon-nanotube aggregate) includes on the surface thereof with the substrate of catalyst The equipment for synthesizing aligned carbon nanotube aggregation.The equipment includes: to form unit, and formation unit execution makes around catalyst Environment becomes reducibility gas environment and heats the forming step of at least catalyst or reducing gas；Growing element, the growth Unit is executed by making the environment around catalyst become the environment of unstrpped gas and by heating at least catalyst or unstripped gas Body synthesizes the growth step of aligned carbon nanotube aggregation；And buanch unit, the buanch unit is at least by substrate from formation Unit is transferred to growing element.Various other methods and apparatus can be used to provide aligned carbon nanotube aggregation.
In some embodiments, the material for being used to form energy storage medium 1 may include in addition to pure carbon (and at present may be used Can be existing or later by the carbon of the diversified forms of invention) except material.That is, may include in energy storage medium 1 The various preparations of other materials.More specifically, and as unrestricted example, can be used in energy storage medium 1 to A kind of few adhesive material, still, this is not suggestion or requires to add other materials (for example, adhesive material).However, one As for, energy storage medium 1 is substantially formed by carbon, and is therefore properly termed as " carbonaceous material ", " carbon containing herein Layer " and other similar term.In short, energy storage medium 1 may include any form although mainly being formed by carbon Carbon (and being considered appropriate or acceptable any additive or impurity) using provide as energy storage medium 1 expectation Functionality.
In one group of embodiment, carbonaceous material includes by mass at least about 60% elemental carbon, and in other realities It applies in scheme, by mass the elemental carbon of at least about 75%, 85%, 90%, 95% or 98%.
Carbonaceous material may include carbon of diversified forms, including carbon black, graphene etc..The carbonaceous material may include carbon Particle (including nano particle, such as the graphene film of nanotube, nanometer rods, sheet form) and/or be formed as cone, stick, ball (Buckie Ball (buckyball)) etc..
Some embodiment conducts of the carbonaceous material of a variety of formation suitable for energy storage medium 1 are provided herein Embodiment.These embodiments provide steady energy storage and are highly suitable in electrode 3.It should be noted that these implementations Example is illustrative, and the embodiment for being not limited to the carbonaceous material suitable for energy storage medium 1.
In certain embodiments, can each electrode of size selection based on each electrolyte energy storage medium 1 Porosity is to improve the performance of capacitor.
It now provided with for configuring example of (compliment) current-collector 2 electrode 3 is arranged for energy storage medium 1 Property method.Referring now to Fig. 2, the substrate 14 of the matrix of the carbonaceous material as carbon nanotube agglomerate (CNT) form is shown. In the embodiment illustrated, substrate 14 includes the substrate 17 for being provided with 18 thin layer of catalyst.
In general, substrate 14 is at least some flexible (that is, substrate 14 is non-friable), and by that can bear energy storage The component for depositing the environment of medium 1 (for example, CNT) deposition is made.For example, substrate 14 can bear about 400 degrees Celsius to about 1100 Hot environment between degree Celsius.As long as it is suitable to determine, multiple material can be used for substrate 14.
Referring now to Fig. 3.Once energy storage medium 1 (for example, CNT) has been fabricated on substrate 14, can be at it Upper setting current-collector 2.In some embodiments, current-collector 2 is about 0.5 micron (μm) to about 25 microns (μm) thick.Some In embodiment, current-collector 2 is about 20 microns (μm) to about 40 microns (μm) thick.Current-collector 2 can behave as thin layer, such as pass through Chemical vapor deposition (CVD), sputtering, electron beam, thermal evaporation or the layer applied by other suitable technology.It is general and Speech, current-collector 2 is for its property such as conductibility, electrochemicaUy inert and compatible with energy storage medium 1 (for example, CNT) Property selects.Some exemplary materials include aluminium, platinum, gold, tantalum, titanium, and may include other materials and a variety of alloys.
Once being arranged current-collector 2 on energy storage medium 1 (for example, CNT), that is, realize electrode member 15.Each Electrode member 15 can be used alone as electrode 3, or can be coupled at least another electrode member 15 to provide electricity Pole 3.
Once having manufactured current-collector 2 according to desired standard, it can set about post-processing processing.Exemplary post-processing includes Heating and cooling energy storage medium 1 (for example, CNT) in the environment of slight oxidation.Manufacture (and optional post-processing) it Afterwards, transfer tool can be applied to current-collector 2.It is referred to Fig. 4.
Fig. 4, which is shown, is applied to current-collector 2 for transfer tool 13.In this embodiment, transfer tool 13 is turned " dry " Hot release band (thermal release tape) used in shifting method.Exemplary hot release band by California Fu Limeng The NITTO DENKO CORPORATION manufacture of Osaka (Osaka) of special (Fremont) and Japan.A kind of suitable transfer band It is sold as REVALPHA.The release band is characterized in that the adhesive tape of good bond at room temperature, and can pass through heating Removing.The suitable embodiment of other of the band and hot release band will be removed at a predetermined temperature.Advantageously, the release band Chemical activity residue is not left on electrode member 15.
During another kind is known as " wet " transfer method, the band designed for chemical stripping can be used.Once application Afterwards, the band is removed by immersing the band in solvent later.The solvent is designed to dissolve adhesive.
In other embodiments, transfer tool 13 uses " pneumatic " method, such as is inhaled by applying to current-collector 2 Power.Suction can for example be applied by the bigger blade (paddle) of the size with multiple perforation for being distributed suction. In another embodiment, suction is applied by the roller with multiple perforation for being used to be distributed suction.The implementation of suction driving Scheme provides automatically controlled advantage and economic advantage, because consumptive material is not used as a part of transfer process.Transfer can be used Other embodiments of tool 13.
Once transfer tool 13 is temporarily coupled to current-collector 2, i.e., gently removed from substrate 14 electrode member 15 (referring to Fig. 4 and Fig. 5).The removal relates generally to since an edge of substrate 14 and energy storage medium 1 (for example, CNT) from substrate 14 removings energy storage medium 1 (for example, CNT).
It is then possible to which transfer tool 13 is separated with electrode member 15 (referring to Fig. 6).In some embodiments, it uses Transfer tool 13 installs electrode member 15.It is, for example, possible to use transfer tools 13, and electrode member 15 is arranged into isolator 5 On.In general, once removing from substrate 14, electrode member 15 is i.e. available.
In the case where it is expected big electrode 3, multiple electrodes element 15 can be matched.It can refer to Fig. 7.As shown in fig. 7, can To make multiple electrodes element 15 for example, by coupling 15 phase of each electrode member of coupling 52 and multiple electrodes element 15 Matching.Matched electrode member 15 provides the embodiment of electrode 3.
In some embodiments, coupling 22 is coupled to each electrode member 15 at weldment 21.Each weldment 21 can be set to ultrasonic bond fitting 21.It has been found that ultra-sonic welding techniques are especially suited well for providing each weldment 21. That is, in general, the aggregation of energy storage medium 1 (for example, CNT) is incompatible with welding, wherein only using for example Nominal current-collector disclosed herein.Therefore, many technologies for connection electrode element 15 are destructive, and damage institute State element 15.However, in other embodiments, having used the coupling of other forms, and coupling 22 is not weldment 21。
Coupling 22 can be foil, net, multiple conducting wires or other forms.In general, coupling 22 is directed to characteristic for example Conductibility and electrochemicaUy inert select.In some embodiments, coupling 22 by with the material phase in the presence of current-collector 2 Same material is made.
In some embodiments, coupling 22 is manufactured by removing oxide layer thereon.It can be for example by mentioning Oxide is removed for etching coupling 22 before weldment 21.Etching can be for example with potassium hydroxide (KOH) Lai Shixian.Electrode 3 can be used in the various embodiments of supercapacitor 10.For example, electrode 3 can be rolled becomes " glue volume (jelly Roll the) " energy storage device of type.
C.Isolator
Isolator 5 can be manufactured by a variety of materials.In some embodiments, isolator 5 is non-woven glass.Isolator 5 can also be manufactured by glass fibre, ceramics and fluoropolymer, and the fluoropolymer is for example usually bright by Delaware State prestige The polytetrafluoroethylene (PTFE) (PTEE) that the DuPont Chemicals of (Wilmington, DE) that pauses is sold with TEFLONTM.For example, using Non-woven glass, isolator 5 may include principal fiber and adhesive fiber, and the fibre diameter of every adhesive fiber is less than every The fibre diameter of principal fiber, and principal fiber is bonded together.
For the long-life of supercapacitor 10 and in order to ensure performance at high temperature, isolator 5 should have reduction Amount impurity, and the moisture of very limited amount being especially contained therein.Particularly, it has been found that expectation about 200ppm Moisture limitation with reduce chemical reaction and extend supercapacitor 10 service life, and provide high temperature application in formedness Energy.Some embodiments for the material in isolator 5 include polyamide, polytetrafluoroethylene (PTFE) (PTFE), polyether-ether-ketone (PEEK), aluminium oxide (Al2O3), glass fibre and glass reinforced plastic (GRP).
In general, the material for isolator 5 is according to moisture content, porosity, fusing point, impurity content, resulting electricity Performance, thickness, cost, utilizability etc. select.In some embodiments, isolator 5 is formed by hydrophobic material.
It is therefore possible to use certain methods ensure to remove excessive moisture from each isolator 5.It can be dry using vacuum Drying method and other technologies.The selection of the material for isolator 5 is provided in table 1.Some relevant property are provided in table 2 It can data.
Table 1
Separator materials
Table 2
Isolator performance data
In order to collect the data of table 2, two electrodes 3 based on carbonaceous material are provided.Two electrodes 3 are oppositely arranged simultaneously And it is facing with each other.Each isolator 5 is arranged between electrode 3 to prevent short circuit.Then three components are soaked simultaneously with electrolyte 6 It forces together.Two aluminium bars and PTFE material are used to enclose gained supercapacitor 10 as external structure.
The test of ESR first is carried out one by one with identical configuration and ESR second is tested.Second test is surveyed first It runs within 5 minutes after examination, leaves the time further infiltrated through in component for electrolyte 6.
In certain embodiments, supercapacitor 10 does not include isolator 5.For example, in a particular embodiment, such as Ensured in physically-isolated embodiment in electrode 3 by the geometry of structure, meeting only has electrolyte 6 between electrode 3.More Specifically, and as a physically-isolated example, a kind of such supercapacitor 10 may include being arranged in shell So that the electrode 3 for ensuring to be isolated on a continuous basis.Desk-top (bench-top) example of one kind will include being arranged in beaker (beaker) supercapacitor 10 in.
D.Storage unit
Once assembling, electrode 3 and isolator 5 provide for storage unit 12.In general, storage element 12 is formed as rolling up Around one of form or prism form, then it is encapsulated in cylindric or prism-shaped shell 7.Once it has accommodated into electrolyte 6, Shell 7 can be sealed airtightly.In various embodiments, encapsulation is by the technology and/or welding technique using laser, ultrasound Airtightly to seal.Other than providing firm physical protection for storage element 12, shell 7 be also configured with external contacts with Offer is electrically connected with each terminal 8 in shell 7.Each terminal 8 is provided to the energy being stored in energy storage medium 1 in turn Electrical connection (a cubic centimetres of ess of electrical), the electrical connection generally drawn by being coupled to the electricity of energy storage medium 1 Line is realized.
In general, supercapacitor 10 disclosed herein is capable of providing leak rate no more than about 5.0 × 10- 6Atm cubic centimetres/second it is gas-tight seal, and no more than about 5.0 × 10 can be shown-10Atm- cubic centimetres/second Leak rate.It is additionally considered that successful hermetically sealed performance is taken the circumstances into consideration to judge by user, designer or producer, and " airtight " Finally indicate the standard defined by user, designer, producer or other shareholders.
Leak detection can be for example realized by using search gas.Being used for leak-testing using search gas such as helium is to have Benefit, because it is dry, quick, accurate and nondestructive method.In one embodiment of the technology, by super electricity Container 10 is put into helium environment.Supercapacitor 10 is set to be subjected to the helium of pressurization.Then, by supercapacitor 10 be placed on can In the vacuum chamber for monitoring the connection of detector (for example, Atomic absorption unit) existing for helium.Using known pressing time, pressure and Internal capacity can determine the leak rate of supercapacitor 10.
In some embodiments, by least one lead (it is alternatively referred to as " contact pin (tab) " herein) electric coupling To that corresponding current-collector 2.More leads (polarity corresponding to supercapacitor 10) can be combined and be coupled to Corresponding terminal 8.In turn, terminal 8 can be coupled to electrical connection, and referred to as " contact " is (for example, shell 7 and external electrode are (at this One of also it is known as " feedthrough component (feed-through) " or " pin (pin) " in text by convention)).It can refer to Figure 28 and Figure 32 To Figure 34.
E. shell
Figure 11 depicts some aspects of exemplary shell 7.The in particular supercapacitor 10 of shell 7 provides structure and physics Protection etc..In this embodiment, shell 7 includes the ontology 20 of ring-shaped cylinder shape shape and the lid of supplement (complimentary) 24.In this embodiment, lid 24 includes the center portion for being removed and being filled with electrical insulator 26.Lid feedthrough component 19 passes through Electrical insulator 26 is worn to provide stored energy for user.In addition, shell further includes inner barrier object 30.
Although This embodiment describes the only one feedthrough components 19 on lid 24, it should be recognized that the construction of shell 7 is unlimited In embodiment discussed in this article.For example, lid 24 may include multiple feedthrough components 19.In some embodiments, ontology 20 Second including circular cylinder opposite end similar lid 24.In addition, it will also be appreciated that shell 7 is not limited to ring-shaped cylinder The embodiment of the ontology 20 of shape shape.For example, shell 7 for clamshell designs, prism-shaped design, bag or any can be suitable for setting Other designs of the needs of meter person, producer or user.
Referring now to fig. 12, it illustrates example energy storage elements 12.In this embodiment, energy storage unit 12 It is " glue volume " type energy storage device.In these embodiments, energy storage material is rolled as compact package part.More are drawn Line generally forms each terminal 8, and provides the electrical connection of the suitable layer of energy storage unit 12.In general, in group When dress, each terminal 8 is electrically coupled to shell 7 (for example, be electrically coupled to each feedthrough component 19 and/or be directly electrically coupled to shell 7).Energy Amount storage element 12 can take many forms.Generally there are more leads (for example, terminal 8) of at least two groups, each current-collector 2 uses One group.For simplicity, one of terminal 8 is only shown in Figure 12, Figure 15 and Figure 17.
It is expected that shell 7 is efficient sealed.That is, preventing the intrusion of external environment (for example, air, moisture etc.) from helping In the pure of the component for maintaining energy storage unit 12.In addition, it prevents electrolyte 6 from leaking from energy storage unit 12.
In this embodiment, the manufacture of lid 24 has the outer diameter for being designed as being closely fit with the internal diameter of ontology 20.In assembling, Lid 24 can be welded into ontology 20, to provide for user gas-tight seal.Illustrative welding technique includes laser welding And TIG weld, as long as and may include the welding for thinking suitable other forms.
Common materials for shell 7 include stainless steel, aluminium, tantalum, titanium, nickel, copper, tin, various alloys, laminate etc.. The structural material more such as material based on polymer can be used in shell 7 (generally combining at least some metal components).
In some embodiments, the material for constructing ontology 20 includes aluminium, may include that designer or producer recognize For suitable any kind of aluminum or aluminum alloy (it is all broadly referred to simply as " aluminium " herein).It can be by various conjunctions Gold, laminate etc. are arranged in the top (for example, cladding) of aluminium (aluminium for being exposed to the inside of ontology 20).Other materials can be used Material (for example, structural material or electrically insulating material, such as some based on the material of polymer) supplements ontology and/or shell 7.If Set that the material above aluminium again may be by designer or producer thinks suitably to select.
In some embodiments, multilayer material is used for internal part.For example, aluminium can be coated with stainless steel to be provided to Multilayer material in a few terminal 8.These embodiments it is some in, a part of aluminium can be removed to expose stainless steel. Then the stainless steel exposed can be used for that terminal 8 is attached to feedthrough component 19 by using simple welding method.
The specific embodiment of covering material can be required using the covering material for internal part.For instance, it may be beneficial to Be using include aluminium (bottom), stainless steel and/or tantalum (middle layer) and aluminium (top layer) covering material, so that its limitation is stainless Steel is exposed to the internal environment of supercapacitor 10.These embodiments can by, for example, polymeric material (for example, PTFE additional coating) improves.
Therefore it provides being provided with energy storage device using the shell 7 of multilayer material, the energy storage device shows and shows There is technology compared to the leakage current with relatively low initial value and leakage current increases at any time significantly slowerly.Significantly, exist When supercapacitor 10 is exposed to environment temperature, the leakage current of energy storage device is existing still in available (i.e. it is desired to ground is low) level There is technology capacitor that will show excessive initial leakage current value and/or leakage current too fast increasing at any time under the environment temperature Add.
In addition, supercapacitor 10 can express as caused by the reacting of reduction between shell 7 and energy storage unit 12 Other benefits.For example, the effective series resistance (ESR) of energy storage device can express value relatively low at any time.In addition, hair The raw unexpected chemical reaction in prior art capacitor often generates unexpected result (for example, deflating or airtightly The bulging of shell 7 in the case where seal casinghousing).In both cases, this causes the structural intergrity of shell 7 and/or energy to be stored up The gas-tight seal of storage is damaged.Finally, this can lead to the leakage of prior art capacitor or catastrophic failure.These influences can lead to It crosses the application of disclosed barrier and significantly reduces or eliminate.
By using multilayer material (for example, covering material), stainless steel can be integrated in shell 7, therefore can made With the component with glass to metal seal part.The component, which can be used technology such as laser or electric resistance welding and fetch, is soldered to packet The stainless steel side of material is covered, and the aluminum side of covering material is solderable is connected to other aluminium parts (for example, ontology 20).
In some embodiments, insulating polymer can be used for the coated portion of shell 7.In this manner, can be sure to be able to The component of amount reservoir is exposed only to the metal (for example, aluminium) of acceptable type.Exemplary insulated polymer include PFA, FEP, TFE and PTFE.Suitable polymer (or other materials) only by system designer or producer needs and each material property The limitation of matter.It is referred to Figure 23, is exposed to sleeve 51 and feedthrough including a small amount of insulating materials 39 to limit electrolyte 6 The stainless steel of part 19.In this embodiment, terminal 8 is coupled to feedthrough component 19, such as by welding, is then applied with insulating materials 39 It covers.
I case lid
Although This embodiment describes the only one feedthrough components 19 on lid 24, it should be recognized that the construction of shell 7 is unlimited In embodiment discussed in this article.For example, lid 24 may include multiple feedthrough components 19.In some embodiments, ontology 20 Second including circular cylinder opposite end similar lid 24.In addition, it will also be appreciated that shell 7 is not limited to ring-shaped cylinder The embodiment of the ontology 20 of shape shape.For example, shell 7 for flip designs, prism-shaped design, bag or any can be suitable for setting Other designs of the needs of meter person, producer or user.
Referring now to fig. 18, show the various aspects of the embodiment of the blank 34 of lid 24.In Figure 18 A, blank 34 is wrapped Include multilayer material.First material layer 41 is aluminium.Second material layer 42 is stainless steel.In the embodiment of Figure 18, stainless ladle It is layed on aluminium, to provide the material for showing desired metallurgical performance combination.That is, in some implementations provided herein In scheme, aluminium is exposed to the inside of energy storage unit (that is, shell), and stainless steel is externally exposed.In this way, it enjoys The advantageous electrical property of aluminium, while the structural property (and metallurgical properties, that is, weldability) of stainless steel is relied on to construct.Only Think suitable, multilayer material may include additional layer.
As mentioned above, first material layer 41 is coated in second material layer 42 that (or first material layer 41 is coated with Second material layer 42).Referring now still to Figure 18 A, in one embodiment, blank is provided using the piece of flat material (as shown) 34 to produce flat lid 24.A part (for example, around lid 24) of second material layer 42 can be removed to facilitate Lid 24 is attached to ontology 20.In Figure 18 B, another embodiment of blank 34 is shown.In this embodiment, blank 34 has There is the covering material sheet for being formed as recessed construction.In Figure 18 C, blank 34 has the covering material sheet for being formed as convex construction.By base The lid 24 of the various embodiments manufacture of part 34 (for example, those shown in Figure 18) is configured to the sheet that bearing is soldered to shell 7 Body 20.More specifically, the embodiment of Figure 18 B is adapted to fit in the internal diameter of ontology 20, and the embodiment of Figure 18 C is suitble to In the top for being assemblied in 20 outer diameter of ontology.In many a alternative embodiments, the layer of covering material can be overturned in piece.
Referring now to fig. 19, show the embodiment of electrode assembly 50.Electrode assembly 50 is designed as being mounted on base In part 34, and provide the electric connection from energy storage medium to user.In general, electrode assembly 50 includes sleeve (sleeve)51.Sleeve 51 surrounds insulator 26, and insulator 26 surrounds feedthrough component 19 in turn.In this embodiment, sleeve 51 is With the annular cylinder at the top of flanged pin.
For group capping 24, the manufacture perforation (not shown) in blank 34.Perforation has size matched electrodes sub-assembly 50 Geometry.Therefore, electrode assembly 50 is inserted into the perforation of blank 34.Once being inserted into electrode assembly 50, electrode combination Part 50 can be labelled to blank 34 by technology (for example, welding).Welding can be laser welding, around the convex of welded sleeve 51 It is welded around edge.Referring to Figure 20, the point 61 welded is shown.In this embodiment, point 61 is provided for welding not This relatively simple welding procedure of suitable position of rust steel to stainless steel.Therefore, introduction herein is provided electrode combination Part 50 is firmly welded to the position on blank 34.
Material for constructing sleeve 51 may include various types of metal or metal alloy.In general, for covering The material of cylinder 51 is selected according to such as structural intergrity and engageable property (to blank 34).Exemplary materials for sleeve 51 Including 304 stainless steels or 316 stainless steels.Material for constructing feedthrough component 19 may include that various types of metals or metal close Gold.In general, the material for feedthrough component 19 is selected according to such as structural intergrity and conductivity.Example for electrode Property material include 446 stainless steels or 52 alloys.
In general, insulator 26 is bonded to sleeve 51 and feedthrough component by known technology (that is, glass-metal engagement) 19.Material for constructing insulator 26 may include but be not limited to various types of glass, including high temp glass, glass-ceramic or Ceramic material.In general, the material for insulator is selected according to such as structural intergrity and resistance (that is, electrical insulation characteristics) It selects.
Dependent on glass-metal engagement component (for example, foregoing embodiments of electrode assembly 50) use and The use of various welding techniques provides the gas-tight seal of energy storage device.It also can be used other component gas-tight seal to provide.This It is close no more than leak rate as defined herein that term " gas-tight seal " used herein generally refers to show leak rate Envelope.However, it is believed that practical leakage efficiency can be carried out better than the standard.
Additional or other technology for electrode assembly 50 to be coupled to blank 34 includes thinking such skill Use cement when art is appropriate (between flange and second material layer 42) below the flange of sleeve 51.
Referring now to Fig. 21, energy storage unit 12 is arranged in ontology 20.Suitably couple at least one 8 (example of terminal Such as, until feedthrough component 19), and lid 24 is matched with ontology 20 supercapacitor 10 is arranged.
Once assembling, lid 24 are i.e. salable with ontology 20.Figure 22 depicts assembled energy storage device (in such case Under, supercapacitor 10) various embodiments.It is flat to produce using flat blank 34 (referring to Figure 18 A) in Figure 22 A Flat lid 24.Once lid 24 is arranged on ontology 20, i.e. welding lid 24 and ontology 20 is to produce sealing element 62.In such case Under, because ontology 20 is annular cylinder, it is welded on around ontology 20 and lid 24 and carries out to provide sealing element 62.? In two embodiments, as shown in Figure 22 B, recessed lid 24 is generated using recessed blank 34 (referring to Figure 18 B).Once the setting of lid 24 is existed On ontology 20, i.e., welding lid 24 and ontology 20 are to produce sealing element 62.In the third embodiment, as shown in fig. 22 c, use is convex Blank 34 (referring to Figure 18 C) produces dished cover 24.Once lid 24 is arranged on ontology 20, can welding lid 24 and ontology 20 with Produce sealing element 62.
In due course, covering material (by technology for example, processing or etching etc.) can be removed to expose in multilayer material Other metals.Therefore, in some embodiments, sealing element 62 may include aluminium-aluminium weldment.Aluminium-aluminium weldment can be with It is aided with other fasteners in due course.
Other technologies can be used and carry out seal casinghousing 7.It is, for example, possible to use laser welding, TIG weld, resistance welding, surpass Sonic soldering connects the mechanical seal with other forms.However, it should be noted that in general, the mechanical seal of individual traditional form is insufficient With provide provided in supercapacitor 10 it is firm gas-tight seal.
Referring now to Fig. 24, wherein depicting the various aspects of another embodiment of group capping 24.Figure 24 A depicts use In the template (that is, blank 34) for the ontology for providing lid 24.The size of the template generally matches the energy storage unit of appropriate type The shell 7 of (for example, supercapacitor 10).Lid 24 can be formed by following steps: it is initially provided of template and forms template, Including the dome 37 (being shown in Figure 24 B) in template；Then it perforates to dome 37 to provide channel 32 (being shown in Figure 24 C). Of course, it is possible to suppress or to provide preceding feature simultaneously by other methods manufacture blank 34 (for example, annular storage part).
In general and these embodiments are considered, lid can be formed by aluminium or its alloy.However, lid can be by making The person of making, user, designer etc. think that suitable any materials are formed.For example, lid 24 can be formed from steel and be passivated (that is, applying Be covered with inertia coating) or by other methods preparation for shell 7.
Referring now to Fig. 25, show another embodiment of electrode assembly 50.In these embodiments, electrode Sub-assembly 50 includes the material of feedthrough component 19 and the semi-spherical shape being arranged in around feedthrough component 19.The material of the semi-spherical shape is used Make insulator 26, and is formed generally as meeting dome 37.Hemispherical insulator 26 can be made of any suitable material with Chemical affect that is gas-tight seal while being resistant to electrolyte 6 is provided.Exemplary materials include PFA (perfluoroalkoxy resin), FEP (fluorinated ethylene propylene copolymer), PVF (polyvinyl fluoride), TFE (tetrafluoroethene), CTFE (chlorotrifluoroethylene), PCTFE (poly- three Fluorine vinyl chloride), it is ETFE (polyethylene tetrafluoroethene), ECTFE (polyethylene-chlorotrifluoroethylene), PTFE (polytetrafluoroethylene (PTFE)), another Kind, which is based on fluoropolymer-containing material and any other, can show that similarity (in various degree) and offer make us full The material of the performance (for example, under the conditions ofs high temperature, low cost etc., in particular, showing high dissolubility resistent, acid resistance) of meaning.
Feedthrough component 19 can be formed by aluminium or its alloy.However, feedthrough component 19 can be by producer, user, designer Etc. thinking that suitable any materials are formed.For example, feedthrough component 19 can be formed from steel and be passivated (that is, being coated with the lazy of such as silicon Property coating) or by other methods preparation be used in electrode assembly 50 in.Example technique for passivation includes that will hydrogenate Amorphous silicon paint deposit on a surface of the substrate and by exposing the substrate to have under pressure and raised temperature One section of adhesive effective time span of at least one unsaturated alkyl carrys out substrate coated by functionalization.By in pressure and One section of silane gas effective time span is exposed the substrate at raised temperature carrys out depositing hydrogenated amorphous silicon paint.
The size of hemispherical insulator 26 can be designed such as realizing when being assembled into lid 24 relative to dome 37 close It is bonded (that is, gas-tight seal).Hemispherical insulator 26 is without hemisphere ratios ideally symmetrical or with classics.Namely It says, hemispherical insulator 26 is substantially hemispheric, and can include such as ratio, moderate flange when being deemed appropriate The fine tuning of (for example, base position) and other features.Hemispherical insulator 26 is generally formed by uniform material, and still, this is not It is necessary condition.For example, hemispherical insulator 26 may include the air or gas being filled in anchor ring (not shown) therein Body, to provide desired expansion or compressibility.
As shown in figure 26, it includes half that electrode assembly 50, which can be inserted in template (that is, being formed by blank 34) to provide, One embodiment of the lid 24 of spherical gas-tight seal.
As shown in figure 27, in many a embodiments, holder 43 can be engaged or be matched by other methods and be covered 24 bottom (that is, inside of the lid 24 towards shell 7 and part towards energy storage unit 12).Holder 43 can pass through Multiple technologies such as aluminium welding (for example, laser, ultrasound etc.) is bonded to lid 24.Other technologies can be used for engaging, including for example rush Pressure (that is, mechanical engagement) and soldering.Engagement can for example occur along the perimeter of holder 43.In general, at least one Junction provides engagement to generate desired sealing element 71.At least one fastener (for example, multiple rivets) can be used will Insulator 26 is sealed in holder 43.
In the embodiment of Figure 27, lid 24 is recessed meter (referring to Figure 18 B).It is also possible, however, to use other are designed.Example Such as, dished cover 24 (Figure 18 C) can be provided, top lid 24 also can be used, and (change programme of the embodiment of Figure 18 C, is configured to According to the discribed installation of Figure 22 C).
For covering and the material of feedthrough component 19 can be considered the thermal expansion of hemispherical insulator 26 and select.In addition, also It can be with design and manufacturing technology to consider to thermally expand.For example, producer can apply to hemispherical insulator 26 in group capping 24 Pressure, at least compress hemispherical insulator 26 to a certain extent.It in this way, is at least some thermal expansions of lid 24 Presence made to prepare without damaging hermetically sealed effect.
In order to further illustrate the supercapacitor of assembling, referring to Figure 28, which provide the section views of supercapacitor 10 Figure.In this embodiment, storage element 12 is inserted into and includes in bodies 20.Every group of more leads are held together and are coupled to Shell 7 is as one of terminal 8.In some embodiments, more leads are coupled to the bottom (in inside) of ontology 20, thus will Ontology 20 becomes cathode contact part 55.Equally, another group of more leads are held together and are coupled to feedthrough component 19, to provide anode Contact 56.The electric isolution between cathode contact part 55 and positive contact 56 is kept by electrical insulator 26.In general, The coupling of lead is realized by welding, such as at least one of laser and ultrasonic welding.Of course, it is possible to when being deemed appropriate Use other technologies.
Ii. inner barrier object
Referring now to fig. 13, shell 7 may include inner barrier object 30.In some embodiments, barrier 30 is to apply Material.In this embodiment, barrier 30 is formed by polytetrafluoroethylene (PTFE) (PTFE).Polytetrafluoroethylene (PTFE) (PTFE) shows various to make this Composition is suited well for the property of barrier 30.The fusing point of PTFE is about 327 degrees Celsius, has excellent dielectric property, rubs Wipe coefficient be about 0.05 to 0.10 (this is that third in any known solid material is low), there is high corrosion-resistant and other are beneficial Property.In general, the interior section of lid 24 may include the barrier 30 being arranged on.
Other materials can also be used for barrier 30.These other materials are (any to be suitably adapted for applying and satisfaction property by ceramics Can standard Types of Pottery), other polymers (preferably high temperature polymer) etc. are formed.Illustrative other polymers include perfluor Alkoxy resin (PFA) and fluorinated ethylene propylene copolymer (FEP) and ethylene-tetrafluoroethylene copolymer (ETFE).
Barrier 30 may include providing the electrification reduced between energy storage unit 12 and shell 7 or the component of shell 7 Learn any materials of type or other kinds of reaction or the combination of material.In some embodiments, which is single The homogeneous dispersion of different materials in layer.In a further embodiment, embodied in combination is the different materials in multiple layers.It can be with Use other combinations.In short, barrier 30 can be considered in electrical insulator and chemical inertness (showing hypoergia) extremely It is one of few, and therefore, it is significant to resist or prevent in the electric interactions and chemical interaction between storage element 12 and shell 7 At least one of.In some embodiments, term " hypoergia " and " low chemical reactivity " refer generally to lower than related side's Pay close attention to horizontal chemical interaction rate.
In general, the inside of shell 7 can accommodate barrier 30, so that covering shell 7 is exposed to all of inside Surface.At least one unprocessed region 31 may include in bodies 20 and on the outer surface of lid 24 36 (referring to Figure 14 A). It in some embodiments, may include untreated region 31 (referring to Figure 14 B) to meet assembling demand, such as will be close The region of envelope or connection (such as passing through welding).
Barrier 30 can be used routine techniques and be applied to interior section.For example, in the case where PTFE, can pass through by Barrier 30 is applied as coating or is sprayed onto interior surface to apply barrier 30.It is unprocessed as ensuring that mask can be used Region 31 retains a part of the method for expectation integrality.In short, barrier 30 can be provided using multiple technologies.
In an exemplary embodiment, barrier 30 with a thickness of about 3 mils to about 5 mils, and be used for barrier 30 material is the material based on PFA.In this embodiment, oxygen is for example used for receiving to constitute the surface of the material of barrier 30 Change aluminium to prepare with blasting treatment.Once then regarding surface cleaning as powder as liquid first to apply material.Pass through heat Treatment process solidifies the material.In some embodiments, heat cycles be about 370 degrees Celsius at a temperature of about 10 minutes To about 15 minutes duration.This leads to the continuous throwing for containing substantially no the barrier 30 of aperture size or smaller defect Light.Figure 15 depicts the assembling of the embodiment according to the supercapacitor 10 instructed herein.In this embodiment, super electricity Container 10 includes: the ontology 20 of the barrier 30 comprising being disposed therein；Lid 24 with the barrier 30 being disposed therein；With And energy storage unit 12.During assembly, lid 24 is arranged on ontology 20.First terminal 8 is electrically coupled to lid feedthrough Part 19, at the same by second terminal 8 usually the bottom of lid 24, side or on be electrically coupled to shell 7.In some embodiments In, second terminal 8 is coupled to another feedthrough component 19 (for example, opposite lid 24).
Using the barrier 30 in the interior surface that shell 7 is arranged in, electrochemical reaction between shell 7 and electrolyte with And other reactions greatly reduce or substantially eliminate.This is in chemical reaction and other usually raised higher temperatures of rate reacted Under it is particularly evident.
Referring now to fig. 16, show the relative performance for being equal to the supercapacitor 10 of supercapacitor compared to other. In Figure 16 A, the leakage current of the prior art embodiment of supercapacitor 10 is shown.In fig. 16b, it shows including resistance The leakage current of the equivalent supercapacitor 10 of parting 30.In fig. 16b, supercapacitor 10 and leakage current are shown in Figure 16 A Super capacitor electrode is equivalent.In both cases, shell 7 is stainless steel, and the voltage for being applied to the unit is 1.75 volts, And electrolyte is not purified.Keep constant 150 degrees Celsius of temperature.Particularly, the leakage current in Figure 16 B shows lower first Initial value and it is significant at any time increase, and the leakage current in Figure 16 A shows relatively high initial value and significant at any time It increases.
In general, barrier 30 provides the suitable material of suitable thickness between energy storage unit 12 and shell 7.Resistance Parting 30 may include homogeneous mixture, heterogeneous mixture and/or at least one layer of material.Barrier 30 can be provided and is completely covered (that is, providing the covering of interior surface area of the shell in addition to electrode contact) or part cover.In some embodiments, it obstructs Object 30 is formed by Multiple components.For example, it is contemplated that being shown below and embodiment shown in fig. 8.
Referring to Fig.1 7, show the various aspects of other embodiments.In some embodiments, energy storage unit 12 is set It sets in encapsulation object (envelope) 73.It is disposed thereon, is packed above it that is, energy storage unit 12 has, Or the barrier 30 that once assembling is applied by other methods to separate energy storage unit 12 and shell 7.Encapsulation object 73 can apply well before energy storage unit 12 is encapsulated into shell 7.Therefore, the use of encapsulation object 73 may be present Certain advantages, such as producer.(it should be noted that encapsulation object 73 is shown as being loosely disposed in energy for purposes of illustration On storage element 12).
In some embodiments, encapsulation object 73 is used in combination with coating, and wherein interior surface is arranged at least in coating In a part.For example, in one embodiment, coating be positioned only at the encapsulation object 73 inside shell 7 can at least partly by In the region of damage (for example, being protruded terminal 8).Encapsulation object 73 and coating are formed together efficient barrier 30.
Therefore, the combination of barrier 30 can provide the leakage current shown compared with prior art with lower initial value And the supercapacitor that leakage current is substantially relatively slowly increased at any time.Significantly, as being exposed to when supercapacitor The leakage current of supercapacitor is still in practical (i.e. it is desired to ground is low) level when environment temperature, and the capacitor of the prior art is at this Excessively big initial leakage current value and/or leakage current will be showed under environment temperature excessively quickly to increase at any time.
It is thus described the embodiment and its many aspects perhaps of barrier 30, it is recognized that supercapacitor 10 can table Reveal other benefits as caused by the reacting of reduction between shell 7 and energy storage medium 1.For example, supercapacitor 10 has Effect series resistance (ESR) can show relatively low value at any time.In addition, unexpected change occurs in prior art capacitor Reaction is learned usually to generate unexpected effect and for example deflate, or in the case where airtightly seal casinghousing shell bulging.? In the case of two kinds, this causes the structural intergrity of shell and/or the gas-tight seal of capacitor to be damaged.Finally, this can lead to existing The leakage of technology capacitor or catastrophic failure.In some embodiments, these results can pass through disclosed barrier 30 use is significantly reduced or is eliminated.
It should be understood that term " barrier " and " coating " is not limited to teaching herein.That is, any use can be used Technology in the inside that suitable material is applied to shell 7, ontology 20 and/or lid 24.For example, in other embodiments, By barrier 30 actually be fabricated onto constitute enclosure body 20 material within or on, then in due course to the material carry out Processing is shaped to form all parts of shell 7.It is some in many possible technologies for applying barrier 30 when considering When, it can be equal suitably by rolling on (roll on), sputtering, sintering, laminated, printing or by other methods apply institute State material.In short, barrier 30 can think suitable any technology using producer, designer and/or user to apply Add.
Material in barrier 30 can be selected according to for example following property: reactivity, dielectric radio, fusing point, with Adherency, coefficient of friction, cost and other such factors of the material of shell 7.The combination of material can be used (for example, dividing It is layer, mixing or combine by other means) desired property is provided.
In some embodiments, electricity can be limited using the shell of enhancing 7 (for example, shell 7 with barrier 30) Solve the deterioration of matter 6.Although barrier 30 show it is a kind of for provide enhancing shell 7 technology, other can also be used Technology.For example, due to the electrochemical properties of aluminium in the presence of electrolyte 6, so the use of the shell 7 being manufactured from aluminium being advantageous 's.But, it is contemplated that the difficulty in the manufacture of aluminium fails always construction (so far) and utilizes the embodiment of the shell 7 of aluminium.
The other embodiments of shell 7 include that aluminium is present in those of all interior surfaces for being exposed to electrolyte in fact Scheme is applied, while providing the ability of welding and airtight seal casinghousing for user.The improved performance of supercapacitor 10 can be with By the inside burn into and the reduction and other reasons using related problem of different metal in transmitting medium of reduction come real It is existing.Advantageously, shell 7 utilizes the prior art, and the electrode package including glass to metal seal part available in this way (and can be with Including by those of stainless steel, tantalum or other advantageous materials and ingredient manufacture), therefore can economically fabricate.
Although being disclosed herein as the embodiment for the shell 7 for being suitable for supercapacitor 10, these implementations Scheme (as having the case where barrier 30) can think that suitable energy storage device is used together with any kind of, and can be with Including any type of possible technique.It is, for example, possible to use the energy storage devices of other forms, including electrochemical cell, especially It is lithium-base battery.
In general, the material being exposed to inside shell 7 is being exposed to electrolyte 6 (that is, advanced electrolyte of the invention System) when show sufficiently low reactivity, therefore be merely illustrative some embodiments without limit teaching herein.
F.The factor that capacitor generally constructs
The importance considered in the construction of supercapacitor 10 is to maintain good chemical hygiene.In order to ensure Component it is pure, in many a embodiments, the dry energy for constituting two electrodes 3 at elevated temperatures in vacuum environment Measure active carbon, carbon fiber, staple fibre, carbon cloth and/or the nanotube of storage medium 1.Isolator 5 is also rising in vacuum environment It is dry at a temperature of high.After electrode 3 and isolator 5 are dried under vacuum, i.e., by they be encapsulated in shell 7 without Lower than finally sealing or cover in the atmosphere of 50 parts/million parts (ppm) water.For example, can be at entirely about 100 degrees Celsius to about Uncapped supercapacitor 10 is dried under vacuum within the temperature range of 300 degrees Celsius.Once the final dry completion Add electrolyte 6, and the seal casinghousing 7 in the atmosphere of relatively dry (for example, atmosphere that moisture is below about 50ppm).Certainly, may be used To use other assemble methods, and some illustrative aspects of the aforementioned sub-assembly for only providing supercapacitor 10.
III. method of the invention
Certain methods for reducing impurity or manufacturing the device of the invention of the invention are described herein below.It is such pure In addition the method for change applies also for any advanced electrolyte system of the invention.
A.The method for reducing impurity
I.AES pollutant
In certain embodiments, advanced electrolyte system (AES) of the invention is purified to remove pollutant And provide the performance characteristics of desired enhancing described herein.Therefore, this disclosure provides a kind of sides for purifying AES Method, this method comprises: water is mixed into advanced electrolyte system to provide the first mixture；Separate the first mixture；From First mixture collects advanced electrolyte system；To collected liquid addition solvent to provide the second mixture；Carbon is mixed It closes into the second mixture to provide third mixture；It is purified to obtain that advanced electrolyte system is separated from third mixture Advanced electrolyte system.In general, this method requires to select electrolyte, addition deionization under controlled conditions Water and active carbon.Then removal deionized water and active carbon, obtain the electrolyte through purifying substantially.Purified electrolyte is especially It is suitable for use in supercapacitor.
This method can be used to ensure the high degree of purity of advanced electrolyte system (AES) of the invention.It should be noted that It is, although this method indicates that the expression is only intended to pure electrolyte with special parameter (such as amount, formula, time etc.) Method example and explanation, be not limited.
For example, this method may also comprise the following steps: or feature in it is one or more: heating the first mixture；Its In, separation includes placing the first mixture uninterruptedly until water and AES are basically separated；Wherein, solvent is added Including addition ether, pentone (pentone), ring pentone (cyclopentone), hexane, hexamethylene, benzene, toluene, At least one of 1-4- dioxane and chloroform；Wherein, mixing carbon includes mixing carbon dust；Wherein, mixing carbon includes Substantially third mixture is constantly stirred；Wherein, separation AES includes filtering out carbon from third mixture and keeping solvent mixed from third Close at least one of object evaporation.
It (is in some embodiments ionic liquid by electrolyte 6 in the first step for the method for pure electrolyte Body) it is mixed with de-ionized water, it is then increased to moderate moisture, is kept for a period of time.In Proof of Concept, by 50 (50) The ionic liquid of milliliter (ml) is mixed with the deionized water of 850 (850) milliliters (ml).The mixture is increased to 60 (60) degree Celsius steady temperature is kept for about 12 (12) hours, and carries out lasting stirring (about 120 (120) rev/min Clock (rpm)).
In the second step, so that ionic liquid is separated with the mixture of deionized water.In this embodiment, pass through funnel The mixture is shifted, the mixture is then made to place for about four (4) hours.
In third step, collection of ions liquid.In this embodiment, the water phase of mixture is located at bottom, ionic liquid Mutually it is located at top.Ionic liquid is mutually transferred in another beaker.
In four steps, solvent is mixed with ionic liquid.It in this embodiment, is about 25 (25) millis by volume The ethyl acetate for rising (ml) is mixed with ionic liquid.The mixture is increased to moderate moisture again and stirs a period of time.
Although using ethyl acetate as solvent, solvent can be at least one of following substance: ether, isoamyl Eneyne (pentone), ring pentone (cyclopentone), hexane, hexamethylene, benzene, toluene, 1-4- dioxane, Chloroform or any combination thereof and the other materials for showing proper property characteristic.Some desired performance characteristics include nonpolarity Those of solvent and high volatility.
In the 5th step, to adding carbon dust in the mixture of ionic liquid and solvent.In this embodiment, to mixture The carbon (about 0.45 micron diameter) of about 20 (20) weight percent (wt%) of middle addition.
In the 6th step, mixed ionic liquid again.In this embodiment, then at about 70 (70) degrees Celsius to tool There is the mixture of carbon dust to carry out constant agitation (120rpm) overnight.
In the 7th step, carbon and ethyl acetate is made to be located away from ionic liquid.In this embodiment, using micro- with glass The Buchner funnel of fabric filter carrys out separation of carbon.(3 times) are filtered for multiple times.Then, make collected ionic liquid by 0.2 Micrometer syringe formula filter is substantially to remove all carbon particles.In this embodiment, then come by using rotary evaporation Solvent is separated with ionic liquid.Specifically, the sample of ionic liquid is stirred, while temperature being increased from 70 (70) degree Celsius It to 80 (80) degree Celsius, and is finally 100 (100) degree Celsius.At each temperature in each temperature, will evaporate into About 15 (15) minutes of row.
It has proven to highly effective for the method for pure electrolyte.For sample ions liquid, with by Ohio brother's human relations The titrator (model: AQC22) that the Mettler-Toledo Inc. in cloth city (Columbus, Ohio) is provided, is surveyed by titrating Measure water content.With the ISE of the Hanna Instruments of Woonsocket offer by Rhode Island (Rhode Island) Instrument (model: AQC22) measures content of halogen.Standard solution for ISE instrument derives from Hanna, and including HI 4007-03 (1000ppm chlorine standard), HI 4010-03 (1000ppm fluorine standard), HI 4000-00 (ISA for halogen electrodes) and HI 4010-00 (the TISAB solution for being only used for fluoride electrode).Before carrying out the measurements, with mixed in deionized water use 0.1, 10, the standard solution of 100 and 1000 parts/million parts (ppm) of standard items corrects ISE instrument.With the ratio of 1:50 into standard items ISA buffer is added to measure Cl- ion.As a result it is shown in Table 3.
Table 3
- 1- the crassitude of butyl containing 1-With the purifying data of the electrolyte of four cyano borate
Impurity (ppm) before (ppm) later Deionized water (ppm)
Cl- 5,300.90 769 9.23E-1
F- 75.61 10.61 1.10E-1
H2O 1080 20 --
Halogen ion is measured using four step rule technique.Firstly, measuring Cl in deionized water-Ion and F-Ion.Then, Ion water making is spent for the ionic liquid solution of 0.01M.Then, Cl is measured in the solution-Ion and F-Ion.Then, pass through use The amount of effects of ion subtracts the amount of water intermediate ion to determine the assessment of content of halogen.
Also by examining the purification standard about electrolyte pollution object composition to the analysis of leakage current.Fig. 9 depicts super The leakage current of not purified electrolyte in grade capacitor 10.Figure 10 depicts purified in the supercapacitor 10 of similar structures The leakage current of electrolyte.As can be seen, initial leakage current significantly reduces, and the leakage current for measuring the aft section at interval is appropriate It reduces.Structure based on each embodiment in table 4 provides more information.
Table 4
Test the construction of supercapacitor
Parameter Fig. 9 Figure 10
Cell size: Open Sub C Open Sub C
Sleeve: Coat P870 Coat P870
Electrode material: Two-sided active carbon (150/40) Two-sided active carbon (150/40)
Isolator: Glass fibre Glass fibre
Electrode size: IE:233 × 34mm OE:256 × 34mm IE:233 × 34mm OE:256 × 34mm
Contact pin: 0.005 " aluminium (3 contact pin) 0.005 " aluminium (3 contact pin)
Temperature: 150℃ 150℃
Electrolyte: Not purified AES Purified AES
Other benefits are also achieved, the raising of the stability of resistance and capacitor including supercapacitor 10.
Leakage current can determine in many ways.Qualitatively, once device has reached equilibrium state, i.e., it is believed that electric leakage Stream is the electric current in introducing device.In fact, always or almost always needing to estimate as generally only can be progressively close flat The practical leakage current for the state that weighs.Therefore, the electric current of supercapacitor 10 can be introduced by measurement to estimate the leakage in given measurement Electric current, while supercapacitor 10 is maintained at substantially stationary voltage and is exposed to substantially stationary environment temperature, keeps phase To long a period of time.In some cases, the relatively long period can be by estimating the current time as exponential function Then function to determine by several (for example, about 3 to 5) characteristic time constants.Often for many supercapacitors For technology, such duration is from about 50 hours to about 100 hour.Alternatively, if such long period for appoint What reason is infeasible, then as the current time function of exponential function or can may think suitable any approximation by estimation Function simply calculates leakage current again.It is worth noting that, leakage current will generally depend on environment temperature.Therefore, it is Performance of the characterization apparatus at a certain temperature or in certain temperature range, it is usually important that will dress when measuring leakage current It sets and is exposed to purpose environment temperature.
A kind of method for paying attention to reduction volume leakage current at a certain temperature is the operation voltage reduced at such a temperature. The method that another kind reduces volume leakage current at a certain temperature is to improve the voidage of supercapacitor.And another is dropped The method of low-leakage current is to reduce the load of the energy storage medium 1 on electrode 3.
The various aspects of the embodiment for pure electrolyte and ionic liquid have been disclosed, it should be appreciated that can be with Realize various embodiments.In addition it is possible to implement various technologies.For example, adjustable step, sequence of step etc..
Ii. water/moisture content and removal
The shell 7 of the supercapacitor 10 of sealing can be opened, and storage element 12 is sampled with checked for impurities.Make The water content of electrode from unit 12, isolator and electrolyte is measured with karl fischer method.It is measured three times simultaneously It is averaged.
In general, the method for characterizing pollutant in supercapacitor includes being open shell 7 to obtain its content Object samples and analyzes sample to content.Disclosed technology can be used for supporting the characterization elsewhere herein.
It should be noted that in order to ensure the standard of impurity in supercapacitor and its component (including electrode, electrolyte and isolator) Really measurement can carry out assembly and disassembly in suitable environment (for example, inert environments in glove box).
By reducing the moisture content in supercapacitor 10 (for example, being reduced to the quality relative to electrolyte and impurity With volume lower than 500 parts/million parts (ppm) to lower than 1000ppm), supercapacitor 10 can over the entire temperature range more It efficiently runs, there is the leakage current (I/L) less than 10 amperes/liter in the temperature and voltage range.
In one embodiment, by making the voltages keep constant of supercapacitor 10 in voltage rating (that is, maximum Fixed working voltage) under 72 (72) hours measure leakage current (I/L) at a certain temperature.During this period, temperature is kept It is relative constant at a certain temperature.The leakage current of supercapacitor 10 is measured at the end of surveying range.
In some embodiments, the maximum voltage rated value of supercapacitor 10 is about 4V at room temperature.Raised At a temperature of (for example, more than 210 degrees Celsius) ensure supercapacitor 10 performance method to reduce (that is, reduce) super capacitor The voltage rating of device 10.For example, it is down to about 0.5V, so as to can obtain at relatively high temperatures that voltage rating is adjustable Extended operation duration.
B.The manufacturing method of supercapacitor
In another embodiment, the present invention provides a kind of method for manufacturing supercapacitor, this method packets It includes following steps: the energy storage unit comprising energy storage medium is arranged in shell；With with advanced electrolyte system (AES) shell is filled, so that supercapacitor is grasped within the temperature range of being fabricated at about -40 degrees Celsius to about 210 degrees Celsius Make.
For example, in a specific embodiment, AES includes novel electrolytes entity (NEE), and wherein NEE is suitable for It is used in high temperature ultracapacitor.In certain embodiments, 80 degrees Celsius to about 210 of ultracapacitor configurations Cheng Yue it is Celsius In the temperature range (for example, in about 80 degrees Celsius to about 150 degrees Celsius temperature range) of degree at a temperature of operate.
In one particular embodiment, AES includes highly purified electrolyte, for example, the wherein highly purified electricity Solution matter is suitable for using in high temperature capacitors.In certain embodiments, 80 degrees Celsius of ultracapacitor configurations Cheng Yue is extremely It is operated at a temperature of within the temperature range of about 210 degrees Celsius, for example, in about 80 degrees Celsius to about 150 degrees Celsius of temperature range.
In one particular embodiment, AES includes the electrolyte combination of enhancing, for example, the electrolyte group wherein enhanced Properly used together in both high temperature ultracapacitor and low temperature supercapacitor.In certain embodiments, super capacitor Device is configured to operate at a temperature of within the temperature range of about -40 degrees Celsius to about 150 degrees Celsius, for example, at about -30 degrees Celsius To about 125 degrees Celsius of temperature range.
In one embodiment, manufactured supercapacitor is herein above super capacitor described in part ii Device.Therefore, and as described above, the advantages of being better than the existing electrolyte of known energy storage device in following improve It is one or more: all-in resistance reduces, the long-time stability of resistance improve, total capacitance increases, the long-time stability of capacitor improve, Energy density increases, voltage stability improves, vapour pressure reduces, the temperature range performance of single capacitor is wider, single capacitor The durability temperature of device improves, ease of manufacture improves and cost-effectiveness is improved.
In certain embodiments, setting steps further include pre-processing the component of supercapacitor to reduce water therein Point, the component of supercapacitor include: electrode, isolator, lead, in assembled energy storage unit and shell at least it One.In specific embodiments, pretreatment includes substantially under vacuum in about 100 degrees Celsius to about 150 degrees Celsius of temperature Selected component is heated in range.Pretreatment may include substantially under vacuum in about 150 degrees Celsius to about 300 degrees Celsius of temperature It spends in range and heats selected component.
In certain embodiments, the setting is carried out in substantially inert environment.
In certain embodiments, constitution step is low chemically reactive including selecting relative electrolyte to show for shell Interior surface material can also include in the signal portion of the inside of shell comprising interior surface material.Interior surface material Material can be selected from aluminium, polytetrafluoroethylene (PTFE) (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene copolymer (FEP), second At least one of alkene-TFE copolymer (ETFE) and ceramic material are used as interior surface material.
In certain embodiments, constitution step includes that the shell is formed by multilayer material, for example, wherein by multilayer material It includes that weldable material is arranged on the outside of shell that material, which forms shell,.
In certain embodiments, constitution step includes at least one of shell manufacture lid and ontology.Manufacturing step can To include that will be arranged in the housing comprising the sealing element of insulator and the electrode for electrically isolating from shell.In addition, setting sealing element can wrap Setting glass to metal seal part is included, for example, welding glass-metal seal is to the outer surface of shell.In specific embodiment In, setting sealing element includes setting hemispherical seal.
In certain embodiments, constitution step includes that fill port is arranged in the housing to be used to fill.
In certain embodiments, manufacturing method can also include manufacture energy storage unit, for example, passing through connection energy Storage medium obtains electrode with current-collector；For example, at least one lead is connected to electrode.In certain embodiments, will It includes that at least one reference marker is arranged on electrode that at least one lead, which is connected to the electrode,.In certain embodiments In, it includes that every lead is positioned at each reference marker that at least one lead, which is connected to electrode,.In certain embodiments, even Connecing at least one lead includes removing energy storage medium from current-collector.In certain embodiments, at least one lead is connected Including lead is ultrasonically welded to current-collector.
Electrode can also be obtained by connecting multiple electrode members manufactured by connection energy storage medium with current-collector. Multiple electrodes element can by connecting element is ultrasonically welded to an electrode member current-collector and another electrode member Current-collector connect.
In certain embodiments, manufacture energy storage units include that isolator is arranged between at least two electrodes. It and can also include being aligned each of electrode with isolator.
In certain embodiments, manufacture energy storage unit include encapsulate at least two electrodes and setting therebetween every From device, for example, wherein the encapsulation package includes the storage element for being rolled into storage element and rolling.
In certain embodiments, manufacture energy storage units include that wrap member is arranged on storage element.
In certain embodiments, setting energy storage unit includes that more leads gather together to provide terminal, For example, wherein more leads, which gather together, becomes one group of lead through being aligned including lead to be aligned together to form end Son.In specific embodiments, this method further includes being arranged in wrap member around one group of lead through being aligned；To one group of warp The lead of alignment is folded, or couples the contact of one group of lead through being aligned to shell.In addition, coupling may include weldering It connects one group of lead through being aligned to contact, or one group of lead through being aligned of welding to one of jumper and bridge and is used for coupling It is connected to the contact of shell.
In certain embodiments, manufacturing method can also be including at least one of electric coupling jumper and bridge to shell The contact of body.It in a particular embodiment, can also include substantially by connecing in insulating materials setting inside housings In contact element.
In certain embodiments, manufacturing method can also include that energy storage unit is hermetically sealed in shell, For example, wherein airtightly sealing includes component pulse welding, laser welding, resistance welding and TIG weld by shell one At least one of rise.
In certain embodiments, manufacturing method can also include by least one lid and Ontology Matching to provide shell, For example, its middle cover includes one of recessed lid, dished cover and flat cover.In a particular embodiment, this method can also include removal At least part of multilayer material is in the shell to provide matching.
In certain embodiments, manufacturing method can also include purifying AES.
In certain embodiments, manufacturing method can also include that fill port is arranged in shell to be used to fill, For example, wherein filling includes that AES is filled through to port setting in the housing.In a particular embodiment, this method further include It completes to seal fill port after filling, for example, by compatible material mating into fill port.In a further step, may be used Such material is then soldered to shell.
In certain embodiments, filling step includes vacuumizing on fill port to shell, for example, wherein vacuum is low In about 150 millitorrs, for example, wherein vacuum is below about 40 millitorrs.
In certain embodiments, step is filled in substantially inert environment.
I. manufacturing technology
Furthermore, it is appreciated that certain firm package techniques may be needed to provide efficient energy storage device.Therefore, It has been now discussed with some technologies for assembling.
Once having manufactured supercapacitor 10, being used for that there is seldom leakage current or there is no leakage current and resistance very In few raised high temperature application.Supercapacitor 10 as described herein can be efficiently at about -40 degrees Celsius to about 210 degrees Celsius At a temperature of operate, wherein leakage current under entire operating voltage and temperature range device be lower than 10 amperes/liter (A/L) body It is normalized in long-pending device volume.In certain embodiments, capacitor can be in the temperature across -40 degrees Celsius to 210 degrees Celsius Lower operation.
As general introduction, the method for the supercapacitor 10 of assembling cylindrical shape is provided.With the beginning of electrode 3, once it will Amount storage medium 1 is connected with current-collector 2, that is, has manufactured each electrode 3.Then more leads are coupled in position Each electrode 3.Then multiple electrodes 3 are oriented and are assembled with suitable number of isolator 5 therebetween to form storage element 12.So Afterwards, storage element 12 can be rolled into cylinder, and is fixed with wrap member.In general, then bundle in lead corresponding lead with Form each terminal 8.
Before electrolyte 6 (that is, advanced electrolyte system of the invention) is integrated to supercapacitor 10 (for example, Before or after assembling storage element 12), all parts of supercapacitor 10 can be dried to remove moisture.This can be right Unassembled component (that is, empty capsid 7 and each electrode 3 and each isolator 5) carries out, then to assembled component (example Such as storage element 12) it carries out.
Drying can carry out at elevated temperatures for example in vacuum environment.Once being dried, then can incite somebody to action Storage element 12 is encapsulated in shell 7, without finally sealing or covering.In some embodiments, being encapsulated in has lower than 50 Part/atmosphere of the water of million parts (ppm) in carry out.Then uncapped supercapacitor 10 can be dried again.For example, can be Supercapacitor 10 is dried under vacuum in about 100 degrees Celsius to about 300 degrees Celsius of temperature range.Once it is final dry to complete this It is dry, i.e., shell 7 then can be sealed in the atmosphere for example with the moisture lower than 50ppm.
In some embodiments, it once completing drying process (process of " toasting " can also be referred to as), that is, can be used lazy Environment around property Gas filled members.Example gases include argon, nitrogen, helium and other gases for showing similarity (and combinations thereof).
In general, fill port (perforation in 7 surface of shell) is included in shell 7, or can add later.One Denier supercapacitor 10 has been filled with electrolyte 6 (that is, advanced electrolyte system of the invention), and fill port can be closed. Being closed fill port can be for example by being welded into fill port or welding for material (for example, metal compatible with shell 7) It is completed on fill port.In some embodiments, fill port can be temporarily closed before filling, be allowed to Supercapacitor 10 is moved on in another environment, for subsequent open, filling and closure again.But as discussed herein, recognize For dry in identical environment and filling supercapacitor 10.
Many methods can be used use desired amount advanced electrolyte system filling shell 7.In general, to filling out The control for filling technique can provide the raising, the reduction of equivalent series resistance (ESR) and the limited waste of electrolyte of capacitor Deng.Vacuum fill method is provided as the technology for filling shell 7 and wetting storage element 12 with electrolyte 6 one is non- Limitative examples.
However, it is initially noted that can measure to ensure to pollute any material of the component of supercapacitor 10 It is all clean, compatible and dry.As convention, it is believed that carry out " good health " with ensure assembling process and Component does not introduce pollutant into supercapacitor 10.
Under " vacuum method ", by receptacle on shell 7 around fill port.Then by a certain amount of electrolyte 6 (that is, advanced electrolyte system of the invention) is placed in a reservoir in the environment substantially free of oxygen and water (that is, moisture). Then it vacuumizes, to extract any air out from shell, and thereby electrolyte 6 is pumped into shell 7 simultaneously in this context.So Afterwards if necessary, ring around can be refilled with inert gas (such as some combinations of argon, nitrogen etc. or inert gas) Border.Supercapacitor 10 can be checked to check whether the electrolyte 6 for being pumped into desired amount.It can according to need the repetition mistake Journey, until there is the electrolyte 6 of desired amount in supercapacitor 10.
It in some embodiments, can be with after filling electrolyte 6 (that is, advanced electrolyte system of the invention) Make material mating to fill port to seal supercapacitor 10.For example, can be can phase with shell 7 and electrolyte 6 for the material The metal of appearance.In one embodiment, material press-fit (force fit) is entered into fill port, in fill port mainly into " cold welding " of row plug.In a particular embodiment, as further discussed herein, press-fit can be aided with other welding skills Art.
In general, the assembling of shell is often related to being arranged in storage element 12 in ontology 20 and with advanced electrolysis plastid System's filling ontology 20.It can carry out another drying process.Exemplary drying includes the heating usually under decompression (for example, vacuum) Ontology 20 with storage element 12 and advanced electrolyte system therein.Once having carried out sufficiently (optionally) drying, i.e., It can carry out final assembling steps.In a final step, the internal electrical connection of manufacture, installs lid 24, and for example, by welding lid 24 Ontology 20 is connected to utilize airtightly seal body 20 of lid 24.
In some embodiments, the manufacture of at least one of shell 7 and lid 24 is at including the material containing multiple layers.Example Such as, first material layer may include aluminium, and second material layer is stainless steel.In this embodiment, stainless steel is coated on aluminium, to mention For showing the combined material of desired metallurgical property.That is, aluminium is exposed in embodiment provided in this article The inside of energy storage unit (that is, shell), and stainless steel is externally exposed.In this way, the advantageous electrical property of aluminium is enjoyed, It is constructed simultaneously dependent on the structural property (and metallurgical property, i.e. weldability) of stainless steel.When being deemed appropriate, multilayer material It may include additional layer.Advantageously, this is provided stainless steel welded to this relatively simple welding procedure of stainless steel.
When the material for constructing ontology 20 includes aluminium, designer or producer think any type of aluminum or aluminum alloy It is all suitable (it is all broadly referred to as " aluminium " herein).Various alloys, lamilate etc. can be arranged (for example, Cladding) on aluminium (aluminium being exposed to inside ontology 20).Can be used additional material (such as structural material or electrical isolation material Material, such as some based on the material of polymer) supplement ontology and/or shell 7.The material on aluminium, which is arranged in, can equally pass through Designer or producer think suitably to select.
The use of aluminium is not inevitable or required.In short, the selection of material can be provided to use designer, manufacture Person or user etc. think suitable any material.Many factors can be considered, such as interact with the electrochemistry of electrolyte 6 Reduction, structural property, cost etc..
The embodiment for showing the supercapacitor 10 of smaller size smaller can be manufactured with prism-shaped form factor, so that super The electrode 3 of capacitor 10 opposite to each other, at least one electrode 3 and glass to metal seal part interior contact, another electrode and outer Shell or glass to metal seal part interior contact.
It can be by the way that several storage elements (such as several gluey are welded are connected together) combination be made in a shell 7 Its electrically in parallel or series connection is obtained to expand the volume of particular super capacitor 10.
In many a embodiments, it might be useful to be used together multiple supercapacitors 10 to provide power supply.In order to mention For reliably operating, each supercapacitor 10 can be tested before the use.In order to carry out various types of tests, Each supercapacitor 10 can be used as single unit, test with attached 10 serial or parallel connection of multiple supercapacitors.Make The ESR of connection can be reduced with the different metal connected by multiple technologies (such as passing through welding) and improves the intensity of connection. Presently describe the various aspects of the connection between supercapacitor 10.
In some embodiments, supercapacitor 10 includes two contacts.The two contacts are that glass-metal is close The entire remainder of sealing pin (that is, feedthrough component 19) and shell 7.When multiple supercapacitors 10 are connected in series, usually It is expected that coupling the mutual disjunctor (in the case where cylindrical housings 7) between 7 bottom of shell, the distance for making to obtain inner lead is minimum Change, therefore there is minimum resistance.In these embodiments, the opposite end of mutual disjunctor is usually coupled to glass to metal seal part Pin.
For mutual disjunctor, common welds types is related to using tip resistance welding machine in parallel.Welding can be by right Mutually the end of disjunctor and direct solder interconnections body are manufactured to pin on neat pin.Mutual disjunctor will be improved using multiple weldments Intensity and connection between pin.In general, when being soldered to pin, the terminal end shape of mutual disjunctor is set with well With pin, to ensure there is no the excess material that will lead to short circuit for overlapping on pin.
Opposite tip resistance welding machine can be used, interconnection piece is soldered to pin, while ultrasonic bonder can be used The bottom of solder interconnections part and shell 7.When included metal is compatible, soldering tech can be used.
For the material used in the mutual disjunctor, the material of the common type for mutual disjunctor is nickel.Due to nickel with it is stainless Steel welding is good and has firm interface, it is possible to use nickel.Other metals and alloy can be used to replace nickel, such as To reduce the resistance in mutual disjunctor.
In general, selected for interconnecting phase of the material because of itself and the material in the material and shell 7 in pin of body Capacitive selects.Illustrative material includes copper, nickel, tantalum, al and ni copper clad.Other metals that can be used include silver, gold, Brass, platinum and tin.
In some embodiments, such as in the case where wherein pin (that is, feedthrough component 19) is made of tantalum, mutual disjunctor can benefit It is connected with intermetallic metal, such as by using short bridge.A kind of connection of exemplary bridged device includes tantalum item, by using Opposite tip resistance welding machine improves to weld aluminium/copper/nickel bar to bridge.Then, it is welded using parallel resistance welding machine Tantalum item is to tantalum pin.
The bridge is also used on the contact of shell 7.For example, can be by a piece of nickel resistance welding to the bottom of shell 7 Portion.Then copper bar can be ultrasonically welded to nickel bridge.The technology helps to reduce the resistance of cell interconnection body.Use difference Metal can reduce the ESR of mutual disjunctor between series unit for each connection.
Thus the steady supercapacitor 10 that can be used for hot environment (that is, up to about 210 degrees Celsius) has been described Various aspects there is presently provided and/or define some other aspects.
Perhaps multiple material can be used for constructing supercapacitor 10.If oxygen and moisture is discharged and to prevent electrolyte 6 Evolution, then the integrality of supercapacitor 10 is necessary.To achieve it, seam weld and any other seal point should meet Air-tightness standard under the desired temperature range for operation.In addition, selected materials should be compatible with other materials, the material Such as it can be used for preparing the ionic liquid and solvent of advanced electrolyte system.
In some embodiments, feedthrough component 19 is formed by metal, at least one of for example following material of the metal: KOVARTM(trade mark of Carpenter Technology Corporation of Reading, Pennsylvania, Middle KOVAR is vacuum fusion, iron-nickel-cobalt, low-expansion alloy, and chemical composition control ensures accurate equal in narrow boundary One hot expansion property), alloy 52 (suitable for by the dilval of glass and ceramic seal to metal), tantalum, molybdenum, niobium, tungsten, no Become rusty steel 446 (providing well tolerable ferrite, non-heat-treatable stainless steel to high temperature corrosion and oxidation) and titanium.
Using glass to metal seal part ontology above-mentioned can by 300 series stainless steels (such as 304,304L, 316 and 316 alloys) it is made.The ontology can be also made by metal is for example at least one of following: a variety of nickel alloys, such as Yin Kenei Your inconel (Inconel) (austenite nickel chromium triangle base superalloy family, to be well suited in the extreme of experience pressure and heat The resistance to oxidation and corrosion-resistant material of environment) and Hastelloy (Hastelloy) (the corrosion resistant metal alloy of height comprising Nickel and the molybdenum of different weight percentage, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminium, carbon and tungsten).
The insulating materials between feedthrough component 19 and surrounding ontology in glass to metal seal part is usually glass, Each manufacturer that group becomes sealing element is all, and depends on whether sealing element under elevated pressure or match.Other insulation Material can be used in glass to metal seal part.For example, multiple polymers are available in the seal.Therefore, term " glass-gold Category " sealing element is the description of seal type, is not intended to imply that sealing element must include glass.
The shell 7 of supercapacitor 10 can be made of such as type 304,304L, 316 and 316L stainless steel.They are also It can construct from some aluminium alloys, such as 1100,3003,5052,4043 and 6061, but not limited to this.It can be used a variety of more Layer material, and may include for example coating to the aluminium of stainless steel.Other workable non-limiting compatible metals include platinum, Gold, rhodium, ruthenium and silver.
The specific embodiment for the glass to metal seal part having been used in supercapacitor 10 includes two distinct types of glass Glass-metal seal.The first is located at the SCHOTT of New York, United States Elmes Ford (Elmsford, NY) from US.It should Embodiment uses stainless steel pin, glass insulator and stainless steel ontology.Second glass to metal seal part comes from Ohio The HERMETIC SEAL TECHNOLOGY of state Cincinnati (Cincinnatti, OH).Second embodiment is drawn using tantalum Foot, glass insulator and stainless steel ontology.Different size of many a embodiments can be provided.
The other embodiments of glass to metal seal part include the embodiment using aluminum seals and aluminium ontology.And Another embodiment of glass to metal seal part includes using epoxides or other insulating materials (such as ceramics or silicon) Aluminum seals.
The many aspects of being permitted of glass to metal seal part can according to need to configure.For example, the size of shell and pin, The material of pin and shell can according to need and change.The pin can also be pipe or solid pin, and cover at one There are multiple pins in object.Although the material of the most common type for pin is stainless steel alloy, copper core stainless steel, molybdenum, platinum- Iridium, various nickel-ferro alloys, tantalum and other metals, but some very gauge materials (such as aluminium) can be used.Shell is usually by stainless Steel, titanium and/or various other materials are formed.
Various tightening technologies can be used in the combination of supercapacitor 10.For example, a variety of welderings can be used for welding Connection technology.Following is the exemplary lists of welds types and a variety of purposes that each type of welding can be used.
Ultrasonic welding can be used for: welding aluminium contact pin to current-collector；It welds contact pin to bottom and coats covering；Weld jumper Contact pin is to the cladding bridge for being connected to glass to metal seal part pin；And mucilage binding volume item is welded together.Pulse or Resistance welding can be used for: the bottom of welding lead to container or to pin；Welding lead is to current-collector；Jumper is welded to packet Cover bridge；Welding coats bridge to terminal 8；Welding lead is to bottom covers etc..Laser welding can be used for: welding is stainless Steel covering is to rustless steel container；Soldering stainless steel bridge is to stainless steel glass-metal seal pin；And welding plug To fill port etc..TIG weld can be used for: sealed aluminum covering to aluminium vessel；With welding aluminum seals in-position etc..Cold welding Connecing and (metal being forced together with very high power) can be used for fitting into fill port by forcing aluminium ball/nail and sealing filled end Mouthful etc..
Ii. the certain Favourable implementations manufactured
Certain Favourable implementations are provided herein below, are not intended to be limiting.
In a specific embodiment, and referring to Figure 29, the component of exemplary electrode 3 is shown.In the embodiment In, electrode 3 will act as negative electrode 3 (still, this is specified and is arbitrary and is served only for referring to).
It can be noted that at least in this embodiment such as from explanation, the general specific energy storage medium of isolator 51 (and Current-collector 2) length it is longer and width is wider.By using biggish isolator 5, providing prevents negative electrode 3 and positive electricity The protection of the short circuit of pole 3.The use of additional materials is also that lead and terminal 8 provide better electric protection in isolator 5.
Referring now to Figure 30, the side view of an embodiment of storage element 12 is provided.In this embodiment, it is layered The energy storage medium 1 of stacking includes the first isolator 5 and the second isolator 5, so that electrode 3 assembles in rolls in storage element 12 It is electrically isolated when the storage element 23 of system.It should be noted that for electrode 3 and the sub-assembly of supercapacitor 10, term " just " and " negative " is only arbitrary, and when configuration is in supercapacitor 10 and stores charge wherein with reference to functionality.It is logical Often the convention suitable for this field is not meant to that charge has stored before assembly, or means except offer Different electrodes Identification physically other than any other aspect.
Before winding storage element 12, negative electrode 3 and positive electrode 3 are aligned relative to each other.Being aligned to for electrode 3 is super Grade capacitor 10 provides more best performance, this is because path length when with highest degree of registration, for ion transmission It is general minimum.In addition, excessive isolator 5 is not included, and therefore supercapacitor by providing high degree of registration 10 efficiency is not damaged.
Referring now to Figure 31, an embodiment of storage element 12 is shown, wherein electrode 3 is rolled into the storage list rolled Member 23.One of isolator 5 exists and as the outermost layer of storage element 12 by the inner part of energy storage medium 1 and shell 7 It separates.
The polarity of most external electrode and ontology 20 in the storage element 23 rolled can be matched using " polarities match " Polarity.For example, in some embodiments, packaging part of the negative electrode 3 in the compact package that provides the storage element 23 rolled In outermost.In these embodiments, another degree of protection of prevention short circuit is provided.That is, being coupled in negative electrode 3 When to ontology 20, negative electrode 3 is as most external electrode arrangement in the storage element 23 rolled.Therefore, if isolator 5 fails (such as being caused by the mechanical wear as caused by the vibration of supercapacitor 10 during use), then supercapacitor 10 will not It can fail because of the short circuit between the most external electrode and ontology 20 in the storage element 23 rolled.
Each embodiment for the storage element 23 rolled, reference marker 72 at least can be in isolators 5.With reference to Label 72, which will be used to provide, is located in each electrode 3 for lead.In some embodiments, lead is provided by calculating Positioning.For example, passing through the overall thickness of the internal diameter and combined isolator 5 and electrode 3 that consider gluey volume, it can be estimated that every is drawn The placement location of line.However, practice display, more efficient and more effective using reference marker 72.Reference marker 72 may include for example Slit in the edge of isolator 5.
In general, each new spec to storage element 12 uses reference marker 72.That is, because storage element 12 new spec may require the different-thickness (in existing embodiment) of wherein at least one layer, so existing reference marker Using may at least some inaccuracy.
It is rolled onto general, reference marker 72 is presented as to pass through from its center up to surrounding single radial line.Therefore, when When lead is installed along reference marker 72, every lead will be aligned (as shown in Figure 10) with remaining lead.However, working as storage element When 12 not rolling (wherein storage element 12 is volume or the embodiment that will become volume), it is believed that reference marker 72 is multiple marks Remember (as shown in figure 32).As convention, regardless of the label of storage element 12 embodiment or appearance why, it is believed that for combining The identification of the position of lead is related to the determination of " reference marker 72 " or " one group of reference marker 72 ".
Referring now to Figure 32, once establishing reference marker 72 (such as by marking the storage element 12 rolled), that is, mention The installation site (that is, being described by reference marker 72) for installing every lead is supplied.Once it is determined that each installation site, For any given construction specification of storage element 12, the relative position in each installation site is for the specific of storage element 12 It is repeated for the other example of construction.
In general, every lead is coupled to each current-collector 2 in storage element 12.In some embodiments, current collection Both device 2 and lead are made of aluminum.In general, lead, which is coupled to current-collector 2, crosses over width W, however lead can coupling widths W Only a part.Coupling can be realized for example, by lead is ultrasonically welded to current-collector 2.In order to realize coupling, can go Except at least some energy storage mediums 1 (in due course), so that every lead is suitably connected with current-collector 2.It is being deemed appropriate When, other can be carried out and prepare and adjust to provide coupling.
It in certain embodiments, may include opposite reference marker 73.That is, with identical as reference marker 72 Mode provide, can make one group of opposite reference marker 73 with consider for opposite polarity lead installation.Namely It says, reference marker 72 can be used for installing lead to first electrode 3, such as negative electrode 3, while opposite reference marker 73 can be used for Lead is installed to positive electrode 3.In the embodiment that the storage element 23 wherein rolled is cylindrical, opposite reference marker 73 The opposite side of energy storage medium 1 is set, and from 72 vertical misalignment of reference marker (as depicted).
Pay attention in Figure 32, both reference marker 72 and opposite reference marker 73 are shown as being arranged on single electrode 3. That is, Figure 29 depicts space (that is, straight line) relationship for being served only for illustrating reference marker 72 Yu opposite reference marker 73 Embodiment.This does not imply that positive electrode 3 and negative electrode 3 share energy storage medium 1.However, it should be noted that referring to wherein In the case that label 72 and opposite reference marker 73 are rolled by the arrangement of storage element 12 and then label isolator 5, with reference to mark Note 72 and opposite reference marker 73 are may be provided in really on single isolator 5.However, in fact, reference marker 72 and opposite Reference marker 73 in only one group can be used for installing for the lead to fixed electrode 3.That is, it is recognized that Tu32Suo Another layer of the energy storage medium 1 of the embodiment of description another electrode 3 (it will have opposite polarity) to be utilized is mended It fills.
As shown in figure 33, aforementioned package technique obtains including at least one set of storage element 12 for being aligned lead.When will roll Storage element 23 be coupled to cathode contact part 55 and positive contact 56 for the moment, the lead 91 of first group of alignment is that especially have , and one group of opposite alignment lead 92 provides energy storage medium 1 being coupled to opposite contact (55,56).
The storage element 23 rolled can be surrounded by wrap member 93.Wrap member 93 can be real in many a embodiments It is existing.For example, wrap member 93 can be provided as KAPTONTM(it is the polyamides Asia developed by the DuPont of Delaware State Wilmington to band Amine film) or PTFE tape.In this embodiment, KAPTONTMBand surrounds and is adhered to the storage element 23 rolled.Wrap member 93 can It is provided as without adhesive, such as slides into the close-fitting wrap member 93 on the storage element 23 rolled.Wrap member 93 can be with Bag is more shown as, such as is generally involved in the bag of the storage element 23 (for example, encapsulation piece 73 discussed above) rolled. In in these embodiments some, wrap member 93 may include the material as shrink film packaging (shrink-wrap), from And provide efficient physics (in some embodiments, chemical) encapsulating of the storage element 23 rolled.In general, wrap member 93 by not interfering the material of the electrochemical function of supercapacitor 10 to be formed.For example, wrap member 93 can also provide as needed Partial covering, to facilitate the storage element 23 that insertion rolls.
In some embodiments, negative wire and positive wire are located at the opposite side of the storage element 23 rolled (in glue In the case where the storage element 23 that shape roll rolls, the lead of negative polarity and the lead of positive polarity can be completely opposite).It is general and Speech, the opposite side for carrying out for the lead of the lead of negative polarity and positive polarity being arranged in the storage element 23 rolled is to help to construct The storage element 23 and the improved electric isolution of offer rolled.
It in some embodiments, i.e., will be in the lead of multiple alignment 91,92 once assembling the lead 91,92 of alignment Each be held together (original position) so that shrink film packaging (not shown) may be provided at multiple alignment lead 91,92 week It encloses.In general, shrink film packaging is formed by PTFE, but any compatible material can be used.
In some embodiments, once shrink film wrap member is arranged in around the lead 91 of alignment, i.e., by alignment Lead 91 is folded into the shape assumed when assembling supercapacitor 10.That is, referring to Figure 34, it is seen that the lead of alignment is assumed For Z-shaped.It, can be with heat shrink film after assigning " Z- folding " and application shrink film packaging for the lead 91,92 of alignment Packaging is activated by other methods, so that shrink film packaging collapses into the position around the lead 91,92 of alignment.Therefore, In some embodiments, it can strengthen and protect the lead 91,92 of alignment by wrap member.When by energy storage medium 1 When being coupled to the feedthrough component 19 being arranged in lid 24, Z- fold using particularly useful.
Furthermore it is possible to implement for by the lead 91,92 (that is, each terminal 8) that every group is aligned be coupled to each contact 55, 56 other embodiments.For example, in one embodiment, middle leads being coupled to one of feedthrough component 19 and shell 7, are made It must facilitate the lead 91,92 being aligned with each group coupling.
In addition, material therefor can be selected according to for example following property: reactivity, dielectric radio, fusing point, with other materials Adhesiveness, weldability, coefficient of friction, cost and other such factors.The combination that material can be used (such as is layered , mixing or combine by other means) desired property is provided.
Iii. particular super Capacitor Embodiments
Some physics aspects of exemplary supercapacitor 10 of the invention have been illustrated below.It should be noted that in the following table, art Language " contact pin " generally refers to " lead " as discussed above；Term " bridge " and " jumper " further relate to some aspects of lead (for example, bridge may be coupled to feedthrough component, or " pin ", while jumper can be used for coupled to bridge to contact pin or lead). It can help to packaging technology using a variety of connections, and utilize certain package techniques.For example, bridge can be with laser welding or electricity Welding resistance is connected to pin, and is coupled to jumper with ultrasonic welding.
Table 5
Table 6
Table 7
Table 8
Figure 35 to Figure 38 is the figure for describing the performance of these exemplary supercapacitors 10.Figure 35 and Figure 36 depicts super Capacitor 10 is in 1.75 volts and 125 degrees Celsius of performance.Figure 37 and Figure 38 depicts supercapacitor 10 and takes the photograph in 1.5 volts and 150 The performance of family name's degree.
In general, supercapacitor 10 can use under a variety of environmental conditions and demand.For example, end voltage can be About 100mV to 10V.Environment temperature can be about -40 degrees Celsius to+210 degrees Celsius.Typical high ambient temperatures are taken the photograph for+60 Family name's degree is to+210 degrees Celsius.
Figure 39 to Figure 43 is the other figure of the performance of depicted example supercapacitor 10.In these embodiments, surpass Grade capacitor 10 is the unit (that is, shell) of closure.Supercapacitor is recycled 10 times, is charged and discharged as 100mA, charges to 0.5 volt, resistance is measured, is discharged to 10mV, 10 seconds is stood, then recycles again.
Table 11 and 12 provides the comparison performance data of the embodiment of supercapacitor 10.Multiple behaviour are had collected as shown Performance data under the conditions of work.
Table 9
Compare performance data
Table 10
Compare performance data
Therefore, provided in table 9 and table 10 statistics indicate that introduction herein makes it possible to realize supercapacitor in pole Performance under the conditions of end.Therefore, manufactured supercapacitor can for example show the unit volume below about 1mA/ milliliters Leakage current, and in 500 hours below about 100% ESR increase (it is maintained at the voltage below about 2V and takes the photograph below about 150 At a temperature of family name's degree).Because can be accepted or rejected between a variety of requirements (for example, voltage and temperature) of supercapacitor, institute It is adjustable to adapt to particular needs the rated performance (for example, increment rate etc. of capacitor, ESR) of supercapacitor can be managed It wants.Pay attention to giving the generally conventional definition of " rated performance " referring to aforementioned, in view of the parameter of description operating condition Value.
Figure 35 to Figure 43, which is depicted, to be had comprising 1- butyl -1- crassitudeWith showing for the AES of four cyano borate Example property supercapacitor in the range of 125 degrees Celsius to 210 degrees Celsius at a temperature of performance.
Figure 44 A and 44B, which are depicted, to be had comprising 1- butyl -1- methyl piperidineBis- (trifluoromethyl sulfonyl) imines The performance data of the exemplary supercapacitor of AES.
Figure 45 A and 45B, which are depicted, to be had comprising three hexyl myristylsThe AES of bis- (trifluoromethyl sulfonyl) imines Exemplary supercapacitor performance data.
Figure 46 A and 46B depict exemplary with the AES comprising bis- (trifluoromethyl sulfonyl) imines of butyl trimethylammonium The performance data of supercapacitor.
Figure 47 A and 47B, which are depicted, to be had comprising 1- butyl -1- crassitudeWith showing for the AES of four cyano borate Performance data of the example property supercapacitor under 125 degrees Celsius.
Figure 48 A and 48B and Figure 49, which is depicted, to be had comprising propylene carbonate and 1- butyl -1- crassitudeWith four The propylene carbonate of the performance data of the exemplary supercapacitor of the AES of the mixture of cyano borate, the mixture presses body Product is calculated as about 37.5%；Capacitor is operated at 125 degrees Celsius (Figure 48 A and 48B) and at -40 degrees Celsius (Figure 49).It is surveyed The another exemplary supercapacitor of examination includes containing 1- butyl -3- methylimidazoleThe AES of tetrafluoroborate.
The another exemplary supercapacitor tested includes containing 1- butyl -3- methylimidazoleBis- (trifluoromethyl sulphurs Acyl group) imines AES.
The another exemplary supercapacitor tested includes containing 1- ethyl-3-methylimidazoleTetrafluoroborate AES。
The another exemplary supercapacitor tested includes containing 1- ethyl-3-methylimidazoleFour cyano borate AES。
The another exemplary supercapacitor tested includes containing 1- hexyl -3- methylimidazoleFour cyano borate AES。
The another exemplary supercapacitor tested includes containing 1- butyl -1- crassitudeBis- (trifluoromethyls Sulfonyl) imines AES.
The another exemplary supercapacitor tested includes containing 1- butyl -1- crassitudeThree (pentafluoroethyl groups) The phosphatic AES of trifluoro.
The another exemplary supercapacitor tested includes containing 1- butyl -1- crassitudeFour cyano borate AES.
The another exemplary supercapacitor tested includes containing 1- butyl -3- methylimidazoleFluoroform sulphonate AES。
The another exemplary supercapacitor tested includes containing 1- ethyl-3-methylimidazoleFour cyano borate AES。
The another exemplary supercapacitor tested includes containing 1- ethyl-3-methylimidazoleWith 1- butyl -1- first Base pyrrolidinesWith the AES of four cyano borate.
The another exemplary supercapacitor tested includes containing 1- butyl -1- crassitudeWith four cyano boric acid The AES of salt and ethylisopropyl base sulfone.
The measurement of (table 9 such as herein and elsewhere shown in) follows commonly known side it should be noted that capacitor and ESR Method.The technology for measuring capacitor is considered first.
Capacitor can measure in many ways.A kind of method is related to voltage shown in monitoring capacitor terminal, while from super Capacitor extracts the current known (during " electric discharge ") or current known is supplied to the supercapacitor (during " charging ").More Specifically, it can use the fact that ideal capacitor follows following equation:
I=C*dV/dt,
Wherein I indicates charging current, and C indicates that capacitor, dV/dt indicate the time-derivative of ideal capacitor voltage V.Desired electrical Container is such capacitor, internal resistance zero, and its capacitor is not dependent on voltage etc..When charging current Iconst, electricity Press V and time in a linear relationship, therefore dV/dt may be calculated the slope of the line or as Δ V/ Δ T.But this method The approximation and voltage difference (ESR reduction) usually provided by the effective series resistance of capacitor should calculate or measure electricity Consider when appearance.Effective series resistance (ESR) generally can be in capacitor consumption or the approximate lamped element of other effects (lumped element).Capacitor line is usually from the ideal capacitor of the resistor in series with resistance value equal to ESR Circuit model.In general, this results in the good approximations with true capacitor behavior.
It is substantially that do not depend on voltage and charge or discharge are substantially in internal resistance in a kind of method for measuring capacitor In the case where fixation, it can largely ignore the influence of ESR reduction.In this case, ESR reduction can be approximated to be often Number, and subtracted naturally from the constant current charging or during discharging in the calculating of voltage change.Then, voltage change base Reflect the variation of stored charge on capacitor in sheet.Therefore, the variation of voltage can be used as the instruction of capacitor by calculating.
For example, during constant current discharge, it is known that constant current I.Voltage change during measurement electric discharge, Δ V, measured Time interval Δ T obtains the approximation of capacitor by current value I divided by Δ V/ Δ T ratio.When the unit of I is ampere, the list of Δ V Position is volt, and when the unit of Δ T is second, capacitor result will be as unit of farad.
As for the assessment of ESR, the effective series resistance (ESR) of supercapacitor can also measure in many ways.One Kind method is related to monitoring the voltage shown at capacitor terminal, and extracts the known electric (during " electric discharge ") from supercapacitor Stream, or current known is supplied to the supercapacitor (during " charging ").More specifically, can use ESR follow it is following The fact that equation:
V=I*R,
Wherein I indicates that, effectively by the electric current of ESR, R indicates the resistance value of ESR, and V indicates the electricity provided by ESR Pressure difference (ESR reduction).ESR generally can be in supercapacitor consumption or the approximate lamped element of other effects.It is super Capacitor line is usually from the circuit model of the ideal capacitor of the resistor in series with resistance value equal to ESR.It is general and Speech, this results in the good approximations with true capacitor behavior.
In a kind of method for measuring ESR, it can start from the capacitor in static state (without large current charge or electric discharge Capacitor) extract discharge current.Cause due to the variation of charge stored by capacitor that wherein capacitor is shown Voltage change be less than measured voltage change time interval during, measured voltage change substantially reflects capacitor ESR.Under these conditions, the instantaneous voltage variation that capacitor is showed can be used as the instruction of ESR by calculating.
For example, extracting discharge current once from capacitor, instantaneous voltage can be showed during measuring interval delta T Changes delta V.As long as the capacitor C of capacitor, is discharged by current known I, obtain being less than measured electricity during measuring interval delta T Press the voltage change of changes delta V, so that it may by the Δ V during time interval Δ T divided by discharge current I, to obtain the close of ESR Seemingly.When the unit that the unit of I is ampere and Δ V is volt, ESR result will be as unit of ohm.
Both ESR and capacitor may depend on environment temperature.Therefore, measurement of correlation can need user by supercapacitor 10 Specific purpose environment temperature is undergone during measurement.
The performance requirement of leakage current is generally limited by the pervasive environments condition in specific application.For example, for volume Practical limitation for the capacitor of 20mL, leakage current can be brought down below 100mA.
The nominal value of normalized parameter can be special multiplied by or divided by normalize by normalized parameter (for example, volume leakage current) (for example, volume) is levied to obtain.For example, volume leakage current is 10mA/ cubic centimetres and volume is 50 cubic centimetres super The nominal leakage current of capacitor is the product 500mA of volume leakage current and volume.Meanwhile volume ESR is 20 milliohms cube li The nominal ESR for the supercapacitor that rice and volume are 50 cubic centimetres is volume ESR and 0.4 milliohm of quotient of volume.
Iv. to the inspection of the filling effect of the supercapacitor including AES
In addition, constructing two classes of supercapacitor 10 to show how fill method influences supercapacitor 10 As embodiment.One is in antivacuum lower filling, the other is filling under vacuum.Two embodiment party are provided in table 11 The electrical property of case.By repeating such measurement, it is noted that realized by applying vacuum to fill supercapacitor 10 Improved performance.It has been determined that generally speaking, it is desirable to the pressure reduction in shell 7 is more particularly dropped to 150 millitorrs are below about Down to below about 40 millitorrs.
Table 11
The comparison performance of fill method
Parameter (in 0.1V) Under antivacuum Under vacuum Deviation
ESR@45°Φ 3.569 ohm 2.568 ohm (- 28%)
Capacitor@12mHz 155.87mF 182.3mF (+14.49%)
Phase@12mHz 79.19 degree 83 degree (+4.59%)
The effect of in order to evaluate vacuum filling technology, tests two different packed units (pouch cell). The packed unit includes two electrodes 3, and each electrode 3 is based on carbonaceous material.Each electrode 3 is positioned opposite and faces that This.Isolator 5 is arranged between the electrode 3 to prevent short circuit, and all immerses all in electrolyte 6.It is outer using two Portion's contact pin provides four measurement points.Isolator 5 used is polyethylene separator 5, and the total volume of the unit is about 0.468ml。
C.Use the method for supercapacitor
The present invention also aim to any usage including energy storage device (for example, supercapacitor) described herein and Whole usages.This includes directly using supercapacitor, or supercapacitor is used in other devices for any application. Such use is intended to include manufacture, sells or provides supercapacitor to user.
For example, in one embodiment, using high temperature rechargeable energy accumulating device the present invention provides a kind of (HTRESD) method of (for example, supercapacitor), this method comprises the following steps: obtaining includes advanced electrolyte system (AES) HTRESD；HTRESD is recycled by being alternately charged and discharged to HTRESD at least twice, while maintaining HTRESD two The voltage at end so that HTRESD show 0.01W/ rise to 150kW/ liter initial spike power density so that HTRESD about- It is operated under environment temperature within the temperature range of 40 degrees Celsius to about 210 degrees Celsius.In certain embodiments, temperature range exists Between about -40 degrees Celsius to about 150 degrees Celsius；Between about -40 degrees Celsius to about 125 degrees Celsius；At about 80 degrees Celsius to about Between 210 degrees Celsius；Between about 80 degrees Celsius to about 175 degrees Celsius；Between about 80 degrees Celsius to about 150 degrees Celsius；Or Between -40 degrees Celsius to about 80 degrees Celsius.In certain embodiments, HTRESD shows about 0.01W/ and rises to about 10kW/ The initial spike power density risen, for example, being risen between about 5kW/ liter in about 0.01W/, for example, being risen to about in about 0.01W/ Between 2kW/ rises.
In another embodiment, the present invention provides a kind of methods using supercapacitor, this method comprises: obtaining It obtains according to claim 1 to supercapacitor described in any one of 85, wherein the supercapacitor shows to be maintained at about Body when under the essentially constant temperature between 100 degrees Celsius to about 150 degrees Celsius below about 10mA/ cubic centimetres Product leakage current (mA/ cubic centimetres)；Super capacitor is recycled with by being alternately charged and discharged to supercapacitor at least twice Device, while the voltage at supercapacitor both ends is maintained, so that supercapacitor is between about -40 degrees Celsius to about 210 degrees Celsius In the range of essentially constant temperature under keep when use 20 hours after show below about 300% ESR increase.At certain In a little embodiments, temperature range is between about -40 degrees Celsius and about 150 degrees Celsius；It is Celsius in about -40 degrees Celsius and about 125 Between degree；Between about 80 degrees Celsius and about 210 degrees Celsius；Between about 80 degrees Celsius and about 175 degrees Celsius；It is Celsius about 80 Between degree and about 150 degrees Celsius；Or between about -40 degrees Celsius and about 80 degrees Celsius.
In another embodiment, the present invention provides one kind provides high temperature rechargeable energy stores dress to user The method set, this method comprises: selection includes the high temperature rechargeable energy storage means of advanced electrolyte system (AES) (HTRESD), the high temperature rechargeable energy storage means are being exposed to about -40 degrees Celsius to about 210 degrees Celsius of temperature model Shown when enclosing interior environment temperature 0.01W/ rise to 100kW/ liter initial spike power density and at least 1 hour, for example extremely Few 10 hours, for example, at least 50 hours, for example, at least 100 hours, for example, at least 200 hours, for example, at least 300 hours, for example At least 400 hours, for example, at least 500 hours, for example, at least 1000 hours durable phases；With deliver storage device so as to being made User provides HTRESD.
In another embodiment, the present invention provides one kind provides high temperature rechargeable energy storage means to user Method, this method comprises: obtain according to claim 1 to Celsius at about -40 degrees Celsius to about 210 described in any one of 85 The volume leakage current below about 10mA/ cubic centimetres is shown when keeping under the essentially constant temperature between degree The supercapacitor of (mA/ cubic centimetres)；With deliver storage device so that give user provide HTRESD.
It is incorporated by reference into
It is by quoting that the full content of all patents referred to herein, the patent application of announcement and other references is all bright Really it is fully incorporated herein herein.
Equivalent
Those skilled in the art will appreciate that or can only determine specific system described herein using only routine experiment The many equivalents of journey.Such equivalent is deemed within the scope of the present invention and is covered by appended claims.In addition, The range of any numerical value presented herein or letter be intended to include those ranges upper limit value and lower limit value.In addition, at least In one embodiment, what any list or grouping were intended to indicate that listed independent embodiments writes a Chinese character in simplified form or facilitates mode；Thus, The each part for being considered as list is individual embodiment.
It should be appreciated that introduction herein is exemplary only and does not limit the invention.In addition, this field It will be recognized that other component, construction, arrangement may be implemented while keeping within the scope of the present invention Deng.For example, the preparation of layer, electrode, lead, terminal, contact, feedthrough component, lid etc. can be with embodiments disclosed herein not Together.In general, the component of supercapacitor and using electrode supercapacitor design and/or application only designed by system Person, producer, operator and/or user needs and appear in demand limitation in any specific situation.
Furthermore, it is possible to include and use various other components for providing the aspect of introduction herein.For example, can be with Other implementation in the range of instructing herein is provided using the redundancy of the combination of additional material, material and/or material Scheme.
Although describing the present invention referring to exemplary implementation scheme, it should be appreciated that, it is of the invention not departing from Various modifications can be made under conditions of range and equivalent can substitute its element.In addition, many modifications will be appreciated that The particular instrument, situation or material that introduction according to the present invention is adapted under conditions of essential scope of the invention are not departed from.Therefore, It, which is intended that, executes best mode of the invention as imagination the present invention is not limited to disclosed specific embodiment but passes through The attached claims herein are explained.

Claims (136)

1. a kind of supercapacitor, comprising:
The intracorporal electrolyte system of gas-tight seal shell and energy storage unit, the unit are electrically coupled to positive contact and cathode Contact, wherein the ultracapacitor configurations at whole operation temperature range at a temperature of operate without it is aobvious in performance Variation is write, and wherein:
The operation temperature includes -40 degrees Celsius to 125 degrees Celsius；And
The electrolyte system includes the mixture of ionic liquid and organic solvent, wherein the operation of the supercapacitor Temperature range is more wider than the operating temperature range of equivalent supercapacitor, the equivalent supercapacitor and the super electricity Container is identical but electrolyte components are replaced with to the electrolyte for mainly forming and being free of the organic solvent by the ionic liquid； And
The mixture includes propylene carbonate and 1- butyl -1- crassitude and four cyano borate, the mixing The propylene carbonate of object is 37.5% by volume.
2. supercapacitor according to claim 1, wherein the electrolyte system includes purified electrolyte.
3. supercapacitor according to claim 2, wherein the purified electrolyte is suitable in the super electricity of high temperature It is used in container.
4. supercapacitor according to claim 1, wherein the electrolyte system includes being suitble at -40 degrees Celsius extremely The electrolyte combination used within the temperature range of 210 degrees Celsius.
5. supercapacitor according to claim 4, wherein the electrolyte combination is suitable in high temperature ultracapacitor With used in both low temperature supercapacitors.
6. supercapacitor according to any one of claim 1 to 5, wherein showing better than known energy accumulating device Have the advantages of electrolyte to be selected from one or more of following improvement: all-in resistance reduces, the long-time stability of resistance improve, total Capacitor increases, the long-time stability of capacitor improve, energy density increases, voltage stability improves, vapour pressure reduces, single capacitor The durability temperature of wider, the single capacitor of the temperature range performance of device improves, ease of manufacture improves and cost-effectiveness changes Into.
7. supercapacitor according to any one of claim 1 to 5, wherein the energy storage unit includes positive electrode And negative electrode.
8. supercapacitor according to claim 7, wherein at least one of described electrode includes carbon containing energy storage Medium.
9. supercapacitor according to claim 8, wherein the carbon containing energy storage medium includes carbon nanotube.
10. supercapacitor according to claim 8, wherein the carbon containing energy storage medium includes activated carbon, carbon At least one of fiber, staple fibre, graphene, aeroge, carbon cloth and carbon nanotube of diversified forms.
11. supercapacitor according to claim 7, wherein each electrode includes current-collector.
12. supercapacitor according to claim 1, wherein the ultracapacitor configurations are in the entire operation temperature The significant changes on durability are operated without at a temperature of degree range.
13. the supercapacitor according to any one of claim 2 to 3, wherein in the purified electrolyte halogen from The content of son is lower than 1000ppm.
14. supercapacitor according to claim 13, wherein halogen ion described in the purified electrolyte contains Amount is lower than 500ppm by weight.
15. supercapacitor according to claim 13, wherein halogen ion described in the purified electrolyte contains Amount is lower than 100ppm by weight.
16. supercapacitor according to claim 13, wherein halogen ion described in the purified electrolyte contains Amount is lower than 50ppm by weight.
17. supercapacitor according to claim 13, the halogen ion in the purified electrolyte is selected from chlorine One of ion, bromide ion, fluorine ion and iodide ion or more.
18. the supercapacitor according to any one of claim 2 to 3, wherein golden in the purified electrolyte The total concentration for belonging to substance is lower than 1000ppm by weight.
19. supercapacitor according to claim 18, wherein the metallics be selected from from Cd, Co, Cr, Cu, Fe, K, the one or more of metals selected in Li, Mo, Na, Ni, Pb and Zn.
20. supercapacitor according to claim 18, wherein the metallics be selected from from Cd, Co, Cr, Cu, Fe, K, one or more of alloys of the metal selected in Li, Mo, Na, Ni, Pb and Zn.
21. supercapacitor according to claim 18, wherein the metallics be selected from from Cd, Co, Cr, Cu, Fe, K, one or more of oxides of the metal selected in Li, Mo, Na, Ni, Pb and Zn.
22. the supercapacitor according to any one of Claims 2 or 3, wherein impurity in the purified electrolyte Total concentration be lower than 1000ppm by weight.
23. the supercapacitor according to any one of Claims 2 or 3, wherein miscellaneous in the purified electrolyte Matter be selected from one of bromoethane, chloroethanes, 1- bromobutane, 1-chlorobutane, 1- methylimidazole, ethyl acetate and methylene chloride or It is more kinds of.
24. the supercapacitor according to any one of Claims 2 or 3, wherein in the purified electrolyte always Water content is lower than 500ppm by weight.
25. supercapacitor according to claim 24, wherein water content total described in the purified electrolyte It is lower than 100ppm by weight.
26. supercapacitor according to claim 24, wherein water content total described in the purified electrolyte It is lower than 50ppm by weight.
27. supercapacitor according to claim 24, wherein water content total described in the purified electrolyte It is lower than 20ppm by weight.
28. supercapacitor according to any one of claim 1 to 5, wherein the gas-tight seal shell includes setting Barrier on the part on surface inside it.
29. supercapacitor according to claim 28, wherein the barrier includes polytetrafluoroethylene (PTFE) (PTFE), perfluor At least one of alkoxy resin, fluorinated ethylene propylene copolymer (FEP) and ethylene-tetrafluoroethylene copolymer (ETFE).
30. the supercapacitor according to claim 28, wherein the barrier includes ceramic material.
31. the supercapacitor according to claim 28, wherein the barrier includes showing corrosion resistance, dielectric Property and chemically inert material.
32. the supercapacitor according to claim 28, wherein the barrier includes multiple material layers.
33. supercapacitor according to any one of claim 1 to 5, wherein the gas-tight seal shell includes multilayer Material.
34. the supercapacitor according to claim 33, wherein the multilayer material includes to cover on the second material The first material.
35. the supercapacitor according to claim 33, wherein the multilayer material include in steel, tantalum and aluminium at least One of.
36. supercapacitor according to any one of claim 1 to 5, wherein the gas-tight seal shell includes at least One hemispherical seal.
37. supercapacitor according to any one of claim 1 to 5, wherein the gas-tight seal shell includes at least One glass to metal seal part.
38. the supercapacitor according to claim 37, wherein the pin of at least one glass to metal seal part One of described contact is provided.
39. the supercapacitor according to claim 37, wherein at least one described glass to metal seal part include by The feedthrough component that material selected from the following is constituted: iron-nickel-cobalt alloy, dilval, tantalum, molybdenum, niobium, tungsten, stainless steel and titanium.
40. the supercapacitor according to claim 37, wherein at least one described glass to metal seal part include by The ontology that at least one material selected from the following is constituted: nickel, molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminium, carbon and tungsten, Yi Jiqi Alloy.
41. supercapacitor according to any one of claim 1 to 5, wherein the energy storage unit includes isolation Device is to provide the electric isolution between positive electrode and negative electrode.
42. the supercapacitor according to claim 41, wherein the isolator includes to be selected from polyamide, polytetrafluoroethyl-ne Alkene (PTFE), polyether-ether-ketone (PEEK), aluminium oxide (Al2O3), glass fibre, in fiberglass reinforced plastics or any combination thereof Material.
43. supercapacitor according to claim 41, wherein the isolator moisture-free.
44. supercapacitor according to claim 41, wherein the isolator is hydrophobic.
45. supercapacitor according to any one of claim 1 to 5, the gas-tight seal of the gas-tight seal shell It shows no more than 5.0 × 10-6The leak rate of atm- cubic centimetres/second.
46. supercapacitor according to any one of claim 1 to 5, the gas-tight seal of the gas-tight seal shell It shows no more than 5.0 × 10-7The leak rate of atm- cubic centimetres/second.
47. supercapacitor according to any one of claim 1 to 5, the gas-tight seal of the gas-tight seal shell It shows no more than 5.0 × 10-8The leak rate of atm- cubic centimetres/second.
48. supercapacitor according to any one of claim 1 to 5, the gas-tight seal of the gas-tight seal shell It shows no more than 5.0 × 10-9The leak rate of atm- cubic centimetres/second.
49. supercapacitor according to any one of claim 1 to 5, the gas-tight seal of the gas-tight seal shell It shows no more than 5.0 × 10-10The leak rate of atm- cubic centimetres/second.
50. supercapacitor according to any one of claim 1 to 5, wherein at least one contact is configured to match Another contact of another supercapacitor.
51. supercapacitor according to any one of claim 1 to 5, wherein the energy storage unit includes setting Wrap member on its outside.
52. the supercapacitor according to claim 51, wherein the wrap member includes it in PTFE and polyimides One.
53. supercapacitor according to any one of claim 1 to 5, wherein volume leakage current is in the operation temperature For lower than 1000 milliamperes/liter in range.
54. supercapacitor according to any one of claim 1 to 5, wherein model of the volume leakage current at 0 to 4 volt For lower than 1000 milliamperes/liter in enclosing.
55. supercapacitor according to any one of claim 1 to 5, wherein the intracorporal moisture of gas-tight seal shell It is horizontal to be lower than 1000ppm by weight.
56. supercapacitor according to claim 55, wherein the intracorporal moisture level of the gas-tight seal shell is pressed Poidometer is lower than 500ppm.
57. supercapacitor according to claim 55, wherein the intracorporal moisture level of the gas-tight seal shell is pressed Poidometer is lower than 350ppm.
58. supercapacitor according to any one of claim 1 to 5, included in the electrode of the supercapacitor By weight be lower than 1000ppm moisture content.
59. supercapacitor according to claim 58 includes in the electrode of the supercapacitor by weight Meter is lower than the moisture content of 500ppm.
60. supercapacitor according to claim 58, wherein the water in the electrode of the supercapacitor Point content is lower than 350ppm by weight.
61. supercapacitor according to any one of claim 1 to 5, included in the isolator of the supercapacitor In by weight be lower than 1000ppm moisture content.
62. supercapacitor according to claim 61 includes pressing in the isolator of the supercapacitor Poidometer is lower than the moisture content of 500ppm.
The moisture 63. supercapacitor according to claim 61, in the isolator of the supercapacitor Content is lower than 160ppm by weight.
64. supercapacitor according to any one of claim 1 to 5, wherein for being selected from electrode, electrolyte and isolation One of component in device, chloride ion content are lower than 300ppm by weight.
65. supercapacitor according to any one of claim 1 to 5, wherein the volume of the supercapacitor is leaked electricity Flow keep constant at a temperature of when lower than 10mA/ cubic centimetres.
66. supercapacitor according to claim 65, wherein the volume leakage current of the supercapacitor is keeping permanent It is lower than 1mA/ cubic centimetres when at a temperature of fixed.
67. supercapacitor according to claim 65, wherein the volume leakage current of the supercapacitor is keeping permanent It is greater than 0.0001mA/ cubic centimetres when at a temperature of fixed.
68. supercapacitor according to claim 65, wherein the volumetric capacitance of the supercapacitor is 6F/ cubes li Between rice and 1mF/ cubic centimetres.
69. supercapacitor according to claim 65, wherein the volumetric capacitance of the supercapacitor is 10F/ cubes Centimetre and 5F/ cubic centimetres between.
70. supercapacitor according to claim 65, wherein the volumetric capacitance of the supercapacitor is 50F/ cubes Centimetre and 8F/ cubic centimetres between.
71. supercapacitor according to claim 65, wherein the volume ESR of the supercapacitor is vertical for 20 milliohms Between square centimetre and 200 milliohm cubic centimetres.
72. supercapacitor according to claim 65, wherein the volume ESR of the supercapacitor is 150 milliohms Between cubic centimetre and 2 ohm of cubic centimetres.
73. supercapacitor according to claim 65 also shows 1.5 ohm of cubic centimetres and 200 ohm The volume ESR of the supercapacitor between cubic centimetre.
74. supercapacitor according to claim 65 also shows 150 ohm of cubic centimetres and 2000 ohm The volume ESR of the supercapacitor between cubic centimetre.
75. supercapacitor according to claim 65, wherein the supercapacitor is kept at least under constant voltage The capacitor less than 60% is shown at 20 hours to be reduced.
76. supercapacitor according to claim 65, wherein the supercapacitor is kept at least under constant voltage The ESR less than 300% is shown at 20 hours to increase.
77. the supercapacitor according to claim 65, wherein the supercapacitor is when being maintained at constant voltage Showing the capacitor less than 60% reduces.
78. a kind of method for manufacturing supercapacitor, includes the following steps:
Energy storage unit comprising energy storage medium is arranged in shell；With
The shell is filled with electrolyte system, so that manufacturing supercapacitor at the temperature in whole operation temperature range Under operate without significant changes in performance, the operating temperature range includes -40 degrees Celsius to 125 degrees Celsius, Yi Jiqi In:
The electrolyte system includes the mixture of ionic liquid and organic solvent, wherein the operation of the supercapacitor Temperature range is more wider than the operating temperature range of equivalent supercapacitor, the equivalent supercapacitor and the super electricity Container is identical but electrolyte components are replaced with to the electrolyte for mainly forming and being free of the organic solvent by the ionic liquid； And
The mixture include propylene carbonate and with 1- butyl -1- crassitudeIt is described mixed with four cyano borate The propylene carbonate for closing object is 37.5% by volume.
79. the method according to claim 78, wherein the electrolyte system includes purified electrolyte.
80. the method according to claim 79, wherein the purified electrolyte is suitable in high temperature ultracapacitor Middle use.
81. the method according to claim 78, wherein the electrolyte system includes being suitble to take the photograph at -40 degrees Celsius to 210 The electrolyte combination used within the temperature range of family name's degree.
82. the method according to claim 81, wherein the electrolyte combination is suitable in high temperature ultracapacitor and low It is used in warm supercapacitor the two.
83. the method according to any one of claim 78 to 82, wherein existing better than known energy accumulating device The advantages of electrolyte is selected from one or more of following improvement: all-in resistance reduces, the long-time stability of resistance improve, total electricity Hold increase, the long-time stability of capacitor improve, energy density increases, voltage stability improves, vapour pressure reduces, single capacitor Wider, the single capacitor of temperature range performance durability temperature improve, ease of manufacture improve and cost-effectiveness improve.
84. the method according to any one of claim 78 to 82, wherein the setting further includes that pretreatment is described super For the component of capacitor to reduce moisture therein, the component of the supercapacitor includes: electrode, isolator, lead, assembled Energy storage unit and at least one of the shell.
85. the method according to claim 84, wherein the pretreatment includes taking the photograph under vacuum at 100 degrees Celsius to 150 The component is heated within the temperature range of family name's degree.
86. the method according to claim 84, wherein the pretreatment includes taking the photograph under vacuum at 150 degrees Celsius to 300 The component is heated within the temperature range of family name's degree.
87. the method according to any one of claim 78 to 82, wherein carrying out the setting in inert environment.
88. the method according to any one of claim 78 to 82, wherein the method also includes selecting for the shell The relatively described electrolyte system shows chemically inert interior surface material.
89. the method according to claim 88 further includes introducing the interior surface material in the inside of the shell.
90. the method according to claim 88, wherein the method also includes selection aluminium, polytetrafluoroethylene (PTFE) (PTFE), complete In Fluoroalkyloxy resin, fluorinated ethylene propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE) and ceramic material At least one be used as the interior surface material.
91. the method according to any one of claim 78 to 82, wherein the method also includes being formed by multilayer material The shell.
92. the method according to claim 91, wherein it is described by the multilayer material formed the shell include will be solderable Material is connect to be arranged on the outside of the shell.
93. the method according to any one of claim 78 to 82, wherein the method also includes manufacturing for the shell At least one of lid and ontology.
94. the method according to any one of claim 78 to 82, wherein the method also includes fill port is arranged To realize the filling in the shell.
95. the method according to claim 93, wherein the manufacture will be including that comprising insulator and will electrically isolate from the shell Electrode sealing element it is disposed in the housing.
96. the method according to claim 95, being provided with the sealing element includes setting glass to metal seal part.
97. the method according to claim 95, being provided with the sealing element includes setting hemispherical seal.
98. the method according to claim 96, being provided with the glass to metal seal part includes by the glass-gold Belong to the outer surface that sealing element is soldered to the shell.
99. the method according to any one of claim 78 to 82 further includes manufacturing the energy storage unit.
100. the method according to claim 99, wherein manufacturing the energy storage unit includes by connecting the energy Storage medium obtains electrode with current-collector.
101. method described in 00 according to claim 1, wherein obtaining the electrode includes that connection is multiple by connecting the energy The electrode member measuring storage medium and current-collector and manufacturing.
102. method described in 01 according to claim 1, wherein connecting the multiple electrode member includes by connecting element ultrasound It is soldered to the current-collector of an electrode member and is ultrasonically welded to the current-collector of another electrode member.
103. the method according to claim 99, wherein manufacturing the energy storage unit includes connecting at least one lead It is connected to electrode.
104. method described in 03 according to claim 1, wherein it includes inciting somebody to action that at least one lead, which is connected to the electrode, At least one reference marker is arranged on the electrode.
105. method described in 04 according to claim 1, wherein it includes inciting somebody to action that at least one lead, which is connected to the electrode, Each lead is arranged at corresponding reference marker.
106. the method according to claim 78, wherein implement described the step of filling the shell with electrolyte system, So that by supercapacitor manufacture at whole operation temperature range at a temperature of operate and do not have the significant changes on durability.
107. method described in 03 according to claim 1, wherein connecting at least one lead includes by the lead ultrasound It is soldered to current-collector.
108. the method according to claim 99, wherein manufacturing the energy storage unit includes that isolator is arranged extremely Between few two electrodes.
109. method described in 08 according to claim 1 further includes being aligned each of described electrode with the isolator.
110. the method according to claim 99, wherein manufacturing the energy storage unit includes at least two electrodes of package With the isolator of setting therebetween.
111. method described in 10 according to claim 1, wherein described includes being rolled into the energy storage unit to roll Storage element.
112. the method according to claim 99, wherein manufacturing the energy storage unit includes that wrap member is arranged in institute It states on energy storage unit.
113. the method according to any one of claim 78 to 82, be provided with the energy storage unit include will be more Root lead gathers together to provide terminal.
114. method described in 13 according to claim 1, wherein described gather together more leads including by the lead Alignment becomes one group of lead through being aligned to form the terminal together.
115. method described in 14 according to claim 1 further includes that wrap member is arranged in one group of lead through being aligned Around.
116. method described in 14 according to claim 1 further includes folding to one group of lead through being aligned.
117. method described in 14 according to claim 1 further includes coupling one group of lead through being aligned to the shell Contact.
118. method described in 17 according to claim 1, wherein the coupling includes the lead weldering by described one group through being aligned It is connected to the contact.
119. method described in 17 according to claim 1, wherein the coupling includes the lead welding by described one group through being aligned To one of jumper and bridge with the contact for being coupled to the shell.
120. the method according to any one of claim 78 to 82, further include in electric coupling jumper and bridge at least One of to the shell contact.
121. method described in 20 according to claim 1 further includes the contact that insulating materials is arranged in the shell On.
122. the method according to any one of claim 78 to 82 further includes that the energy storage unit is airtightly close It is enclosed in the shell.
123. the method according to any one of claim 78 to 82 further includes by least one lid and Ontology Matching to mention For the shell.
124. method described in 23 according to claim 1, wherein at least one described lid includes it in recessed lid, dished cover and flat cover One.
125. method described in 23 according to claim 1, further include remove at least part of multilayer material in the shell with The matching is provided.
126. method described in 22 according to claim 1, wherein airtightly sealing includes that the component of the shell is passed through pulse At least one of welding, laser welding, resistance welding and TIG weld weld together.
127. the method according to any one of claim 78 to 82 further includes purifying the electrolyte system.
128. the method according to any one of claim 78 to 82 further includes that fill port is arranged in the shell To provide the filling.
129. method described in 28 according to claim 1 further includes sealing the fill port after completing the filling.
130. method described in 29 according to claim 1, wherein the sealing includes that material is installed to the fill port In.
It further include that the material is soldered to the shell is intracorporal described to be filled out 131. method described in 30 according to claim 1 It fills in port.
132. the electrolyte system is arranged described wherein the filling bag includes for method described in 28 according to claim 1 On the fill port in shell.
133. method described in 32 according to claim 1, the filling includes taking out to the fill port in the shell Vacuum.
134. method described in 33 according to claim 1, wherein the vacuum is lower than 150 millitorrs.
135. method described in 33 according to claim 1, wherein the vacuum is lower than 40 millitorrs.
136. method described in 28 according to claim 1, wherein carrying out the filling in inert environment.
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