CN101563797A

CN101563797A - Copper-based energy storage device and method

Info

Publication number: CN101563797A
Application number: CNA2007800472227A
Authority: CN
Inventors: 吉列尔莫·D·扎皮; 查尔斯·D·亚科范格洛; 小戴维·C·博格丹; 史蒂文·A·泰索; 迈克尔·A·瓦兰斯; 卡西克·V·古里斯汉卡; 哈里·N·塞沙德里; 古鲁普拉萨德·森达拉拉詹
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 2006-12-19
Filing date: 2007-11-20
Publication date: 2009-10-21

Abstract

An energy storage device is provided that includes a cathodic material in electrical communication with a separator. The cathodic material includes copper. The separator has a first surface that defines at least a portion of a first chamber, and a second surface that defines a second chamber. The first chamber is in ionic communication with the second chamber through the separator. The separator has at least one of the following attributes: the separator is a composite of alumina and a rare earth oxide, or the separator is a composite of alumina and a transition metal oxide, or the separator comprises a plurality of grains, and the grains define grain boundaries that define interstitial spaces, and the interstitial spaces defined by the grain boundaries are free of sodium aluminate prior to an initial electrical charging of the energy storage device or are free of the cathodic material after the initial electrical charging of the energy storage device, or the separator comprises a continuous phase of an alkali-metal-ion conductor and a continuous phase of a ceramic oxygen-ion conductor.

Description

Copper-based energy storage device and method

The cross reference of related application

The present invention requires to be called in the name that on December 19th, 2006 submitted to the U.S. Provisional Application No.60/870 of " ENERGY STORAGEDEVICE AND METHOD ", and 843 priority and right are incorporated herein its full content as a reference.

Technical field

The present invention relates to the melten salt electriochemistry battery.The present invention relates to use the method for electrochemical cell.The present invention relates to energy storage device and the energy management apparatus (energy managementdevice) that comprises energy storage device.

Background technology

For rechargeable battery, carried out the development that sodium is used for negative pole.Sodium has 2.71 volts reduction potential, and weight is less, and is nontoxic relatively, and relative rich is produced, can obtain and cost low.Sodium uses with liquid form, and the fusing point of sodium is 98 ℃.Should be pointed out that interior thermal cycle, pressure differential and the vibration of battery in use may destroy beta-alumina dividing plate electrode (separatorelectrode) (BASE) in some cases.Thereby thicker wall can be given BASE better intensity and durability, makes the correlated performance deterioration but may cause resistance to increase because of wall is thicker.

May expect to obtain the melten salt electriochemistry battery different with the chemical characteristic of existing electrochemical cell.May expect to obtain the energy storage device different with existing method.May expect to obtain the energy storage device different with existing apparatus.

Summary of the invention

According to embodiment of the present invention, provide a kind of energy storage device.This energy storage device comprises the positive electrode with the dividing plate electric connection.Positive electrode comprises copper.Dividing plate has the first surface of at least a portion that defines first locellus and defines the second surface of second locellus.First locellus is via the dividing plate and the second locellus ionic communication.Dividing plate has at least a in the following Column Properties: dividing plate is the compound of aluminium oxide and rare-earth oxide; Perhaps dividing plate is the compound of aluminium oxide and transition metal oxide; Perhaps dividing plate comprises a plurality of crystal grain that define crystal boundary, crystal boundary defines space, brilliant crack (interstitial space), and is not being contained sodium aluminate before the energy storage device primary charging or do not contained positive electrode after the energy storage device primary charging by the space, brilliant crack that crystal boundary defines; Perhaps dividing plate comprises the continuous phase of alkali metal ion conductor and the continuous phase of ceramic oxygen ion conductor.

According to embodiment of the present invention, a kind of method is provided, this method comprises via dividing plate transmits sodium ion between first locellus and second locellus, this dividing plate and the positive electrode electric connection that comprises copper.Dividing plate has at least a in the following Column Properties: dividing plate is the compound of aluminium oxide and rare-earth oxide; Perhaps dividing plate is the compound of aluminium oxide and transition metal oxide; Perhaps dividing plate comprises a plurality of crystal grain that define crystal boundary, and crystal boundary defines space, brilliant crack, and is not being contained sodium aluminate before the energy storage device primary charging or do not contained positive electrode after the energy storage device primary charging by the space, brilliant crack that crystal boundary defines; Perhaps dividing plate comprises the continuous phase of sodium ion conductor and the continuous phase of ceramic oxygen ion conductor.This method comprises that also prevention copper infiltrates space, brilliant crack in the sodium ion transmission course.

According to embodiment of the present invention, provide a kind of energy-storage system.This system comprises dividing plate.Dividing plate transmits sodium ion between first locellus and second locellus.Dividing plate and the positive electrode electric connection that comprises copper.Dividing plate has at least a in the following Column Properties: dividing plate is the compound of aluminium oxide and rare-earth oxide; Perhaps dividing plate is the compound of aluminium oxide and transition metal oxide; Perhaps dividing plate comprises a plurality of crystal grain that define crystal boundary, and crystal boundary defines space, brilliant crack, and is not being contained sodium aluminate before the energy storage device primary charging or do not contained positive electrode after the energy storage device primary charging by the space, brilliant crack that crystal boundary defines; Perhaps dividing plate comprises the continuous phase of sodium ion conductor and the continuous phase of ceramic oxygen ion conductor.This system also comprises the mechanism (means) that stops copper to infiltrate space, brilliant crack in the sodium ion transmission course.

Description of drawings

Fig. 1 is the schematic diagram according to the goods of one embodiment of this invention.

Fig. 2 is a series of designs (Fig. 2 A-2J) that are used for embodiment of the present invention.

Fig. 3 is the polarization curve according to the embodiment of one embodiment of this invention.

Fig. 4 is the performance chart according to the embodiment of one embodiment of this invention.

Fig. 5 is according to the embodiment of one embodiment of this invention and the comparison diagram of comparative sample.

Embodiment

The present invention relates to the melten salt electriochemistry battery.The present invention relates to use the method for electrochemical cell.The present invention relates to energy storage device and the energy management apparatus that comprises energy storage device.

As used herein, positive electrode is the material that electronics is provided in charging process, and in its reaction side as the part of redox reaction about 5 weight % greater than the electrochemical reactant that participates in reaction.As used in the specification and claims, can use approximate statement to modify any quantitative expression, allow quantitative expression under the situation that does not change its related basic function, to change.Thereby by term as " pact " modify value be not limited to the exact value of defined.In some cases, Jin Si statement can be corresponding to the precision of measuring the used instrument of numerical value.

According to embodiment of the present invention, provide a kind of energy storage device.This energy storage device comprises the positive electrode with the dividing plate electric connection.Positive electrode comprises copper.Dividing plate has the first surface of at least a portion that defines first locellus and defines the second surface of second locellus.First locellus is via the dividing plate and the second locellus ionic communication.Dividing plate has at least a in the following Column Properties: dividing plate is the compound of aluminium oxide and rare-earth oxide; Perhaps dividing plate is the compound of aluminium oxide and transition metal oxide; Perhaps dividing plate comprises a plurality of crystal grain that define crystal boundary, and this crystal boundary defines space, brilliant crack, and is not being contained sodium aluminate before the energy storage device primary charging or do not contained positive electrode after the energy storage device primary charging by the space, brilliant crack that crystal boundary defines; Perhaps dividing plate comprises the continuous phase of alkali metal ion conductor and the continuous phase of ceramic oxygen ion conductor.

According to another embodiment of the present invention, energy storage device comprises multiple positive electrode.Except other function, positive electrode and the current potential when having chemism thereof, the ratio between the positive electrode, positive electrode be the selection of the method for operation of the relative position in energy storage device and energy storage device each other, can also indicate energy storage device charged state (state of charge, SOC).Described other function can comprise peak value of pulse charging, peak value of pulse discharge, additives for overcharge protection, over, the power of increase and/or the energy density of increase.

In order to realize the charged state indication, first positive electrode can be most reactive metal, and second positive electrode can match with first positive electrode.Second positive electrode can have different charging, and this charging obviously is different from the charging of the reactive metal of first positive electrode.In alternative embodiment, the difference of second positive electrode and first positive electrode can be to have lower activation voltage or higher activation voltage, perhaps has higher and lower activation voltage in some cases simultaneously.For example, at use copper base first positive electrode and under, can use zinc-base second positive electrode with the situation of chlorine as halogen.Copper has activity in the time of 2.6 volts, zinc has activity in the time of 2.2 volts.In the case, zinc can serve as discharge off indication body (end of dischargeindicator), make and be reduced under the situation of copper at all CuCl, because second positive electrode can be used for reaction, and makes anodal operating voltage (operating cathode voltage) (OCV) reduce to 2.2 volts from 2.6 volts.

In some embodiments, have following condition: if first positive electrode or second positive electrode are nickel, then another positive electrode is not iron, arsenic or tin; If first positive electrode or second positive electrode are copper, then another positive electrode is not arsenic or tin.

In order to realize the charged state indication, to compare with first positive electrode, the amount of second positive electrode can be less relatively.The ratio of first positive electrode and second positive electrode can be less than about 100: 1.In one embodiment, described ratio can be about 100: 1 to about 75: 1, about 75: 1 to about 50: 1, about 50: 1 to about 25: 1, about 25: 1 to about 15: 1, about 15: 1 to about 5: 1, or about 5: 1 to greater than about 1: 1.

The combination of first positive electrode and second positive electrode can improve the energy density of energy storage device, and can provide over respect to single positive electrode system.In order to realize over, can select second positive electrode, to have the activation voltage that is lower than first positive electrode but is higher than support electrolyte (supporting electrolyte) (for example alchlor).Thereby, use up with whole Cu in the system that copper is only arranged, make AlCl ₃In continuous firing or crossing under the low-voltage situation difference that the form with aluminium deposits out, the Zn in the Cu/Zn system can react prior to alchlor.

In one embodiment, first positive electrode is a zinc, and second positive electrode is a copper.In the case, Cu is the SOC indication body, and it indicates when all zn all is oxidized to ZnCl ₂, this moment, anodal operating voltage rose to 2.6 volts from 2.24 volts when Cu at first begins to be oxidized to CuCl.In addition, copper can provide additives for overcharge protection.Be copper with oxidized rather than support electrolyte (AlCl for example ₃) be oxidized to Cl ₂

In one embodiment, two or more positive electrodes are mixed.In another embodiment, first positive electrode is coated on second positive electrode.Thereby second positive electrode does not expose physically or is unavailable on electrochemistry, is removed or by electrochemical conversion until first positive electrode.This painting method can be applicable to following situation: the reactive metal (for example Zn and Cu) that is dissolved in anodal melt is first positive electrode, and the metal (for example Ni) that is insoluble to anodal melt is second positive electrode.

Pulse current charge and pulsed discharge feature similarly form show.In order to realize pulse current charge/discharge, can add second positive electrode, to provide faster or have more that active electric energy sucks and output with respect to first positive electrode.Can decide the amount of second positive electrode according to the specific requirement of final use, because the type of second positive electrode, position and amount can be based on the pulsed quantities of expection.For example plug-in hybrid vehicle (plug-in hybrid vehicle) (PHEV) in, when low rates of discharge (for example 10kW per hour), the energy of 11 kilowatt hours (kWh) may be needed, yet 40kW to 50kW may be needed for 3 to 10 seconds transient pulse.In two positive electrode system, second positive electrode can carry out charge or discharge under the electric current that is higher than first positive electrode.Voltage in the time of can selecting material to have activity, and can select voltage with respect to electrolytical puncture voltage.

For example, in conjunction with above-mentioned Cu/Zn example, for constant resistance in the positive pole be 0.005 ohm and before electrolyte punctures cut-ff voltage be 3.4 volts situation, copper can 544 watts power (3.4-2.6/0.005) under the electric currents of 3.4 volts voltage and 160 peaces, work, zinc can 816 watts power (3.4-2.2/0.005) under the electric currents of 3.4 volts voltage and 240 peaces, work, compare relative higher pulse current charge ability with the situation that copper is only arranged to provide.Zinc also can provide the pulsed discharge ability by the standard discharge potential of control Cu positive pole.Under the identical situation of cell resistance, the power (2.6-2.2/0.005) that copper can 176 watts discharges being higher than 2.2 volts voltage and being higher than under the electric currents of 80 peaces.In conventional electrochemical cell Comparative Examples, this discharge mode can make battery discharge in about 32 minutes---be called 2C speed.

In one embodiment, in order to be implemented in pulsed discharge under the bigger electric current, cell voltage can be low to moderate 1.8 volts, so that first and second positive electrodes can discharge simultaneously, rather than discharge successively.When occurring following situation in the battery, can need this function: because the reaction front of positive electrode moves and away from dividing plate, makes resistance increase along with charged state to anodal depths.With respect to standard cell, resistance rises to 0.025 Europe from 0.005 Europe, and in this embodiment along with the lifting of charged state, the power that is derived from first positive electrode (for example above-mentioned copper) is reduced to about 57.6 watts from 176 watts.Cell voltage may be kept above 2.2 volts, make be positioned near the dividing plate second positive electrode (for example above-mentioned zinc) 0.005 Europe than still available under the low resistance, thereby allow output pulses discharge with 144 watts.

First positive electrode and second positive electrode are separated, rather than select, may be to use the suitable method of embodiment of the present invention by voltage.For example, in elongated tubular, first positive electrode can be placed the top, and second positive electrode can be placed the bottom with top and bottom.Prevent that the plate that positive electrode in use mixes from can separate first positive electrode and second positive electrode.Which kind of positive electrode lays respectively at two collector bodies in the active anode compartment material separately can control and charge and discharge on electricity.

Alternatively, positive electrode alternation radially.Gradient can followingly form: first positive electrode is arranged in the layer near baffle surface, second positive electrode is arranged on center near the anodal locellus of axis.First positive electrode with respect to the concentration of second positive electrode along with the distance of distance baffle surface difference, perhaps different along with the distance (moving radially in opposite direction) of distance axis.In one embodiment, first positive electrode is the metal that has than overactivity voltage, for example zinc; Second positive electrode is the metal with low activation voltage, for example nickel.Because at least a portion of second positive electrode is available under any charged state, thereby this concentration gradient is arranged any time realization maximum power pulse that can make in the cycle.

Another feature of two positive poles can comprise the alloy current potential.Alloy oxidation product possibility conductibility is better, solubility is better, and has the dynamics that is better than any single positive electrode.For example, in Ni-Zn or Cu-Zn, the alloying that is reduced to two kinds of metals in the process of metal at chloride can form the alloy that charging performance can improve relatively.

The non-limiting example of the positive electrode pairing that reckons with can comprise:

Ni and Cu:

Cu/CuCl can provide the SOC indication body

Cu/CuCl and CuCl/CuCl ₂Additives for overcharge protection can be provided

CuCl/CuCl ₂Pulse current charge can be provided

Ni and Zn, Sn:

Zn, Sn can provide the SOC indication body when finishing near discharge

Zn, Sn can provide additives for overcharge protection

Zn, Sn can provide pulsed discharge (if regular picture keeps greater than 2.2 volts)

Zn, Sn can provide pulse current charge

Zn can metal, be dissolved in the ZnCl of melt ₂, ZnS form add

Sn can metal or the form of salt add

Ni and W, Mo:

W, Mo can provide the SOC indication body

Cu and W, Mo:

W, Mo can provide the SOC indication body

Cu and Zn, Sn:

The effect of Zn, Sn is with identical in the situation of above-mentioned Ni

Zn and Cu, Ni, Sn:

Ni and Cu can provide SOC indication body, additives for overcharge protection, pulsed discharge

Unless otherwise noted, positive electrode can be arranged on second minute indoor.For the dividing plate of energy storage device, second locellus can be arranged on first minute indoor, and can be elongated to define axis.Thereby first locellus can center on the axis coaxle setting.In addition, with further reference to dividing plate, dividing plate can have circle, triangle, square, cross or the star cross section profile perpendicular to axis.Alternatively, dividing plate can be roughly plane.Planar structure (or slightly arching) can be used for the prismatic or the coin shape battery structure of dividing plate arching or nick.Similarly, dividing plate can be plate shaped or waveform.Below will further specify separator material.

The size and dimension that can set shell is to have square, polygon or circular cross-section; And shell can have greater than about 1: 10 length-width ratio.In one embodiment, length-width ratio is about 1: 10 to about 1: 5, about 1: 5 to about 1: 1, and about 1: 1 to about 5: 1, about 5: 1 to about 10: 1, about 10: 1 to about 15: 1.Shell can be made by metal, pottery or compound; Metal can be selected from nickel or steel, and pottery can be a metal oxide.

Randomly, one or more gasket constructions can be set in the opposite end of dividing plate.Gasket construction is portion's supporting clapboard in the enclosure.Gasket construction can protect dividing plate to avoid that battery moves the vibration that causes in the use, and then reduces or eliminates moving of dividing plate opposite shell.If exist, gasket construction can serve as the collector body of shell.If the lifting in charge and discharge process of the current potential of fusion negative pole, then using gasket construction may be favourable as collector body.Gasket construction can provide the narrow gap of contiguous dividing plate, to promote the core sucting action (wicking) of fusion negative material thin layer to baffle surface.Described core sucting action may be irrelevant with the charged state of battery, and irrelevant with the head height (head height) of negative material.

In one embodiment, first locellus can comprise the negative material that can serve as negative pole, for example sodium.Other suitable negative material can comprise a kind of in lithium and the potassium or comprise lithium and potassium, and can replace with sodium and use or use with sodium.In use can be with the negative material fusion.First locellus can receive and deposit the negative material storage.The additive that is applicable to negative material can comprise the metal oxygen scavenger.Suitable metal oxygen scavenger can comprise one or more in manganese, vanadium, zirconium, aluminium or the titanium.Other useful additive can comprise the infiltrating material of raising fusion negative material to baffle surface.In addition, some additives can improve the order of contact or the wettability of the relative collector body of dividing plate, flow through whole dividing plate to guarantee basic electric current uniformly.

Second locellus can hold positive electrode, and positive electrode can be one or more in first positive electrode, second positive electrode or the 3rd positive electrode for example.First positive electrode can exist according to the form of charged state with simple substance form or salt.Promptly first positive electrode exists with the form of simple substance form and/or salt, and the ratio of the percentage by weight of first positive electrode that exists of the percentage by weight of first positive electrode that exists with simple substance form and form with salt can be based on charged state.The material that is suitable for use as first positive electrode can comprise aluminium, nickel, zinc, copper, chromium, tin, arsenic, tungsten, molybdenum and iron.In one embodiment, first positive electrode is in fact only by a kind of composition the in zinc, copper or the chromium.In one embodiment, first positive electrode is in fact only formed by two kinds in nickel, zinc, copper, chromium or the iron.In one embodiment, first positive electrode is in fact only formed by three kinds in aluminium, nickel, zinc, copper, chromium, tin, arsenic, tungsten, molybdenum and the iron.Second positive electrode is different with first positive electrode with the 3rd positive electrode.First positive electrode, second positive electrode and the 3rd positive electrode can mix mutually, can be adjacent, or can spatially and/or on the electricity remove mutually.

If exist, second positive electrode is different with first positive electrode, and can comprise aluminium, nickel, zinc, copper, chromium and iron.Other second suitable positive electrode can comprise tin and/or arsenic.Other second suitable positive electrode can comprise tungsten, titanium, niobium, molybdenum, tantalum and vanadium.First positive electrode can be lower than about 100: 1 ratio with respect to second metal and exist.In one embodiment, first positive electrode can exist by following proportion with respect to the metal that adds: about 100: 1 to about 50: 1, and about 50: 1 to about 1: 1, about 1: 1 to about 1: 50, about 1: 50 to about 1: 95.

First positive electrode can be self-supporting or liquid/fusion, and positive electrode is arranged on the supporting construction in one embodiment.Alternatively, second positive electrode with different activation voltages can support described positive electrode.Supporting construction can be foams, net, fabric, felt pan, perhaps a large amount of filler particles, fiber, whisker.Suitable supporting construction can be formed by carbon.Suitable carbon foam is a reticulated vitreous carbon.

First positive electrode can be fixed in the supporting construction outer surface.Supporting construction can have big surface area.First positive electrode on the supporting construction can be close to the first surface of dividing plate and extend out from described baffle surface.Supporting construction can reach greater than about 0.01 millimeter thickness from described first surface extension.In one embodiment, described thickness is about 0.01 millimeter to about 0.1 millimeter, about 0.1 millimeter to about 1 millimeter, and about 1 millimeter to about 5 millimeters, about 5 millimeters to about 10 millimeters, about 10 millimeters to about 15 millimeters, about 15 millimeters to about 20 millimeters.For the bigger electrochemical cell of capacity, described thickness can be greater than 20 millimeters.

By first positive electrode is placed on the supporting construction surface, rather than be placed in second locellus, can avoid liquid to homogenize with the liquid melts form.Promptly be placed on specific material is located in electrochemical cell.For example, near the position of dividing plate to distance dividing plate position far away, the concentration of first positive electrode of simple substance form may be different.It is such to be similar to onion, can have a plurality of first positive electrode material layers, and first positive electrode in described a plurality of layers exists with different concentration or amount according to residing position in electrochemical cell.Similarly, can form gradient, resistance increases for example to tackle, and perhaps changing along with the use of reactant in the reaction front zone and leaving provides more stable reactant availability when baffle surface is advanced in the cell body.As used herein, gradient can comprise the stepped of concentration, thereby is configured and can serves as the charged state indication body.

Be applicable to that it is I family metal, for example sodium that negative material provides the material of transmission ion.The salt of negative material can be metal halide.Suitable halide can comprise chloride.Alternatively, halide can comprise bromide, iodide or fluoride.In one embodiment, halide can comprise chloride, and one or more additional halide.Suitable additional halide can comprise iodide or fluoride.In one embodiment, additional halide is sodium iodide or sodium fluoride.Additional halid amount can be greater than about 0.1 percentage by weight.In one embodiment, the scope of described amount is extremely about 0.5 percentage by weight of about 0.1 percentage by weight, and about 0.5 percentage by weight is to about 1 percentage by weight, and about 1 percentage by weight is to about 5 percentage by weights, and about 5 percentage by weights are to about 10 percentage by weights.

In one embodiment, electrolyte can comprise the salt of first metal, the salt of second metal and the salt of the 3rd metal, to form the ternary melt at height to the working temperature that is enough to make the salt fusion.The ternary melt can be MCl for example ₂: NaCl: AlCl ₃, wherein M represents first metal.The metal that is suitable for use as first metal " M " comprises transition metal.

MCl ₂: NaCl: AlCl ₃Suitable proportion can make MCl ₂Content mostly be about 20 percentage by weights most.AlCl in the ternary melt ₃Amount can be based on gross weight greater than about 10 percentage by weights.In one embodiment, AlCl in the ternary melt ₃Amount be about 10 percentage by weights to about 20 percentage by weights, about 20 percentage by weights are to about 30 percentage by weights, about 30 percentage by weights are to about 40 percentage by weights, about 40 percentage by weights are to about 50 percentage by weights, about 50 percentage by weights are to about 60 percentage by weights, or about 60 percentage by weights are to about 70 percentage by weights.In one embodiment, AlCl ₃Weight greater than the weight of NaCl.In another embodiment, the weight of NaCl is greater than AlCl ₃Weight.

In one embodiment, multiple electrolytic salt comprises the mixture of two kinds of slaines, to form binary melt under working temperature.Suitable binary melt can comprise MCl ₂: NaCl or MCl ₂: AlCl ₃In one embodiment, binary melt is in fact by MCl ₂: AlCl ₃Form.MCl ₂Suitable amount can be greater than 10 percentage by weights.In one embodiment, MCl ₂Amount be about 10 percentage by weights to about 20 percentage by weights, about 20 percentage by weights are to about 30 percentage by weights, about 30 percentage by weights are to about 40 percentage by weights, about 40 percentage by weights are to about 50 percentage by weights, about 50 percentage by weights are to about 60 percentage by weights, about 60 percentage by weights are to about 70 percentage by weights, and about 70 percentage by weights are to about 80 percentage by weights, or about 80 percentage by weights are to about 90 percentage by weights.

Sulfur-bearing or phosphorous additive can be arranged in the positive electrode.The existence of sulphur or phosphorus has suppressed the crystallization again and the grain growth of salt in the positive pole.For example, elemental sulfur, vulcanized sodium or triphenyl sulfide (triphenyl sulfide) can be arranged in the positive pole.

The suitable working temperature of energy storage device can and can be selected according to composition and performance requirement greater than 150 ℃.In one embodiment, working temperature is about 150 ℃ to about 200 ℃, about 200 ℃ to about 250 ℃, about 250 ℃ to about 300 ℃, about 300 ℃ to about 350 ℃, about 350 ℃ to about 400 ℃, about 400 ℃ to about 450 ℃, about 450 ℃ to about 500 ℃, or about 550 ℃ to about 600 ℃.

Dividing plate is the sodium ion conductor solid electrode that in use conducts sodium ion.Suitable dividing plate can comprise the compound of aluminium oxide and metal (pottery) oxide.Aluminium can be beta-alumina, β "-aluminium oxide or their mixture, and sodium ion had quick conductibility.The compositing range of beta-alumina is by Na ₂O-Al ₂O ₃Phasor defines.Beta-alumina has hexagonal crystallographic texture and contains the 1 mole of Na that has an appointment ₂The about 9 moles of Al of O- ₂O ₃β "-aluminium oxide has higher Na ₂O-Al ₂O ₃Ratio contains the 1 mole of Na that has an appointment ₂The about 5 moles of Al of O- ₂O ₃, and have oblique square structure.In one embodiment, the part of dividing plate is an Alpha-alumina, and another part of dividing plate is a beta-alumina.Sealing and/or manufacturing that Alpha-alumina may be easier to engage (for example pressurization engages) and help energy storage device than beta-alumina.

Can make dividing plate stable by adding a small amount of (being not limited to) lithia, magnesium oxide, zinc oxide, yittrium oxide or similar oxide.These stabilizers can use separately or use with these stabilizers self or other combination of materials.BASE can comprise one or more dopants.Suitable dopant can comprise the oxide of the transition metal of chosen from Fe, nickel, copper, chromium, manganese, cobalt or molybdenum.Dividing plate is called β sometimes "-aluminium oxide dividing plate electrolyte (BASE), have the sodium ion conductivity that is higher than beta-alumina.A kind of β of form "-aluminium oxide dividing plate electrolyte sodium ion conductivity in the time of 300 ℃ is about 0.2ohm ^-1Cm ^-1To about 0.4ohm ^-1Cm ^-1

β "-amount of the stabilizer of aluminium oxide can be greater than 0.5 percentage by weight.In one embodiment, described amount is based on β "-gross weight of alumina material is that about 0.5 percentage by weight is to about 1 percentage by weight; about 1 percentage by weight is to about 2 percentage by weights; about 2 percentage by weights are to about 3 percentage by weights; about 3 percentage by weights are to about 4 percentage by weights; about 4 percentage by weights are to about 5 percentage by weights; about 5 percentage by weights are to about 10 percentage by weights, about 10 percentage by weights are to about 15 percentage by weights, about 15 percentage by weights are about 20 percentage by weights extremely, or greater than about 20 percentage by weights.

Described metal oxide can be alkali metal oxide, alkaline earth oxide, transition metal oxide or the rare-earth oxide that is fit to arbitrarily.In one embodiment, described metal oxide can be the metal oxide through mixing.In another embodiment, described metal oxide comprises mixed-metal oxides.Suitable metal oxide can comprise zirconia, yittrium oxide, hafnium oxide, cerium oxide and thorium oxide.Other suitable mixed-metal oxides can comprise the zirconia of stabilized with yttrium oxide, the zirconia that rare-earth oxide mixes, zirconia, rare-earth oxide doping of cerium oxide, alkaline earth oxide doping of cerium oxide or the stable hafnium oxide that scandium oxide mixes.In one embodiment, described metal oxide comprises zirconia.Described in one embodiment metal oxide can comprise the zirconia (YSZ) of stabilized with yttrium oxide.The suitable amount of yittrium oxide can be greater than about 1 percentage by weight among the YSZ, or can be less than about 10 percentage by weights.In one embodiment, the amount of yittrium oxide can be about 1 percentage by weight to about 2 percentage by weights, 2 percentage by weights are to about 3 percentage by weights, 3 percentage by weights are to about 4 percentage by weights, and 4 percentage by weights are to about 5 percentage by weights, and 5 percentage by weights are to about 6 percentage by weights, 6 percentage by weights are to about 7 percentage by weights, 7 percentage by weights are to about 8 percentage by weights, and 8 percentage by weights are about 9 percentage by weights extremely, or greater than about 9 percentage by weights.To discuss further crystal grain subsequently, the existence of metal oxide can reduce and form the crystallite dimension chance of the crystal grain of increase relatively.

Suitable preparation method comprises sintering, randomly subsequently sinter is forged, and for example adopts that flux growth method makes crystal growth.In one embodiment, the ceramic body (ceramic monolith) that can use additive to affect to generate.Zirconium, YSZ or selenium can be in forming process as the additive of composite diaphragm material.For polycrystalline or half polycrystalline material, can realize control by the interpolation order of selection raw material, material and the type and the method for addition and formation to crystallite dimension, crystal boundary, crystal boundary place chemical property.

Alternatively, the compound of preparation Alpha-alumina and oxygen ion conductor is exposed to this compound the steam, flue gas or the plasma that contain alkali metal oxide subsequently and can be made into suitable dividing plate.Suitable oxygen ion conductor can comprise a kind of in above-mentioned metal oxide and the stable metal oxide.Suitable alkali metal oxide can comprise sodium oxide molybdena.Steam, flue gas or plasma can comprise one or more aforementioned stable agent, to suppress β "-aluminium oxide changes beta-alumina into.Alternatively or extraly, can in described compound, add stabilizer.

The suitable dividing plate that is formed by ceramic complexes can at first form the green compact that formed by Alpha-alumina and oxygen ion conductor.Can be by suppressing, extrude, flow casting (slip casting), injection moulding, curtain coating (tape casting) etc., sintering or hot pressing is subsequently processed green compact.The physical property major part of end article depends on the physical property of initial ceramic complexes and the processing technology of green compact.

The Alpha-alumina that exists in the green compact and the amount of oxygen ion conductor be enough to form Alpha-alumina mutually with oxygen ion conductor successive substrates (continuous matrice) mutually.Two kinds of continuous also networks of IPN are provided thus.The amount of Alpha-alumina can be about 90vol.% and can be extremely about 30vol.% of about 10vol.% to the amount of about 70vol.% and oxygen ion conductor.As previously mentioned, green compact can be exposed to the suitable ionic species (as metal oxide) of alkali metal oxide steam, flue gas or plasma form under greater than about 800 ℃ and high temperature less than about 1700 ℃ (normal pressures).Described temperature can be based on the evaporation loss of alkali metal oxide.

Described steam, flue gas or plasma can comprise alkali metal oxide and (β if desired " form) optional stabilizing ion.Green compact can be placed the precursor powder of steam, flue gas or plasma, described precursor generates steam, flue gas or plasma when being heated to reaction temperature.In conversion process, oxonium ion transmits by oxygen ion conductor, and sodium ion transmits by green compact.For two kinds of ions provide transmission channel to improve reaction power.Reaction power can be based on alkali metal-β of reaction front place or β "-formation of aluminium oxide; Reaction front is to separate Alpha-alumina (with oxygen ion conductor) and formed alkali metal-β or β "-border of aluminium oxide (with oxygen ion conductor).The activity of sodium ion when forming (and without sintering) by control steam, flue gas or plasma forms and seldom or not forms liquid phase.And in space, brilliant crack, form or deposition seldom or do not form or deposit for example sodium aluminate.Less crystallite dimension also can reduce the volume in space, brilliant crack or eliminate space, brilliant crack.

In addition, about the crystal grain of dividing plate, described dividing plate has the microstructure that comprises a plurality of crystal grain.In one embodiment, as described herein, described a plurality of crystal grain can comprise some stabilizers (as the zirconia) crystal grain that is in IPN phase or the matrix.Stabilizer crystal grain can be greater than about 10% with respect to the crystal grain of other material in the compound dividing plate.In one embodiment, the stabilizer crystal grain in the compound dividing plate can account for about 10% to about 20%, about 20% to about 30%, about 30% to about 40%, or about 40% to about 50%.

In another embodiment, the compound dividing plate can have the stabilizer crystal grain concentration of alternation along its thickness.Make the concentration alternation of designated substance change cross section difference.Unless otherwise noted, alternation comprises change in concentration and the multiple stage type change in concentration that slope is level and smooth.The concentration of stabilizer crystal grain is alternation vertically, but also and then because of dividing plate has the border blocks in the extensible certain distance of crystal grain described at least one embodiment, and the opposite side on described border is an Alpha-alumina.

In addition, the microstructure of compound dividing plate in use may not change or deterioration significantly.The crystal grain of compound can have the crystal boundary that defines space, brilliant crack, and space, described brilliant crack does not contain ternary melt or binary melt.In one embodiment, a plurality of crystal grain can have the crystal boundary that defines space, brilliant crack, and described crystal boundary does not contain ternary melt or binary melt.Space, described brilliant crack provides higher relatively sodium ion conductivity.

Dividing plate can be oxygen ion conductor and β-or β "-ceramic complexes of aluminium oxide.In one embodiment, the BASE dividing plate is β "-aluminium oxide and zirconic compound.Zirconia has good strength characteristics and good chemical stability.Thereby the dividing plate of gained can have higher mechanical strength, more durable and more reliable.Because can improving the reliability of electrochemical cell, the chemical stability and the intensity that are produced, compound BASE dividing plate also allows to use the low thin dividing plate of wall that also keeps proper resistor simultaneously of ionic resistance.The wall that the compound dividing plate is thin can provide higher relatively intensity in the suitable high ion-conductivity of maintenance.

Dividing plate can be the tubular container with at least one wall in one embodiment.Described tube wall can have certain thickness; And thickness can be partly depended in the ionic conductivity and the impedance of passing through described tube wall.Suitable thickness can be less than 5 millimeters.In one embodiment, described thickness is about 5 millimeters to about 4 millimeters, about 4 millimeters to about 3 millimeters, about 3 millimeters to about 2 millimeters, about 2 millimeters to about 1.5 millimeters, about 1.5 millimeters to about 1.25 millimeters, about 1.25 millimeters to about 1.1 millimeters, about 1.1 millimeters to about 1 millimeter, about 1 millimeter to about 0.75 millimeter, about 0.75 millimeter to about 0.6 millimeter, about 0.6 millimeter to about 0.5 millimeter, about 0.5 millimeter to about 0.4 millimeter, about 0.4 millimeter to about 0.3 millimeter, or less than about 0.3 millimeter.

In one embodiment, cation promoter material (cation facilitator material) can be set at least one surface of dividing plate.The cation promoter material can comprise for example selenium.At least one surface of dividing plate has the surface roughness RMS greater than about 10 nanometers.In one embodiment, surface roughness RMS is that about 10 nanometers are to about 20 nanometers, about 20 nanometers are to about 30 nanometers, about 30 nanometers are to about 40 nanometers, and about 40 nanometers are to about 50 nanometers, and about 50 nanometers are to about 60 nanometers, about 60 nanometers are to about 70 nanometers, about 70 nanometers are to about 80 nanometers, and about 80 nanometers are to about 90 nanometers, and about 90 nanometers are to about 100 nanometers.

Dividing plate can be by means of the inner surface sealing of hermetically-sealed construction and shell.Hermetically-sealed construction can contain nature of glass composition.Hermetically-sealed construction can operationally keep the sealing between inclusion and environment under greater than about 100 ℃ temperature.In one embodiment, working temperature is about 100 ℃ to about 200 ℃, about 200 ℃ to about 300 ℃, and about 300 ℃ to about 400 ℃, about 400 ℃ to about 500 ℃, about 500 ℃ to about 600 ℃.Corrosion can not take place or pit not occur under the situation of halogen and negative material existence in dividing plate.

Suitable nature of glass composition can include but not limited to phosphate, silicate, borate, germanate, vanadate, zirconates, arsenate, and their multi-form for example borosilicate, aluminosilicate, calcium silicates, binary alkali metal silicate, alkali borate, or the wherein combination of two or more.Alternatively, the end of dividing plate can comprise Alpha-alumina.Alpha-alumina can directly engage with the lid of sealing second locellus.Suitable joint method can comprise hot press, diffusion bond or film metal plating, and wherein each method can be used in conjunction with welding or soldering tech.

Goods can have a plurality of collector bodies, comprise negative electrode collector and positive electrode collector.The negative electrode collector and the first locellus electric connection, the inclusion electric connection of the positive electrode collector and second locellus.The material that is applicable to negative electrode collector can comprise Ti, Ni, Cu, Fe or the wherein combination of two or more.Other material that is applicable to negative electrode collector can comprise steel or stainless steel.The other material of negative electrode collector that is applicable to can comprise carbon.Collector body can stand plating or coating.Positive electrode collector can be silk, blade or the aperture plate of being made by Pt, Pd, Au, Ni, Cu, C or Ti.The thickness of described a plurality of collector bodies can be greater than 1 millimeter (mm).In one embodiment, described thickness is about 1 millimeter to about 10 millimeters, about 10 millimeters to about 20 millimeters, and about 20 millimeters to about 30 millimeters, about 30 millimeters to about 40 millimeters, or about 40 millimeters to about 50 millimeters.Coating layer on the collector body (if exist) can be coated on collector body and reach thickness greater than 1 μ m.In one embodiment, the thickness of described coating layer is about 1 micron (μ m) extremely about 10 μ m, and about 10 μ m are to about 20 μ m, and about 20 μ m are to about 30 μ m, and about 30 μ m are to about 40 μ m, or about 40 μ m are to about 50 μ m.

Below in conjunction with shown in the working method of embodiment explanation goods and the function of electrochemical cell.With reference to accompanying drawing, embodiment of the present invention have been described, but have the invention is not restricted to this.

Fig. 1 shows the goods 100 according to embodiment.Goods 100 can be used as energy-producing electrochemical cell.This device comprises shell 102.Shell comprises the dividing plate 104 with outer surface 106 and inner surface 108.Outer surface defines first locellus 110, and inner surface defines second locellus 112.First locellus is the negative pole that comprises sodium, and second locellus is the positive pole that comprises multiple salt.First locellus and second locellus are via the dividing plate electric connection.First locellus and second locellus also comprise negative electrode collector 114 and positive electrode collector 116, to collect the electric current that is produced by electrochemical cell.

These goods can be electrochemical cells.Electrochemical cell can be assembled under discharge condition.Can between the negative pole of electrochemical cell and positive pole, apply voltage and make that electrochemical reaction is reverse carries out, electrochemical cell is charged.In charging process, the sodium chloride in the positive pole forms sodium ion and chloride ion owing to applying electrical potential decomposes.Sodium ion conducts via dividing plate under the effect of applying electrical potential and combines and form the sodium electrode with electronics from external circuit, the transition metal reaction in the chloride ion and first material and form metal chloride and supply with the external circuit electronics.In discharge process, sodium ion reacts reverse carrying out via the dividing plate reverse conduction, and produces electronics.Cell reaction is as follows:

2NaCl+ positive electrode → (positive electrode) Cl ₂+ 2Na

With reference to Fig. 2, show a plurality of energy storage devices (Fig. 2 A to 2J) with the multiple design alternative of example.In Fig. 2 A to 2J, identical mark is used to represent identical part (the identical function that is meant is identical).Thereby set 200 comprises the energy storage device with elongate housing 210, and described elongate housing 210 defines axis 220.The inner surface of shell wall defines volumetric spaces (volume).This volumetric spaces comprises the negative pole 230 and anodal 240 that separates by dividing plate 250 and core body 260 mutual physics.Described core body is arranged on the dividing plate surface outward and liquid negative material is flowed on baffle surface and transmits via dividing plate.Because dividing plate is respectively to hold capped confined space, thereby in volumetric spaces, have two locellus effectively---interior locellus and outside locellus.

Some designs are self-evident; Other will illustrate in greater detail.Fig. 2 C comprises a plurality of dividing plates, and wherein each dividing plate all can have core body and collector body.For Fig. 2 D-2E, have following phenomenon: along with first material in use is consumed, the forward position surface area of untapped material does not obviously change.Relative with it, for example the reaction front surface area of first material diminishes along with the use of first material (being similar to cylinder) in Fig. 2 A.

Design is different is with other for Fig. 2 I, and negative pole 270 is in dividing plate 274, and anodal 272 beyond dividing plate 274, and described dividing plate 274 has core body 276 on the surface within it.Be similar to the embodiment shown in Fig. 2 C, have a plurality of dividing plates.Shell 290 can be made by material high temperature resistant, resistance to chemical attack.

For any previous designs, first positive electrode can be deposited on the foam support body.Yet, in Fig. 2 I, but backing material supporting clapboard also.Described supporter can reduce or eliminate the destruction of being caused by thermal cycle, pressure differential and vibration.

With reference to Fig. 2 J, provide a kind of dividing plate that to have two cross sections be oval-shaped " supporting leg ".Owing to be perspective view, the whole syndeton that is positioned in the course of the work on " supporting leg " is not shown.Overall structure may look similar a pair of trousers.For the situation with even number dividing plate, axis and at least one dividing plate are non co axials.

A plurality of electrochemical cells can be arranged in the energy-storage system.But a plurality of battery serial or parallel connections are arranged to form stacked body.The rated power of stacked body and energy may depend on the factors such as number of batteries in stacked body size for example or the stacked body.Other factors may be based on the concrete standard of final application.

The multiple embodiments of energy storage device can store the energy of about 0.1 kilowatt hour (kWh) to about 100kWh.A kind of embodiment of energy storage device has the energy/weight ratio greater than 100 watt-hour/kilograms, and/or greater than 160 watt-hours/liter energy/volume ratio.Another embodiment of energy storage device has the specified unit power greater than 150 watts/kilogram.

Suitable energy storage device can have the application units' power/energy ratio less than 10: 1.In one embodiment, unit power/energy ratio is about 1: 1 to about 2: 1, about 2: 1 to about 4: 1, and about 4: 1 to about 6: 1, about 6: 1 to about 8: 1, or about 8: 1 to about 10: 1.In other embodiments, unit power/energy ratio is about 1: 1 to about 1: 2, about 1: 2 to about 1: 4, and about 1: 4 to about 1: 6, about 1: 6 to about 1: 8, or about 1: 8 to about 1: 10.

In a kind of embodiment of energy-storage system, controller is communicated by letter with a plurality of batteries.Controller can respond the feedback signal of each battery status in the pilot cell group, and electric load is distributed to battery selected in the battery pack.Described controller is operationally implemented rewarming measure (rewarm method), wherein starts the condense part of a series of heating elements with the fusion energy storage device in turn.In another embodiment, controller can be distributed to electric load and be positioned at the selected positive electrode that each battery is determined the position.

Suitable controller can be proportional plus integral plus derivative controller (a PID controller).This controller can be measured available from the value of technology or miscellaneous equipment and make this value and the reference settings value compares.Difference (or " error " signal) can be used for adjusting some technology input values and is its required set point so that process measurements is replied.

Heat management device (if existence) keeps the temperature of energy storage device.If cross coldly, then heat management device can heat energy storage device, if overheated then can cool off energy storage device.Heat management system comprises can make first locellus and second locellus keep minimum temperature (heat level) to melt pattern (thaw profile) with what prevent that the cell reaction thing from solidifying.

Another embodiment of the present invention provides EMS, and this EMS comprises second energy storage device different with described energy storage device.This double-energy storage apparatus system can solve the problem of the ratio of power and energy, wherein can optimize first energy storage device and discharge (power delivery) to realize effective energy storage and to optimize second energy storage device to realize power.Control system can be obtained energy from arbitrary energy storage device as required, and for needing arbitrary energy storage device charging of charging.

Second energy storage device that is applicable to power component (power piece) comprises primary cell, secondary cell, fuel cell or ultracapacitor.Suitable secondary cell can be lithium battery, lithium ion battery, lithium polymer battery or Ni-MH battery.

Embodiment

Following embodiment only is intended to example method of the present invention and embodiment, and should not be construed as the restriction to claim.Unless otherwise mentioned, all the components all can be from such as AlphaAesar, and Inc. (WardHill, Massachusetts), (Gardena, California) etc. Spectrum Chemical Mfg.Corp. buys by common commercial chemicals suppliers.

The preparation of embodiment 1 electrode

By suitably using copper layer or nickel dam that foamy carbon is electroplated, prepared several actual measurements and be the metal deposition carbon foam electrode of 1.25cm * 1.25cm * 2mm (thickness).Carbon foam can be available from ERGMaterial and Aerospace Corp. (Auckland, California).Described foam electrode has reticulated vitreous carbon (RVC) foam framework of carbon containing.The void density of described carbon foam is 100 hole per inch (PPI), about 100 microns of aperture average out to.

Plating can suitably be carried out in the aqueous solution of copper or nickel.Coating carbon coated foams and form prepared metal deposition porous electrode substrate.Some nickel plating porous electrodes are further immersed zinc solution, metallic zinc is plated on the nickel dam.

Made metal deposition carbon foam electrode is analyzed and characterized.When under light microscope, observing, present smooth and glossiness copper facing electrode base board surface with 200 times multiplication factor.The effective density of copper is about 0.01g/cm ³When under light microscope, observing, present smooth and glossiness nickel coating electrode substrate surface with 200 times multiplication factor.The effective density of nickel is about 0.01g/cm ³When under light microscope, observing, present dimness and be granular zinc-plated nickel electrode substrate surface with 200 times multiplication factor.The effective density of zinc is about 0.49g/cm ³The metallic zinc of plating is thick about 0.2 micron on the nickel electrode, and work electrode has 1.5 centimetres the square-section thickness and 2 millimeters the degree of depth.

The preparation of embodiment 2 dividing plates

A plurality of dividing plates have been prepared.Described a plurality of dividing plate comprises two groups of dividing plates, and each is organized dividing plate and has dissimilar stabilizer phases.Two kinds of dissimilar zirconias comprise (i) 8mol.%Y mutually ₂O ₃Stable cubic phase zircite (8YSZ) and (ii) 4.5mol.%Y ₂O ₃Stable four directions phase and cubic phase zircite (4.5YSZ).

The dividing plate that uses stable zirconia to form is made three kinds of disks.Described three kinds of disks comprise two kinds of belonging to type (i) and belong to (ii) a kind of of type.Described three kinds of samples are characterised in that to have following composition: (a) 50vol.% Alpha-alumina+50vol.%8YSZ; (b) 70vol.% Alpha-alumina+30vol.%8YSZ; And (c) 50vol.% Alpha-alumina+50vol.%4.5YSZ.Be prepared as follows to have and form (a) and (b) and thickness (c) is 2.5 millimeters (mm)) the disc sample: use required mixture of powders, carry out mold pressing, wait static pressure subsequently, then in 1600 ℃ of sintering in air.Sintered wafer is placed mixture of powders.The Na that consists of 8.85wt.% of described mixture of powders ₂The Li of O, 0.75wt.% ₂The Al of O and 90.45wt.% ₂O ₃Be in disk 2 hours in the powder in 1250 ℃ of calcinings, thereby form sodium-β "-aluminium oxide, and in course of reaction as the source of sodium lithium oxide.Sample was 1450 ℃ of insulations 2 hours to about 16 hours.Described sample is blocked and measures formed sodium-β "-thickness of aluminium oxide.

A kind of sample with composition (a) further carries out the long period heat treatment of (32 hours) to guarantee that sample is converted into sodium-beta-alumina fully under 1450 ℃.The conductivity (σ) of measurement during from about 200 ℃ to about 500 ℃.Recording activation energy is every mole of about 15.7 kilojoule (kJ/mol).Conductivity in the time of 300 ℃ is every centimetre of 0.0455 Siemens (S/cm) (resistivity is 22 ohm-cms (Ω cm)).This sample has the 50vol.% zirconia.In addition, the crystallite dimension of sodium-beta-alumina is several microns.The conductivity that records is consistent with the given value of the sodium-beta-alumina of aplitic texture.

The formation and the test of embodiment 3 test batteries

Battery structure that is used to test among the embodiment 3 and structure shown in Figure 1 are basic identical.Form (a) according to the process using of embodiment 2 and prepared cylindrical composite thing dividing plate pipe.This cylindrical size is as follows: long is 228mm, and internal diameter is 36mm, and external diameter is 38mm.This compound dividing plate pipe is isolated by the glass and the Alpha-alumina collar (alpha alumina collar).This assembly is placed stainless cylinder of steel.Described jar is of a size of about 38mm * 38mm * 230mm.Described compound dividing plate comprises 50 gram (g) Cu, 22 gram NaCl, 25 gram NaAlCl ₄In addition, adding 11 gram reticulated vitreous carbon in positive pole precipitates between discharging and recharging to prevent CuCl.Electric heater is around battery.In the course of the work, battery is heated to 300 ℃ working temperature.Make battery charging and discharge under the electric current of 4 peaces and 12 peaces.Through after several charge and discharge cycles, battery is cut off, cool off and detect.Micro-examination to dividing plate crystal grain shows do not have copper to infiltrate brilliant crack.

The collector body that is used for work electrode and auxiliary electrode is the rectangular paddle that is made of titanium, and has cross sectional shape and the area identical with the foams base electrode.Described blade is welded to the Ti silk of 1-mm.Pile up the thickness that several pieces non-woven borosilicate glass fiber filter medias (Whatman GF/C) reach 0.15 centimetre (cm).The additional glass filter medium is placed the back side of Ti blade.The titanium silk of long 1-mm is bent into W shape and makes spring.Described spring is pressed on the back side of titanium blade, thereby makes the slight pressurized of whole assembly.Additional glass medium on the vacuum side of blade provides electric insulation, makes spring can not set up electric pathway between two electrodes.

The connecting line of three electrodes passes the conical plug in the center bottleneck that is assemblied in flask.Utilize N ₂The dry glove box of purge connects the sodium electrode to the moisture sensitivity at last.Described connecting line is adjusted so that foam electrode immerses in the fused salt fully.Approaching work/auxiliary electrode the assembly of sodium reference electrode, but be in beyond work/auxiliary electrode assembly.

Outside line end and computer interface galvanostat are (continuous and measure constant current data available from AMETEK Princeton AppliedReserch (Oak Ridge, PARSTAT 2272 TN)).Work electrode at first 100 milliamperes (mA) following oxidation 3600 seconds, reduced 900 seconds under 400 milliamperes subsequently.The open circuit potential that records with respect to Na is 2.077 volts.Charging voltage is 2.17 volts, and discharge voltage is 2.02 volts.When the zinc in the plating Ni foams all exhausted, open circuit voltage was 2.58 volts.

The formation of embodiment 4 test energy storage devices

Use β "-alumina tube and copper pipe formation energy storage device.β "-alumina tube has the internal diameter of 6.5mm, the external diameter of 8.6mm, the total length of 68mm.The size and dimension of setting copper pipe is to hold β "-alumina tube.Copper pipe has the internal diameter of 12.7mm.With β "-alumina tube places copper pipe.Except that copper pipe, at β "-1.2 gram sodium chloride and 3.4 gram electrolyte AlCl placed in the space between the inner surface of alumina tube and the outer surface of copper pipe ₃: NaCl.At β "-0.2 gram and diameter placed in the alumina tube and be the sodium that the nickel wire (as collector body) of 1mm contacts.

Energy storage device main body and β "-nickel collector body in the alumina tube is connected with PAR barostat/galvanostat Model 2273.Electric heater is around energy storage device.In test process, described heater (and subsequently energy storage device) is heated to 300 ℃ working temperature.

After the process initial charge circulates the total charge volume that reaches 1360 coulombs under the electric current of 0.025 peace, make energy storage device at 0.5 peace (61.8mA/cm ²) electric current under discharge and recharge 140 times.The charge volume of each circulation is 500 coulombs.Voltage between the circulation time battery terminal vibrates between about 2 volts to 3.2 volts.Polarization curve as shown in Figure 3.Show discharge curve (300,304,308,312) and the charging curve (302,306,310,314) of representing 10 circulations, 50 circulations, 90 circulations, 120 circulations respectively.Not observing cell resistance increases.

The formation of embodiment 5 test energy storage devices

Formed two energy storage devices, each energy storage device includes commercially available cylindrical beta "-alumina tube.These pipes do not comprise stabilizer, and each Guan Jun contains the sodium aluminate that is present in intergranule, and the size of crystal grain is enough big.Each pipe has the internal diameter of 36mm, the external diameter of 38mm, the total length of 228mm.Make nickel foil and Alpha-alumina collar hot press.β "-alumina tube is isolated to form assembly by the Alpha-alumina collar of glass and paper tinsel coating.Described assembly is positioned over size to be approximately in the square stainless steel casing of 38mm * 38mm * 230mm.Described assembly is welded in shell to form gas-tight seal.The described nickel foil and the Alpha-alumina collar define the perforate in the assembly.By described perforate to described β "-fill positive electrode and other material in the alumina tube.Described β "-be filled with 100 gram copper, 44 gram sodium chloride, 1 gram aluminium and 48 gram NaAlCl in the alumina tube ₄The electrolyte of form.The nickel rod is placed described β "-center of alumina tube and contact to serve as collector body with negative material.Described perforate is covered by metal cap.Described metal cap is welded on the collar to form the battery of sealing fully.The theoretical capacity of described battery is 20.18 amp hrs.Electric heater is around energy storage device.Open described heater, make the temperature of shell rise to about 350 ℃ working temperature.After the initial trickle charge circulation of process under the electric current of 2.0 peaces reaches total charge volume of 17.95 amp hrs (64,620 coulombs), described energy storage device is discharged and recharged under the electric current of 2 peaces and 4 peaces (6 peaces and 12 that are equal to fuel cell are pacified).The performance of described energy storage device is shown in Figure 4.

The voltage of two kinds of energy storage devices is close each other, and in discharge cycles held stationary.The capacity of described battery depends on temperature: 2 of equivalence lay electricity and obtain 2.25 amp hrs in the time of 300 ℃, and 2 lay electricity and obtain 8.75 amp hrs in the time of 380 ℃.

Fig. 5 comprises test battery and standard Na/NiCl ₂The comparison of the resistance of battery in charging process.As shown in the figure, test battery has relatively low resistance and along with the less resistance that amp hr has that is filled rises.Only after through circulation several times, each β "-alumina tube promptly breaks.Copper at most migration passes β "-about 1/3 distance of alumina tube tube wall.

The formation of embodiment 6 energy storage devices

Make energy storage device in the mode identical with the energy storage device of embodiment 5, different is to add 11 gram carbon in positive electrode.The carbon that is added prevents that CuCl from precipitating during battery charger operation mode and discharge mode of operation.Electric heater is around energy storage device.Start described heater so that described energy storage device is heated to about 300 ℃ working temperature.

Under the electric currents of 3 to 15 peaces through initial constant voltage charge after circulation reaches total charge volume of 10 amp hrs, make the charging and discharging under the electric currents of 4 peaces and 12 peaces of described energy storage device.The charging performance of the energy storage device of the charging performance of this battery and embodiment 4 is roughly the same.Discharge voltage is also roughly the same.The consumption higher (85%) (mean value of the device of embodiment 4 is 50%) of CuCl when being to discharge with the difference of the energy storage device of embodiment 4.Only after through circulation several times, the dividing plate pipe promptly breaks.Copper at most migration passes β "-about 1/3 distance of alumina tube tube wall.

The formation of embodiment 7 test energy storage devices

With with embodiment 6 in identical mode form energy storage device, that different is β "-the alumina tube difference.β among this embodiment "-alumina tube is by vapor infiltration method (vapor phase impregnation process) preparation.Compare described β with pipe used among the embodiment 5 and 6 "-less sodium aluminate is contained in mutually in the brilliant crack of alumina tube.The energy storage device of the performance of the energy storage device of this embodiment and embodiment 6 is similar.Different is, does not have copper penetration or moves to described β after using "-tube wall of alumina tube in.

Embodiment as herein described is the example with composition corresponding to the key element of the described key element of the present invention of claim, structure, system and method.This specification can be implemented those skilled in the art and is utilized the embodiment that has equally corresponding to the replaceability key element of the described key element of the present invention of claim.Thereby scope of the present invention comprises composition, structure, the system and method different with the statement of claim, also comprises other structure, the system and method that do not have substantial differences with the statement of claim.Although this paper is example and described some features and embodiment only, those skilled in the art can make multiple improvement and change.Claims cover all these improvement and change.

Claims

1. energy storage device comprises:

The positive electrode that comprises copper; And

Dividing plate with described positive electrode electric connection, this dividing plate has the first surface of at least a portion that defines first locellus and defines the second surface of second locellus, described first locellus and second locellus be via the dividing plate ionic communication, and described dividing plate has at least a in the following Column Properties:

Dividing plate is the compound of aluminium oxide and rare-earth oxide, perhaps

Dividing plate is the compound of aluminium oxide and transition metal oxide, perhaps

Dividing plate comprises a plurality of crystal grain that define crystal boundary, described crystal boundary defines space, brilliant crack, and do not containing sodium aluminate before the described energy storage device initial charge or after described energy storage device initial charge, do not containing described positive electrode by the space, brilliant crack that described crystal boundary defines, perhaps

Dividing plate comprises the continuous phase of alkali metal ion conductor and the continuous phase of ceramic oxygen ion conductor.

2. the energy storage device of claim 1, wherein said first locellus and described second locellus are electronic isolations.

3. the energy storage device of claim 1, wherein said second locellus be arranged on described first minute indoor.

4. the energy storage device of claim 1, wherein said second locellus is elongated and defines axis.

5. the energy storage device of claim 4, wherein said first locellus is around described axis coaxle setting.

6. the energy storage device of claim 1, wherein said dividing plate is roughly plane.

7. the energy storage device of claim 6, wherein said dividing plate is plate shaped or waveform.

8. the energy storage device of claim 6, wherein said dividing plate arching or nick.

9. the energy storage device of claim 4, wherein said dividing plate has circle, triangle, square, cross or the star cross section profile perpendicular to described axis.

10. the energy storage device of claim 1, wherein said dividing plate is the alkali metal ion conductor and comprises alkali metal-beta-alumina, alkali metal-β "-aluminium oxide, alkali metal-β-gallate or alkali metal-β "-at least a in the gallate.

11. the energy storage device of claim 10, the alkali metal ion conductor in the wherein said dividing plate do not contain the crystal boundary liquid phase that sintering forms mutually.

12. the energy storage device of claim 1, wherein said dividing plate comprise one or more metal oxides that are selected from zirconia, yittrium oxide, hafnium oxide, cerium oxide and the thorium oxide.

13. the energy storage device of claim 12, the amount of wherein said metal oxide is less than about 10 percentage by weights.

14. the energy storage device of claim 12, wherein said dividing plate comprise the zirconia of stabilized with yttrium oxide or the zirconia that scandium oxide mixes.

15. the energy storage device of claim 1, wherein said dividing plate comprise the metal oxide of one or more stabilisations in zirconia, rare-earth oxide doping of cerium oxide and the alkaline earth oxide doping of cerium oxide that is selected from the rare-earth oxide doping.

16. the energy storage device of claim 1, wherein said positive electrode also comprises aluminium or zinc.

17. the energy storage device of claim 1, wherein said positive electrode also comprise one or more metals that are selected from nickel, chromium and the iron.

18. the energy storage device of claim 1, wherein said positive electrode is made up of copper basically.

19. the energy storage device of claim 1 also comprises the negative material that is arranged in described first locellus.

20. the energy storage device of claim 1, wherein said negative material comprise one or more metals that are selected from sodium, lithium, potassium and the calcium.

21. the energy storage device of claim 20, wherein said negative material also comprises aluminium.

22. the energy storage device of claim 1, wherein said positive electrode comprise one or more halide that are selected from chloride, fluoride, bromide and the iodide.

23. the energy storage device of claim 1, wherein said positive electrode also are included in the support electrolyte greater than fusion under 150 ℃ the working temperature.

24. the energy storage device of claim 23, wherein said fusion support electrolyte and comprise the ternary melt.

25. the energy storage device of claim 24, wherein said ternary melt comprises NaCl:AlCl ₃: CuCl.

26. the energy storage device of claim 23, wherein said support electrolyte comprises sulphur or phosphorus.

27. the energy storage device of claim 1 also comprises at least one the surperficial cation promoter that is arranged at described dividing plate.

28. the energy storage device of claim 27, wherein said cation promoter material comprises selenium.

29. the energy storage device of claim 1, wherein at least one baffle surface has about 10 nanometers to about 100 microns surface roughness value (RMS).

30. the energy storage device of claim 1, hermetically-sealed construction and another sealing structure that wherein said dividing plate constitutes by means of nature of glass composition.

31. the energy storage device of claim 1, wherein said hermetically-sealed construction be in about 100 ℃ of sealings that operationally keep to about 600 ℃ temperature between described at least positive electrode and the environment, and randomly do not corrode under the situation that halogen exists or pit do not occur.

32. energy-storage system that comprises the energy storage device of claim 1.

33. the energy-storage system of claim 32, wherein said energy-storage system can be stored the energy greater than 10 kilowatt hours.

34. the energy-storage system of claim 32, wherein said energy-storage system have greater than the rated energy/weight ratio of 100 watt-hour/kilograms and greater than 160 watt-hours/liter rated energy/volume ratio.

35. the energy-storage system of claim 32, wherein said energy-storage system have the specified unit power greater than 150 watts/kilogram.

36. the energy-storage system of claim 32, wherein said energy-storage system have the power/energy ratio less than 1: 1.

37. a method comprises:

Between first locellus and second locellus, transmit sodium ion via dividing plate, described dividing plate with comprise the positive electrode electric connection of copper, and this dividing plate has at least a in the following Column Properties:

Dividing plate is the compound of aluminium oxide and rare-earth oxide, perhaps

Dividing plate comprises a plurality of crystal grain that define crystal boundary, and described crystal boundary defines space, brilliant crack, and is not being contained sodium aluminate before the energy storage device primary charging or do not contained positive electrode after the energy storage device primary charging by the space, brilliant crack that described crystal boundary defines, perhaps

Dividing plate comprises the continuous phase of sodium ion conductor and the continuous phase of ceramic oxygen ion conductor; And

Stop copper in the sodium ion transmission course, to infiltrate space, described brilliant crack.

38. a system comprises:

Can between first locellus and second locellus, transmit sodium ion and with the dividing plate of the positive electrode electric connection that comprises copper, described dividing plate has at least a in the following Column Properties:

Dividing plate is the compound of aluminium oxide and rare-earth oxide, perhaps

Dividing plate comprises the continuous phase of sodium ion conductor and the continuous phase of ceramic oxygen ion conductor; And be used for stoping copper to infiltrate the mechanism in space, described brilliant crack in the sodium ion transmission course.

39. an energy storage device comprises:

Dividing plate, described dividing plate have the first surface of at least a portion that defines first locellus and define the second surface of second locellus, and described first locellus and described second locellus are via described dividing plate ionic communication; And

Multiple positive electrode, described multiple positive electrode comprises first positive electrode and second positive electrode at least, described two kinds of positive electrodes are all with described dividing plate electric connection and all can form metal halide,

Condition is, if any in described first positive electrode or described second positive electrode is transition metal, then another kind of positive electrode is not iron, arsenic or tin.

40. the energy storage device of claim 39, wherein said first positive electrode comprises zinc, and described second positive electrode comprises copper.

41. the energy storage device of claim 39, wherein said first positive electrode comprises nickel, and described second positive electrode comprises copper.

42. the energy storage device of claim 39, wherein said first positive electrode comprises nickel, and described second positive electrode comprises zinc.

43. the energy storage device of claim 39, wherein said first positive electrode comprises nickel, and described second positive electrode comprises zinc, and described multiple positive electrode also comprises the 3rd positive electrode, and the 3rd positive electrode comprises copper.

44. the energy storage device of claim 39, wherein said first positive electrode comprises nickel, and described second positive electrode comprises zinc or copper, and described multiple positive electrode also comprises the 3rd positive electrode, and the 3rd positive electrode comprises molybdenum or tungsten.

45. the energy storage device of claim 39, wherein said first positive electrode comprises nickel, and described second positive electrode comprises zinc or copper, and described multiple positive electrode also comprises the 3rd positive electrode, and the 3rd positive electrode comprises tin or arsenic.

46. the energy storage device of claim 39, wherein said first positive electrode comprises zinc, and described second positive electrode comprises copper, and described multiple positive electrode also comprises the 3rd positive electrode, and the 3rd positive electrode comprises molybdenum or tungsten.

47. the energy storage device of claim 39, wherein said first positive electrode comprises zinc, and described second positive electrode comprises copper, and described multiple positive electrode also comprises the 3rd positive electrode and the 4th positive electrode, the 3rd positive electrode comprises nickel, and the 4th positive electrode comprises tin or arsenic.

48. the energy storage device of claim 39, the multiple positive electrode of wherein obeying described condition comprises two or more metals that are selected from nickel, zinc, copper, chromium and the iron.

49. the energy storage device of claim 39, wherein said first positive electrode comprises nickel, and described second positive electrode comprises aluminium or chromium.

50. the energy storage device of claim 39, wherein said first positive electrode comprises copper, and described second positive electrode comprises aluminium or chromium.

51. the energy storage device of claim 39, wherein said first positive electrode comprises zinc or copper, and described second positive electrode comprises at least two kinds in tin, arsenic, aluminium or the chromium.

52. the energy storage device of claim 39, wherein said multiple positive electrode comprise three kinds or the more kinds of metal that is selected from nickel, zinc, copper, chromium and the iron.

53. the energy storage device of claim 39, wherein said multiple positive electrode comprises nickel, zinc, copper, chromium and iron.

54. the energy storage device of claim 39 is wherein obeyed the multiple positive electrode of described condition, is made up of two kinds of metals that are selected from nickel, zinc, copper, chromium, tungsten, molybdenum and the iron in fact.

55. the energy storage device of claim 39 is wherein obeyed the multiple positive electrode of described condition, is made up of three kinds of metals that are selected from aluminium, nickel, zinc, copper, chromium, tin, arsenic, tungsten, molybdenum and the iron in fact.

56. the energy storage device of claim 39, wherein said first positive electrode is about 1: 1 to about 5: 1 with respect to the amount of described second positive electrode.

57. the energy storage device of claim 39, wherein said first positive electrode is about 5: 1 to about 20: 1 with respect to the amount of described second positive electrode.

58. the energy storage device of claim 39, wherein said first positive electrode is about 20: 1 to about 50: 1 with respect to the amount of described second positive electrode.

59. the energy storage device of claim 39, wherein said multiple positive electrode comprises one or more halide that are selected from chloride, fluoride, bromide and the iodide.

60. the energy storage device of claim 39, wherein said multiple positive electrode is included in the support electrolyte greater than fusion under about 150 ℃ working temperature.

61. the energy storage device of claim 60, wherein said fusion support electrolyte and comprise the ternary melt.

62. the energy storage device of claim 60, wherein said fusion support electrolyte and comprise binary melt.

63. the energy storage device of claim 39, wherein said fusion support electrolyte and comprise sulphur or phosphorus.

64. the energy storage device of claim 39 also comprises negative material, described negative material comprises sodium.

65. the energy storage device of claim 64, wherein said negative material also comprises aluminium or titanium.

66. the energy storage device of claim 39, wherein said dividing plate comprises β "-aluminium oxide and at least a stabilizer, described stabilizer is alkali metal oxide, alkaline earth oxide, transition metal oxide or rare-earth oxide.

67. the energy storage device of claim 66, wherein said stabilizer comprise blended metal oxide that transmits oxygen or the mixed-metal oxides that transmits oxygen.

68. the energy storage device of claim 39, wherein said dividing plate comprise at least a in zirconia, yittrium oxide, hafnium oxide, cerium oxide or the thorium oxide.

69. energy-storage system that comprises the energy storage device of claim 39.

70. the energy-storage system of claim 69, wherein said energy-storage system can be stored the energy greater than 10 kilowatt hours.

71. the energy-storage system of claim 69, wherein said energy storage device have greater than the rated energy/weight of 100 watt-hour/kilograms and greater than 160 watt-hours/liter rated energy/volume.

72. the energy-storage system of claim 69, wherein said energy storage device have the specified unit power greater than 150 watts/kilogram.

That 73. the energy-storage system of claim 31, wherein said energy storage device have is about 1 (hour ^-1) to about 10 (hour ^-1) the power/energy ratio.

74. a system comprises:

The mechanism of transmission sodium ion between first locellus and second locellus; And

With first positive electrode and second positive electrode of described transport sector electric connection, and

Condition is, if any in described first positive electrode or described second positive electrode is transition metal, then another kind of positive electrode is not iron, arsenic, or tin.